TW201930075A - Copper foil with insulating resin layer - Google Patents

Abstract

An object of the invention is to provide a copper foil with an insulating resin layer, which can be used favorably on thin printed circuit boards on which high-precision micro-wiring is formed, and on substrates for mounting semiconductor elements. The copper foil with an insulating resin later of the present invention includes a copper foil and an insulating resin layer laminated to the copper foil, wherein the arithmetic mean roughness (Ra) of the surface of the copper foil that contacts the insulating resin layer is in a range from 0.05 to 2 [mu]m, and the insulating resin layer is formed from a resin composition that contains (A) a thermosetting resin, (B) a spherical filler, and (C) short glass fibers with a mean fiber length of 10 to 300 [mu]m.

Description

Copper foil with insulating resin layer

The present invention relates to a copper foil provided with an insulating resin layer. Specifically, the present invention relates to a copper foil with an insulating resin layer which is effective as a stacking material of a printed wiring board or a substrate for mounting a semiconductor element.

In recent years, high-performance and miniaturization of semiconductor packages widely used in electronic equipment, communication equipment, and personal computers have been accelerated. As a result, the thickness of printed wiring boards and semiconductor element mounting substrates in semiconductor packages has been increasingly demanded.

With regard to a method for manufacturing a thin printed wiring board and a substrate for mounting a semiconductor element, for example, Patent Document 1 discloses that a copper layer that can be peeled off in a later step is formed on a thick and rigid support substrate (carrier plate) such as stainless steel. On the obtained laminated body, a circuit pattern is formed by pattern plating, and then an insulating layer such as glass fiber covered with epoxy resin is laminated and heated and pressurized. Finally, the supporting substrate is peeled off and removed. Method for manufacturing thin printed wiring board. In this manner, the circuit pattern and the insulating material are laminated on the support substrate having high rigidity and thickness, and the support substrate is finally peeled off and removed, so that a thin printed wiring board and a substrate for mounting a semiconductor element can be manufactured even by using an existing manufacturing apparatus.

In addition, for multilayer printed wiring boards and substrates for mounting semiconductor elements, in order to improve the mounting density of electronic components, miniaturization of conductor wiring has also progressed. For conductor wiring, a conductive layer is usually formed by using electroless plating and electrolytic plating on an insulating resin layer. Patent Document 2 describes a resin composition that can be used to form an insulating resin layer of a printed wiring board.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 59-500341
[Patent Document 2] Japanese Patent Laid-Open No. 2015-67626

[Problems to be Solved by the Invention]

However, when trying to manufacture printed wiring boards and semiconductor element mounting substrates without using a supporting substrate for thinness, if a conventional manufacturing apparatus is used, the printed wiring boards and semiconductor element mounting substrates may be bent, or The printed wiring board and the substrate for mounting a semiconductor element are wound on a conveyor or the like. Therefore, it is difficult to manufacture a printed wiring board and a semiconductor element mounting substrate for the purpose of thickness reduction using the existing manufacturing apparatus.

In addition, the adhesive film specifically disclosed in Patent Document 2 is formed of a resin composition layer on a film of polyethylene terephthalate (hereinafter sometimes referred to as "PET") as a support. Made. Patent Document 2 is a method of peeling a PET film from the adhesive film, curing the resin composition to form an insulating resin layer (insulating layer), and using the insulating resin layer for a printed wiring board.

However, since the surface roughness of the hardened insulating resin layer is low, the adhesion to a conductor layer formed by using electroless plating and / or electrolytic plating is low. Therefore, in order to obtain adhesiveness, the insulating resin layer is generally subjected to a roughening treatment such as desmear treatment before the electroless plating or electrolytic plating. On the surface of the insulating resin layer that has been roughened, inorganic substances such as glass fibers in the resin composition are exposed (protruded), and the surface is roughened. In addition, there is a problem that large-scale recessed holes are formed in the insulating resin layer because inorganic substances may fall off from the insulating resin layer. In addition, since inorganic substances such as glass fibers are exposed from the surface of the hole, when a laser processing machine is used to form a multilayer printed wiring board (hereinafter sometimes referred to as "BVH"), there may be abnormal precipitation of plated matter and BVH. The problem of connection reliability deterioration. It is difficult to form high-density fine wiring on the surface of such an insulating resin layer, and it is difficult to manufacture a printed wiring board and a semiconductor element mounting substrate on which high-density fine wiring is formed from the adhesive film in Patent Document 2.

The present invention has been made in view of such problems, and an object thereof is to provide a copper foil with an insulating resin layer, which can be ideally used for manufacturing thin printed wiring boards and semiconductors having fine wirings with high density and good via holes. Component mounting substrate.
[Means for solving problems]

The inventors of the present invention have repeatedly conducted in-depth studies in order to solve the above-mentioned problems. As a result, they have found that by using a copper foil having high rigidity and excellent adhesion to an insulating resin layer, an insulating resin having high adhesion to the copper foil and high toughness is laminated The layered copper foil with an insulating resin layer can obtain a thin printed wiring board having a high density of fine wiring and a good via hole, and a substrate for mounting a semiconductor element, and has completed the present invention.

That is, the present invention is as follows.
[1] A copper foil provided with an insulating resin layer, comprising: a copper foil; and an arithmetic average roughness of the surface of the copper foil laminated on the insulating resin layer of the copper foil and in contact with the insulating resin layer ( Ra) is 0.05 to 2 μm, and the insulating resin layer is composed of a resin composition containing (A) a thermosetting resin, (B) a spherical filler, and (C) short glass fibers having an average fiber length of 10 to 300 μm.

[2] The copper foil according to [1], wherein the thickness of the insulating resin layer is 3 to 50 μm.
[3] The copper foil according to [1] or [2], wherein the thickness of the copper foil is 1 to 18 μm.
[4] The copper foil according to any one of [1] to [3], wherein a fiber diameter of the short glass fibers is 1 to 15 μm.
[5] The copper foil according to any one of [1] to [4], wherein the content of the short glass fibers is 5 to 450 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[6] The copper foil according to any one of [1] to [5], wherein the short glass fibers are milled fibers.
[7] The copper foil according to any one of [1] to [6], wherein a content of the spherical filler is 50 to 500 parts by mass based on 100 parts by mass of a resin solid content in the resin composition.
[8] The copper foil according to any one of [1] to [7], wherein the thermosetting resin contains a material selected from the group consisting of epoxy resin, cyanate compound, maleimide compound, and phenolic compound. Resin, thermosetting modified polyphenylene ether resin, benzopyrene At least one of the group consisting of a compound, an organic-based modified polysiloxane, and a compound having a polymerizable unsaturated group.
[9] The copper foil according to any one of [1] to [8], which is used as a stacking material for a printed wiring board or a substrate for mounting a semiconductor element.
[Effect of the invention]

According to the present invention, a copper foil with an insulating resin layer, which has a high adhesion strength between the copper foil and the insulating resin layer and is laminated with a highly resilient insulating resin layer on the copper foil, can be obtained. By using the copper foil with an insulating resin layer of the present invention, it is possible to obtain a thin printed wiring board having a high density of fine wirings and a good via hole, and a substrate for mounting a semiconductor element.
In addition, when manufacturing a printed wiring board or a substrate for mounting a semiconductor element, even if copper plating is applied after the copper foil is etched, the copper foil surface is transferred to the insulating resin layer. Therefore, between the insulating resin layer and the plated material The adhesion will be improved.

Hereinafter, the embodiment for implementing the present invention (hereinafter simply referred to as "this embodiment") will be described in detail, but the present invention is not limited to the following embodiment. Various changes can be made in the present invention without departing from the gist thereof. In this specification, although the laminated body is formed by adhering the layers to each other, the respective layers may be peeled from each other as needed.

In this embodiment, "resin solid content" or "resin solid content in resin composition" means a component after removing a solvent and a filler in a resin composition unless otherwise specified, and "resin solid content 100 parts by mass" "" Means that the total of the components after removing the solvent and filler in the resin composition is 100 parts by mass.

[Copper foil with insulating resin layer]
The copper foil with an insulating resin layer in this embodiment is obtained by laminating an insulating resin layer made of a resin composition on a copper foil. The arithmetic mean roughness (Ra) of the copper foil surface which the copper foil and the insulating resin layer contact in this embodiment is 0.05-2 micrometers. The resin composition of this embodiment contains (A) a thermosetting resin, (B) a spherical filler, and (C) short glass fibers having an average fiber length of 10 to 300 μm.

This embodiment is a copper foil laminate having high rigidity and excellent adhesion to the insulating resin layer and an insulating resin layer having high adhesion and high toughness to the copper foil. Therefore, even if the insulating resin layer with the insulating resin layer of this embodiment is used Copper foil is used to manufacture a printed wiring board. In the manufacturing process, the thin insulating resin layer is not damaged, and the copper foil and the insulating resin layer are not peeled off. Further, a well-shaped via hole can be formed.

The copper foil with an insulating resin layer in this embodiment can be used for manufacturing electronic equipment, communication equipment, personal computers, and the like, and is effective as a stacked material for printed wiring boards or substrates for mounting semiconductor elements. When the copper foil with an insulating resin layer in this embodiment is used as a stacking material for a printed wiring board and a substrate for mounting a semiconductor element, the copper foil can be laminated on the outermost surface of the printed wiring board and the substrate for mounting a semiconductor element, so that it can be used. The circuit pattern is directly formed on the outermost copper foil. In addition, when manufacturing a printed wiring board or a substrate for mounting a semiconductor element, even if copper plating is applied after the copper foil is etched, the copper foil surface is transferred to the insulating resin layer. Therefore, between the insulating resin layer and the plated material The adhesion will be improved. Therefore, by using the copper foil with an insulating resin layer of this embodiment, a thin printed wiring board and a semiconductor element mounting substrate on which high-density fine wiring is formed can be obtained.

[Copper foil]
The copper foil of this embodiment is a copper foil or a copper film used for a general printed wiring board, and if the arithmetic average roughness (Ra) of the copper foil surface in contact with the insulating resin layer is 0.05 to 2 μm, there is no Special restrictions. Specific examples of the copper foil include electrolytic copper foil, rolled copper foil, and copper alloy thin films. The copper foil or copper film may be subjected to a known surface treatment such as a felting treatment, a corona treatment, a nickel treatment, and a cobalt treatment.

Considering the viewpoint of improving the adhesion strength between the copper foil and the insulating resin layer and preventing the layer from peeling when used for a long time, the arithmetic average roughness (Ra) of the copper foil surface usually falls within the range of 0.05 to 2 μm, and preferably falls within 0.08 The range of ˜1.7 μm is more preferably in the range of 0.2 to 1.6 μm, considering the viewpoint of obtaining better adhesion between the copper foil and the insulating resin layer. In this embodiment, the copper foil with an insulating resin layer including a copper foil having an arithmetic average roughness falling within the aforementioned range can be ideally used for manufacturing a printed wiring board having a high-density fine wiring and a substrate for mounting a semiconductor element. . In addition, if the arithmetic average roughness is less than 0.05 μm, there is a concern that the bonding strength between the copper foil and the resin cannot be obtained. If it exceeds 2 μm, there is a possibility that pin residues are likely to occur during wiring formation and fine wiring cannot be formed. The arithmetic mean roughness can be measured using a commercially available shape measuring microscope (laser microscope, for example, VK-X210 (trade name) manufactured by KEYENCE Corporation). The specific measurement method is as described in the examples.

The thickness of the copper foil is not particularly limited as long as it exhibits the effects of this embodiment. It should fall within the range of 1 to 18 μm. Considering that a thin printed wiring board and a substrate for mounting a semiconductor element can be ideally obtained, the thickness is 2 to 15 μm. Within the range is better. If the thickness of the copper foil is less than 1 μm, it is difficult to roughen the surface of the copper foil, and if it is more than 18 μm, it is not conducive to cost surface or hole processability.

As the copper foil, for example, GHY5 (trade name, 12 μm thick copper foil) made by JX Metal (stock), 3EC-VLP (trade name, 12 μm thick copper foil), 3EC- III (trade name, 12 μm thick copper foil) and 3EC-M2S-VLP (trade name, 12 μm thick copper foil), Furukawa Electric Industrial Co., Ltd. copper foil GTS-MP (trade name, 12 μm thick copper foil), and JX A commercially available product of JXUT-I (trade name, 1.5 μm thick copper foil) made of metal.

[Resin composition]
(A) Thermosetting resin Considering the viewpoints of heat resistance, insulation, and adhesion of a plated material, the resin composition of this embodiment contains a thermosetting resin. The thermosetting resin is not particularly limited as long as it is a resin used for an insulating layer of a printed wiring board.

Specific examples of the thermosetting resin include epoxy resin, cyanate compound, maleimide compound, phenol resin, thermosetting modified polyphenylene ether resin, and benzofluorene. Compounds, organic-modified polysiloxanes, and compounds with polymerizable unsaturated groups.
These thermosetting resins may be used singly or as a mixture of two or more kinds as appropriate.

Among these thermosetting resins, considering the viewpoint of obtaining an insulating resin layer having excellent peeling strength, the resin composition should preferably contain an epoxy resin and a cyanate compound. Compounds containing bismaleimide are more preferred.

The epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule, and any conventional epoxy resin can be used.
Considering that the adhesiveness and flexibility are better, the epoxy equivalent of the epoxy resin is preferably 250 to 850 g / eq, and more preferably 250 to 450 g / eq. The epoxy equivalent can be measured by a conventional method.

Specific examples of the epoxy resin include polyoxynaphthyl epoxy resin, biphenylaralkyl epoxy resin, naphthalene 4-functional epoxy resin, xylene epoxy resin, and naphthalene. Phenolic aralkyl epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol A novolac epoxy resin, trifunctional phenol epoxy resin, 4-functional phenol epoxy resin , Naphthalene type epoxy resin, biphenyl type epoxy resin, aralkyl novolac type epoxy resin, alicyclic epoxy resin, polyhydric alcohol type epoxy resin, epoxypropylamine type epoxy resin, epoxy resin A propyl ester epoxy resin, a compound obtained by epoxidizing a double bond such as butadiene, and a compound obtained by reacting a polysiloxane resin containing a hydroxyl group with epichlorohydrin. Among them, from the viewpoints of adhesion and flame retardancy of plated copper, polyoxynaphthyl epoxy resin, biphenylaralkyl epoxy resin, naphthalene 4-functional epoxy resin, and xylene are preferable. Type epoxy resin, naphthol aralkyl type epoxy resin. These epoxy resins can be used individually by 1 type or in mixture of 2 or more types suitably.

In this embodiment, the content of the epoxy resin is not particularly limited. Considering the heat resistance and hardenability, it is preferably within the range of 10 to 80 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. It is particularly preferable to fall within the range of 30 to 70 parts by mass.

The cyanate ester compound has excellent characteristics such as chemical resistance and adhesion, and can form a uniform roughened surface due to its excellent chemical resistance. Therefore, it can be preferably used as a component of the resin composition of this embodiment.

Specific examples of the cyanate compound include, for example, an α-naphthol aralkyl type cyanate compound represented by the formula (1), a novolac type cyanate compound represented by the formula (2), and ( 3) Biphenylaralkyl-type cyanate ester compound, 1,3-dicyanooxybenzene, 1,4-dicyanooxybenzene, 1,3,5-tricyanoxybenzene, bis (3 , 5-dimethyl-4-cyanooxyphenyl) methane, 1,3-dicyanooxynaphthalene, 1,4-dicyanooxynaphthalene, 1,6-dicyanooxynaphthalene, 1,8 -Dicyanoxynaphthalene, 2,6-Dicyanoxynaphthalene, 2,7-Dicyanoxynaphthalene, 1,3,6-Tricyanoxynaphthalene, 4,4'-Dicyanoxybiphenyl , Bis (4-cyanooxyphenyl) methane, bis (4-cyanooxyphenyl) propane, bis (4-cyanooxyphenyl) ether, bis (4-cyanooxyphenyl) sulfide, Bis (4-cyanooxyphenyl) fluorene, 2,2'-bis (4-cyanooxyphenyl) propane, bis (3,5-dimethyl-4-cyanooxyphenyl) methane. These cyanate ester compounds can be used individually by 1 type or in mixture of 2 or more types suitably.

Among them, an α-naphthol aralkyl type cyanate compound represented by formula (1), a novolac type cyanate compound represented by formula (2), and a biphenylaralkyl type represented by formula (3) A cyanate ester compound is preferable because it has excellent flame retardancy, high hardenability, and a low thermal expansion coefficient of a cured product.

[Chemical 1]

In formula (1), R ¹ represents a hydrogen atom or a methyl group, and n ¹ represents an integer of 1 or more. n ^{1 is} preferably an integer from 1 to 50.

[Chemical 2]

In formula (2), R ² represents a hydrogen atom or a methyl group, and n ² represents an integer of 1 or more. n ^{2 is} preferably an integer from 1 to 50.

[Chemical 3]

In formula (3), R ³ represents a hydrogen atom or a methyl group, and n ³ represents an integer of 1 or more. n ³ should be an integer from 1 to 50.

In this embodiment, the content of the cyanate ester compound is not particularly limited. Considering the heat resistance and the adhesiveness of the copper foil, the content of the resin solid content in the resin composition is preferably 15 to 85 parts by mass. It is more preferable to fall within the range of 25 to 65 parts by mass.

Since the maleimide compound can improve the moisture absorption and heat resistance of the insulating resin layer, it can be preferably used as a component of the resin composition of this embodiment.
The maleimide compound is not particularly limited as long as it has two or more maleimide groups in one molecule, and any conventional maleimide compound can be used.

Specific examples of the maleimidoimine compound include bis (4-maleimidoiminophenyl) methane and 2,2-bis (4- (4-maleimidoiminobenzene) (Oxy) phenyl) propane, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimide Bismaleimide compounds such as phenyl) methane and bis (3,5-diethyl-4-maleimidophenyl) methane; polyphenylmethanemaleimide. In addition, they may be blended in the form of a prepolymer of these maleimide compounds or a prepolymer of a maleimide compound and an amine compound. These maleimide compounds may be used alone or as a mixture of two or more thereof.

Among them, from the viewpoint of heat resistance, a bismaleimide compound is preferable, and bis (3-ethyl-5-methyl-4-maleimidephenyl) methane is more preferable.

In this embodiment, the content of the maleimide compound is not particularly limited. Considering the heat resistance and the adhesiveness with copper foil, it is preferable to fall in the range of 5 to 75 with respect to 100 parts by mass of the resin solid content in the resin composition. It is more preferable to fall within the range of 5 to 45 parts by mass in the range of parts by mass.

The phenol resin is not particularly limited as long as it is a resin having two or more phenolic hydroxyl groups in one molecule, and any conventional phenol resin can be used.
Specific examples of the phenol resin include phenol novolac resin, alkylphenol novolac resin, bisphenol A novolac resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, and terpene-modified phenol resin. A compound in which two or more hydrogen atoms bonded to an aromatic ring in one molecule, such as a resin, a polyvinyl phenol, and an aralkyl phenol resin, are substituted with a hydroxyl group. These phenol resins can be used singly or as a mixture of two or more kinds.

Thermosetting modified polyphenylene ether resin is blended with thermoplastic polyphenylene ether resin and epoxy resin and dissolved in a solvent such as toluene, and then 2-ethyl-4-methylimidazole is added as a catalyst to crosslink and Into the resin.

Benzopyrene For compounds, if The ring is not particularly limited as a basic skeleton. In this embodiment, benzopyrene Naphthofluorene Polycyclic fluorene A skeleton compound.

The organic-modified polysiloxane is not particularly limited, and specific examples thereof include bis (methylamino) polydimethylsiloxane, bis (ethylamino) polydimethylsiloxane, and (Propylamino) polydimethylsiloxane, bis (epoxypropyl) polydimethylsiloxane, bis (epoxybutyl) polydimethylsiloxane. These organic-modified polysiloxanes can be used singly or in combination of two or more kinds.

The compound having a polymerizable unsaturated group is not particularly limited, and examples thereof 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, trimethylolpropane di (meth) acrylate, trimethylol (Meth) acrylates of unit alcohols or polyhydric alcohols such as propane tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate; bis Epoxy (meth) acrylates such as phenol A epoxy (meth) acrylate and bisphenol F epoxy (meth) acrylate; benzocyclobutene resin and the like. These compounds having a polymerizable unsaturated group may be used singly or in combination of two or more kinds as appropriate.

(B) Spherical fillers Considering the viewpoints of low thermal expansion, moldability, filling properties, and rigidity, the resin composition of this embodiment contains spherical fillers. The spherical filler is not particularly limited as long as it is a spherical filler used for an insulating layer of a printed wiring board.

The spherical filler is not particularly limited, but the average particle diameter (D50) should preferably fall within a range of 0.01 to 5 μm. In addition, D50 means a median particle diameter, and is a particle diameter in which the larger side and the smaller side when the measured particle size distribution of the powder is divided into two sides become the same amount. The D50 value of the spherical filler is generally measured by a wet laser diffraction-scattering method.

Examples of spherical fillers include: magnesium hydroxide; magnesium oxide; natural silicon dioxide, fused silicon dioxide, amorphous silicon dioxide, hollow silicon dioxide and other silicon dioxide; molybdenum disulfide, oxide Molybdenum compounds such as molybdenum and zinc molybdate; alumina; aluminum nitride; glass; titanium oxide; zirconia. These spherical fillers can be used singly or in combination of two or more kinds as appropriate.

In terms of spherical fillers, spherical fused silica is preferred from the viewpoint of low thermal expansion. As for commercially available spherical fused silica, there are: SC2050-MB, SC2500-SQ, SC4500-SQ, SO-C2, SO-C1 manufactured by Admatechs; SFP-130MC and so on.

The average particle diameter of the spherical silica is not particularly limited. It should fall within the range of 0.01 μm to 5 μm, more preferably fall within the range of 0.05 μm to 3 μm, and more preferably fall within the range of 0.1 μm to 2 μm. It is more preferable to fall between 0.3 μm and 1.5 μm. The average particle diameter of the spherical silica can be measured by a laser diffraction-scattering method based on the Mie scattering theory. Specifically, the measurement can be performed by using a laser diffraction scattering particle size distribution measuring device to prepare a particle size distribution of spherical silica on a volume basis, and making the median particle diameter the average particle diameter. As the measurement sample, a spherical silicon dioxide is preferably dispersed in water using ultrasonic waves. As a laser diffraction scattering type particle size distribution measuring device, LA-500 manufactured by Horiba, Ltd. can be used.

In this embodiment, the content of the spherical filler is not particularly limited. Considering the viewpoint of moldability, it is preferably within a range of 50 to 500 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. Particularly preferred is in the range of 400 parts by mass.

The spherical filler of this embodiment may be surface-treated with a silane coupling agent or the like. As a silane coupling agent, the silane coupling agent mentioned later can be used.

(C) Short glass fibers having an average fiber length of 10 to 300 μm. In the resin composition of this embodiment, in order to obtain excellent adhesion to copper foil, impart toughness to the resin composition, and obtain a resin composition having a low thermal expansion coefficient, On the other hand, short glass fibers with an average fiber length of 10 to 300 μm are included. The glass short fiber of this embodiment is not particularly limited as long as it contains SiO ₂ , Al ₂ O ₃ , CaO, MgO, B ₂ O ₃ , Na ₂ O, and K ₂ O as its main component and the average fiber length is 10 to 300 μm. .

From the viewpoint of reducing the thermal expansion rate, the average fiber length of the short glass fibers is preferably 20 μm or more, and more preferably 30 μm or more. From the viewpoint of improving the dispersibility of short glass fibers, the thickness is preferably 250 μm or less, more preferably 200 μm or less, and even more preferably 150 μm or less.

The fiber diameter of the short glass fibers is not particularly limited. Considering that the thermal expansion coefficient can be further reduced, it is preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 4 μm or more. From the viewpoint of smoothness, it is preferably 15 μm or less, more preferably 13 μm or less, and even more preferably 11 μm or less.

The average fiber length and fiber diameter of the glass short fibers can be measured using an optical microscope, an electron microscope, or the like.

Specific examples of short glass fibers include milled fibers (also referred to as milled fibers in this embodiment), glass wool, and micro rods, and when they are blended in an insulating resin layer, It can obtain excellent adhesion to copper foil, and considering the low cost, it is suitable to be milled fiber. These glass short fibers may be used singly or as a mixture of two or more kinds.

In this embodiment, the content of short glass fibers is not particularly limited. Considering the thermal expansion rate, imparting toughness, and moldability, it is preferable to fall in the range of 5 to 450 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. Within the range, it is particularly preferable to fall within the range of 10 to 400 parts by mass.

In this embodiment, the blending ratio of (B) spherical filler and (C) short glass fiber is not particularly limited. In consideration of formability, (B) spherical filler: (C) mass ratio of short glass fiber It is 1:20 to 100: 1, more preferably 1:10 to 150: 1, and even more preferably 1: 2 to 10: 1.

(Other ingredients)
The resin composition of this embodiment may contain (A) a thermosetting resin, (B) a spherical filler, and (C) a glass short fiber, and may contain 1 or 2 or more other components.
As for other components, for example, in order to improve the moisture absorption and heat resistance of the insulating resin layer according to this embodiment, a silane coupling agent may be contained in the resin composition of this embodiment. 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. Specific examples include aminosilane-based silane coupling agents (e.g., γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane) , Silane-based silane coupling agent (e.g. γ-glycidoxypropyltrimethoxysilane), Silane-based silane coupling agent (e.g. γ-methacryloxypropyltrimethoxysilane), Cationic silane-based silane coupling agents (for example, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride), phenylsilane-based silane coupling agents, and the like. These silane coupling agents may be used alone or as a mixture of two or more thereof.

In this embodiment, the content of the silane coupling agent is not particularly limited. Considering the viewpoint of improving the moisture absorption heat resistance, it is preferable to fall within a range of 0.05 to 5 parts by mass and fall within a range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the spherical filler. It is more preferably within a range of 3 parts by mass. In addition, when two or more kinds of silane coupling agents are used in combination, their total amount is preferably within the above range.

For the purpose of improving the manufacturability of the insulating resin layer, the resin composition of the present embodiment may contain a wetting and dispersing agent. The wetting and dispersing agent is not particularly limited as long as it is a wetting and dispersing agent generally used in paints and the like. Specific examples include: Disperbyk (registered trademark) -110, Disperbyk-111, Disperbyk-180, Disperbyk-161, BYK (registered trademark) -W996, BYK-W9010, BYK-W903 Wait. These wetting and dispersing agents may be used alone or as a mixture of two or more of them as appropriate.

In this embodiment, the content of the wetting and dispersing agent is not particularly limited, and considering the viewpoint of improving the manufacturability of the insulating resin layer, it is preferably within the range of 0.1 to 5 parts by mass relative to 100 parts by mass of the spherical filler, It is more preferably within a range of 0.5 to 3 parts by mass. In addition, when two or more kinds of wetting and dispersing agents are used in combination, their total amount is preferably within the above range.

In consideration of the purpose of adjusting the curing speed, etc., the resin composition of the present embodiment may contain a curing accelerator. The hardening accelerator is not particularly limited as long as it is a commonly used hardening accelerator such as a hardening accelerator used in an epoxy resin or a cyanate compound. Specific examples include organometallic salts containing metals such as copper, zinc, cobalt, nickel, and manganese (for example, zinc octoate, cobalt naphthalate, nickel octoate, manganese octoate), imidazoles, and derivatives thereof (for example, 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 2,4,5-triphenylimidazole), tertiary amines (such as triethylamine, tributylamine). These hardening accelerators can be used individually by 1 type or in mixture of 2 or more types suitably.

In this embodiment, the content of the hardening accelerator is not particularly limited. Considering the viewpoint of obtaining a high glass transition temperature, the content is preferably in the range of 0.001 to 5 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. It is more preferable to fall within the range of 0.01 to 3 parts by mass. In addition, when two or more hardening accelerators are used in combination, their total amount is preferably within the above range.

The resin composition of this embodiment may contain other various polymer compounds and / or flame-retardant compounds. The polymer compound and the flame-retardant compound are not particularly limited as long as they are ordinary users.

The polymer compound includes, in addition to the thermosetting resin (A), various thermosetting resins and thermoplastic resins, and oligomers and elastomers thereof. Specific examples include polyimide, polyimide, imine, polystyrene, polyolefin, styrene-butadiene rubber (SBR), isoprene rubber (IR), and butadiene rubber. (BR), acrylonitrile-butadiene rubber (NBR), polyurethane, polypropylene, (meth) acrylic oligomer, (meth) acrylic polymer, and silicone resin. In view of compatibility, an acrylonitrile butadiene rubber is preferable.

Specific examples of the flame-retardant compound include, in addition to (B) the spherical filler and (C) the short glass fiber, compounds containing phosphorus (for example, phosphate esters, melamine phosphate, and epoxy resin containing phosphorus), Compounds containing nitrogen (e.g. melamine, benzoguanamine), Cyclic compounds, polysiloxane compounds, etc. These polymer compounds and / or flame retardant compounds may be used alone or as a mixture of two or more thereof.

The resin composition of this embodiment may contain various additives for various purposes. Specific examples of the additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, and dispersants. , Leveling agent and brightener. These additives may be used alone or as a mixture of two or more thereof.

(Resin composition and manufacturing method thereof)
The resin composition of this embodiment is prepared by mixing (A) a thermosetting resin, (B) a spherical filler, (C) short glass fibers having an average fiber length of 10 to 300 μm, and other components as required. Got. In addition, the resin composition may be in the form of a solution in which these components are dissolved in an organic solvent, if necessary. The solution of such a resin composition can be preferably used as a varnish when producing the copper foil with an insulating resin layer of this embodiment mentioned later. The organic solvent is not particularly limited as long as each component can be individually dissolved or dispersed as desired and the effect of the resin composition of this embodiment can be exhibited. Specific examples of the organic solvent include alcohols (for example, methanol, ethanol, and propanol), ketones (for example, acetone, methyl ethyl ketone, and methyl isobutyl ketone), and amines (for example, dimethylacetamide). And dimethylformamide), aromatic hydrocarbons (such as toluene and xylene). These organic solvents may be used alone or as a mixture of two or more thereof.

(Insulating resin layer made of resin composition)
The insulating resin layer of this embodiment can be obtained from the resin composition of this embodiment. There is no particular limitation on the thickness of the insulating resin layer. From the viewpoint of smoothness and the orientation of short glass fibers, it should be in the range of 3 to 50 μm. From the viewpoint of further obtaining good moldability, it is more preferably 6 to 45 μm. From the viewpoint of further obtaining good adhesion between the copper foil and the insulating resin layer, it is more preferably 8 to 40 μm.

(Manufacturing method of copper foil with insulating resin layer)
In this embodiment, the method of manufacturing the copper foil with an insulating resin layer of this embodiment laminated | stacking the insulating resin layer which consists of a resin composition on a copper foil is not specifically limited. For the manufacturing method, for example, a solution (varnish) obtained by dissolving or dispersing a resin composition in an organic solvent is applied to the surface of a copper foil, dried under heating and / or reduced pressure, and the solvent is removed. A method of curing a resin composition to form an insulating resin layer.
There are no particular restrictions on the drying conditions. The content ratio of the organic solvent to the insulating resin layer is usually dried to 10 parts by mass or less relative to 100 parts by mass of the insulating resin layer. the following. The conditions for achieving drying vary depending on the amount of organic solvent in the varnish. For example, in the case of a varnish containing 30 to 60 parts by mass of an organic solvent with respect to 100 parts by mass of the varnish, it is dried under heating conditions at 50 to 160 ° C. 3 to 10 minutes.

[Printed wiring board]
The printed wiring board of this embodiment can be used as a stacking material of the copper foil with an insulating resin layer of the present embodiment by completely hardening an insulating resin layer called a core substrate base material. Foil. In this embodiment, a thin copper layer with an insulating resin layer is used, which is formed by laminating a copper foil having high rigidity and excellent adhesion to the insulating resin layer, and an insulating resin layer having high adhesion to the copper foil and high toughness. Foil, it is possible to manufacture a thin printed wiring board without using a thick supporting substrate (carrier plate). The printed wiring board obtained by using the copper foil with an insulating resin layer of this embodiment is thin, has fine wiring with high density, and has few appearance defects.

The surface of the metal foil-clad laminate is a conductor circuit formed by using a generally used metal foil of the metal foil-clad laminate and / or a conductor layer obtained by peeling the metal foil and then plating. The base material of the metal foil-clad laminate is not particularly limited, and is mainly a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate.

In this embodiment, the term "stacking" refers to an insulating resin layer in a copper foil provided with an insulating resin layer on the surface of a metal foil-clad laminated board and / or a conductor laminated layer.

In general, when an insulating resin layer (resin composition layer) is laminated on a metal foil-clad laminate using an adhesive film or the like as a stacking material, an insulating resin layer is provided on one or both sides of the printed wiring board obtained. Although a conductive layer is formed on the insulating resin layer, the surface roughness of the hardened insulating resin layer is low. Therefore, it is generally roughened by a roughening treatment including a slag removal treatment, and then electroless plating is used. And / or electrolytic plating to form a conductor layer. However, on the surface of the insulating resin layer subjected to the roughening treatment, inorganic substances such as glass fibers in the resin composition are exposed (protruded), and the surface is roughened. In addition, there is a problem that large-scale recessed holes are formed in the insulating resin layer because inorganic substances may fall off from the insulating resin layer. Therefore, it is difficult to form high-density fine wiring on the surface of such an insulating resin layer. In addition, when via holes such as via holes and / or through holes are formed, inorganic substances such as glass fibers tend to remain and adversely affect reliability.

However, when a copper foil with an insulating resin layer as a stacking material is laminated on a metal-clad laminate, the obtained printed wiring board has copper foil on one or both sides. The circuit pattern can be directly formed on the copper foil even without a plating treatment, so high-density fine wiring can be formed. In addition, when manufacturing a printed wiring board or a substrate for mounting a semiconductor element, even if copper plating is applied after the copper foil is etched, the copper foil surface is transferred to the insulating resin layer. Therefore, between the insulating resin layer and the plated material The adhesion will be improved.

When manufacturing a printed wiring board, a hole such as a via hole and / or a through hole is applied to electrically connect the conductor layers as necessary. When this hole-cutting process is performed, although a roughening process including a desmearing process is performed later, in this embodiment, the surface of the printed wiring board is protected by a copper foil with excellent adhesion to the insulating resin layer. The surface of the printed wiring board is not roughened by performing the roughening treatment.

Drilling is usually performed using a mechanical drill, carbon dioxide laser, UV laser, and YAG laser. In this embodiment, since the surface of the printed wiring board is protected by copper foil, the energy of these drills or lasers can be enhanced. Therefore, according to this embodiment, as shown in the schematic diagram of FIG. 1, inorganic substances such as glass fibers that are exposed from the surface of the hole can be ideally removed during the hole-cutting process.

The roughening treatment generally includes a swelling step, a surface roughening and slag dissolving step, and a neutralization step.

The swelling step is performed by swelling the surface of the insulating resin layer with a swelling agent. As for the swelling agent, if it can improve the wettability of the surface of the insulating resin layer, and swell the surface of the insulating resin layer to the extent that it will promote oxidative decomposition in the subsequent surface roughening and slag dissolution steps , There are no special restrictions. Examples of the swelling agent include an alkali solution and a surfactant solution.

The surface roughening and slag dissolution steps are performed using an oxidizing agent. Examples of the oxidizing agent include an alkaline permanganate solution and the like. Specific examples include an aqueous potassium permanganate solution and an aqueous sodium permanganate solution. The oxidant treatment is called wet deslagging. In addition to the wet deslagging, mechanical polishing and sandblasting for dry deslagging and polishing wheels such as plasma treatment or UV treatment can also be appropriately combined. It is implemented by other well-known roughening processes.

The neutralization step neutralizes the oxidizing agent used in the previous step with a reducing agent. Examples of the reducing agent include amine-based reducing agents, and specific examples include acidic aqueous solutions such as a hydroxylamine sulfate aqueous solution, an ethylenediaminetetraacetic acid aqueous solution, and a nitrogen triacetic acid aqueous solution.

In this embodiment, after the via hole and / or the via hole are provided, or after the slag removal treatment is performed on the via hole and / or the via hole, in order to electrically connect the conductor layers, a metal plating treatment is preferably performed. In this embodiment, even if a metal plating process is applied, the copper foil surface is transferred to the insulating resin layer, so the adhesion between the insulating resin layer and the metal plating is improved.

There is no particular limitation on the method of metal plating treatment, and a method of metal plating treatment generally used when manufacturing a multilayer printed wiring board can be appropriately used. The method of metal plating and the type of chemical solution used for the plating are not particularly limited, and the method and chemical solution of metal plating generally used in the manufacture of multilayer printed wiring boards can be suitably used. The chemical solution used for the metal plating process may be a commercially available product.
There is no particular limitation on the metal plating treatment method, and examples thereof include: treatment by degreasing solution, treatment by softetching solution, acid cleaning, treatment by prepreg solution, treatment by catalyst solution, promotion Treatment of liquid solution, treatment of chemical copper liquid, acid cleaning and treatment of immersion in copper sulfate solution and current flow.

When a copper foil with an insulating resin layer in a semi-hardened state is used and stacked, a printed wiring board can usually be obtained by subjecting the insulating resin layer in a semi-hardened state to heat treatment or the like to completely harden it. In this embodiment, another copper foil with an insulating resin layer in this embodiment may be further laminated on the obtained printed wiring board.

The lamination method in the stacking method is not particularly limited, and a vacuum pressure type laminator can be preferably used. In this case, the copper foil provided with an insulating resin layer in this embodiment can be laminated with an elastomer such as rubber. The lamination conditions are not particularly limited as long as they are conditions used for lamination of a general printed wiring board, for example, at a temperature of 70 to 140 ° C, a contact pressure in a range of 1 to 11 kgf / cm ² and 20 hPa or less. It is carried out under reduced pressure. After the lamination step, the laminated adhesive film can be smoothed by hot pressing with a metal plate. The lamination step and the smoothing step can be performed continuously using a commercially available vacuum pressure laminator. It is also possible to have a heat-hardening step after the lamination step or after the smoothing step. By using the thermal curing step, the insulating resin layer can be completely cured. The thermal curing conditions differ depending on the types of components contained in the resin composition, etc., but usually the curing temperature is 170 to 190 ° C and the curing time is 15 to 60 minutes.

Examples of the method for forming a circuit pattern on the single-sided or double-sided copper foil of the printed wiring board of this embodiment include a semi-additive method, a full-additive method, and a subtractive method. Subtractive method and so on. Among them, a semi-additive method is preferable in view of forming a fine wiring pattern.

As an example of a method for forming a circuit pattern by a semi-additive method, electrolytic plating (pattern plating) can be selectively applied using a plating resist, and thereafter, the plating resist is peeled off, and the whole is appropriately etched. Method for forming wiring pattern. The circuit pattern formed by the semi-additive method is implemented by combining electroless plating and electrolytic plating. At this time, it is preferable to perform drying after electroless plating and after electrolytic plating. Drying after electroless plating is not particularly limited. For example, it is preferably performed at 80 to 180 ° C for 10 to 120 minutes. Drying after electrolytic plating is not particularly limited. For example, it is preferably performed at 130 to 220 ° C for 10 to 120 minutes. The plating should be copper plating.

As an example of a method of forming a circuit pattern by a subtractive method, a method of forming a wiring pattern by selectively removing a conductor layer using a resist may be mentioned. Specifically, it can be implemented in the following manner, for example. Under the conditions of a temperature of 110 ± 10 ° C and a pressure of 0.50 ± 0.02 MPa, a dry film photoresist (Laminated by Hitachi Chemical Co., Ltd. RD-1225 (trade name)) was laminated on the entire surface of the copper foil. Then, exposure and masking are performed along the circuit pattern. Thereafter, the dry film photoresist was developed using a 1% sodium carbonate aqueous solution, and finally, the dry film photoresist was peeled using an amine-based photoresist stripping solution. This allows the copper foil to be patterned.

In this embodiment, an insulating resin layer and / or a conductor layer may be further laminated on the printed wiring board to obtain a multilayer printed wiring board. The inner layer of the multilayer printed wiring board may have a circuit board. The insulating resin layer of the copper foil provided with an insulating resin layer in this embodiment is one of an insulating resin layer and a conductor layer constituting a multilayer printed wiring board.

The lamination method is not particularly limited, and a method generally used in general lamination molding of a printed wiring board can be used. Examples of the lamination method include a multilayer press, a multilayer vacuum press, a laminator, a vacuum laminator, an autoclave forming machine, and the like. The temperature at the time of lamination is not particularly limited. For example, it is appropriately selected and implemented in the range of 100 to 300 ° C. The pressure is not particularly limited. For example, it is in the range of 0.1 to 100 kgf / cm ² (about 9.8 kPa to about 9.8 MPa). The heating time is appropriately selected and implemented, and for example, the heating time is not particularly limited. For example, the heating time is appropriately selected and implemented in a range of 30 seconds to 5 hours. Further, if necessary, post-hardening may be performed in a temperature range of 150 to 300 ° C. and the degree of hardening may be adjusted.

[Semiconductor element mounting substrate]
For the substrate for mounting a semiconductor element, for example, a copper foil with an insulating resin layer according to this embodiment is laminated on a metal foil-clad laminate, and the surface or one side of the obtained copper foil is masked and patterned. And made. The masking and patterning may be performed using a known masking and patterning method used in the manufacture of a printed wiring board, and is not particularly limited, but it is preferable to use the aforementioned subtraction method to form a circuit pattern. The circuit pattern may be formed on only one side of the laminate or on both sides.

The substrate for mounting a semiconductor element obtained by using the copper foil provided with an insulating resin layer of this embodiment is thin, has fine wiring with high density, and has few appearance defects.
[Example]

Although the examples of this embodiment will be described, this embodiment is not limited to these examples.

[1. Evaluation of copper foil]
(1) Arithmetic average roughness Using a shape measuring microscope (laser microscope, VK-X210 (trade name) manufactured by KEYENCE Co., Ltd.), the copper foil surface was photographed at an objective lens magnification of 150 times (15-inch screen magnification: 3000 times) . Then, the height distribution on a straight line with a length of 90 μm randomly selected among the captured images is obtained by image processing, and the arithmetic average roughness (Ra) is calculated.

[2. Evaluation of metal foil-clad laminates]
(1) Moldability A metal foil-clad laminate described later is etched to remove copper foil. The surface of the obtained resin substrate (insulating resin layer) was visually confirmed and evaluated as "C" when cracks or voids, prominent streaks, or unevenness in resin were observed during molding, and the evaluation was "A"".

(2) Transportability test The metal foil-clad laminate described later is etched to remove copper foil. After the obtained resin substrate (insulating resin layer) was adjusted to a rectangle of 100 mm × 50 mm, the peeling part (the peeling part of the EMINENTO type development etching peeling part line, the pressure was 0.1 MPa, manufactured by Tokyo Chemical Industry Co., Ltd.) was washed It is conveyed to confirm whether the resin substrate is damaged.
When the resin substrate is damaged or missing, it is evaluated as "C" when it is 1% or more of the mass before the input, and when it is less than 1%, it is evaluated as "A".

In Comparative Examples 3 and 4, the obtained polyethylene terephthalate film of the adhesive film was peeled off, and a copper foil of 12 μm thickness was disposed on both sides so as to contact the felted surface of the copper foil (Mitsui Metals 3EC-III (trade name) made by Co., Ltd.) was formed at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes to obtain a metal foil-clad laminate. The obtained formability and transportability test were performed on the obtained metal-clad laminate.

(3) Laser processing test The metal foil-clad laminate to be described later was subjected to a half-etching treatment (Clean Etch (registered trademark) CPE-770 (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the thickness of copper was etched from 12 μm to 5 μm. Then, a laser pre-treatment (BONDFilm (registered trademark) LDD101 (trade name) made by Atotech Japan) was performed. A carbon dioxide laser processing machine for printed circuit boards (ML605GTW3 (H) -5200U (trade name), mask 1.1 mm, manufactured by Mitsubishi Electric Corporation) was used for the laminated board after the laser pre-treatment. Hole processing. After that, the cross section of the opening was polished, and then the surface of the opening was observed at a magnification of 500 times using a SEM (scanning electron microscope, VE-7800S (trade name) manufactured by KEYENCE Corporation). The obtained SEM image was used to find the glass fiber protruding from the cross section of the opening, and the distance from the root to the tip of the glass fiber protruding portion was measured 5 times, and the average value was calculated. When the average value was 5 μm or less, it was evaluated as “A”, and when it was larger than 5 μm, it was evaluated as “C”.

In Comparative Examples 3 and 4, the obtained laminated substrates (without slag removal treatment) were used with a carbon dioxide laser processing machine for printed substrates (ML605GTW3 (H) -5200U (trade name) manufactured by Mitsubishi Electric Corporation). The cover (1.1 mm) is processed with a blind guide hole (opening) having an opening diameter of φ80 μm. Thereafter, it was performed in the same manner as the laser processing test described above, and the average value of the distance from the root to the tip of the protruding portion of the glass fiber was calculated and evaluated.

(4) Appearance after deslagging treatment The deslagging treatment was performed on the laminated substrates described in Comparative Examples 3 and 4. The slag removal treatment is immersed in a swelling liquid for removing slag (PTH-B103 (trade name) manufactured by Okuno Pharmaceutical Industry Co., Ltd.) at 65 ° C for 5 minutes, and then swelled at 80 ° C. PTH1200 (commercial name) and PTH1200NA (commercial name), Okano Pharmaceutical Industry Co., Ltd. for 8 minutes, and finally immersed in a neutralizing solution for removing rubber residue at 45 ° C (Okuno Pharmaceutical Industry Co., Ltd. PTH-B303 (trade name) )) 5 minutes to implement. Thereafter, the surface state of the laminated substrate after the slag removal treatment was confirmed, and the evaluation was "A" when the surface was uniform, and the evaluation was evaluated as "C" when the uneven surface shape was observed and the glass fibers were peeled off or the glass fibers were exposed on the surface. ".

(5) Peel strength measurement A test piece (30 mm x 150 mm x 0.8 mm thick) of a metal foil-clad laminate described later was used, and the measurement was performed three times using a coating bar according to the test method (5.7 Peel strength) described in JIS C6481. The average peeling strength (kN / m) of the insulating resin layer provided on the copper foil and the peeling strength of the copper foil was calculated.
In the same manner, using the laminated substrates described in Comparative Examples 3 and 4 which had been subjected to plating treatment, the peeling strength of the copper plating layer and the insulating resin layer was measured three times, and the average value was determined ( kN / m).
From the obtained average value, the peel strength was evaluated according to the following criteria.
A: 0.6kN / m or more
B: 0.4kN / m or more and less than 0.6kN / m
C: less than 0.4kN / m

[3. Production of resin composition and copper foil with insulating resin layer]
(Synthesis of α-naphthol aralkyl cyanate compound)
The reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux cooler was cooled to 0 to 5 ° C with brine in advance, and 7.47 g (0.122 mol) of cyanogen chloride and 9.75 g (0.0935 of 35% hydrochloric acid) were cooled. mol), 76 ml of water and 44 ml of dichloromethane were fed. Then, the temperature in the reactor was maintained at -5 to + 5 ° C and the pH was 1 or less, and the aralkyl α-naphthol represented by the following formula (4) was added dropwise using a dropping funnel over 1 hour while stirring. (SN485 (trade name) manufactured by Nippon Steel Chemical Co., Ltd., OH group equivalent: 214 g / eq., Softening point: 86 ° C) 20 g (0.0935 mol) and triethylamine 14.16 g (0.14 mol) were dissolved in dichloromethane 92ml solution. After the dropwise addition was completed, 4.72 g (0.047 mol) of triethylamine was added dropwise over a further 15 minutes.

[Chemical 4]

In the formula (4), n ⁴ falls within a range of 3 to 4 as an average value.

After completion of the dropwise addition, after stirring at the same temperature for 15 minutes, the reaction solution was separated, and the organic layer was separated and extracted. After the obtained organic layer was washed twice with 100 ml of water, dichloromethane was distilled off under reduced pressure using an evaporator, and finally concentrated and dried at 80 ° C. for 1 hour, thereby obtaining α- represented by the following formula (5): 23.5 g of naphthol aralkyl cyanate compound.

[Chemical 5]

In the formula (5), n ⁵ falls within a range of 3 to 4 as an average value.

[Example 1]
50 parts by mass of an α-naphthol aralkyl cyanate compound represented by the above formula (5), and bis (3-ethyl-5-methyl-4-maleiminophenyl) methane ( 10 parts by mass of BMI-70 (trade name) by K.I. Kasei Co., Ltd. and polyoxynaphthalene-based epoxy resin (EXA-7311 (trade name) by DIC (share)), epoxy equivalent: 277 g / eq .) 40 parts by mass are dissolved in methyl ethyl ketone. Then, 3 parts by mass of a wetting and dispersing agent (Disperbyk (registered trademark) -161 made by BYK), spherical fused silica (average particle diameter: 0.4 to 0.6 μm, Admatechs (shares)) 250 parts by mass of SC2050-MB (trade name)), 0.02 parts by mass of zinc octoate, 5 parts by mass of acrylonitrile butadiene rubber (N220S (trade name) manufactured by JSR) and milled fibers (Central Glass ( EFDE50-31 (trade name) made of strands, average fiber length: 50 μm, fiber diameter: 6 μm), 21 parts by mass of varnish. The varnish obtained by diluting with methyl ethyl ketone was applied to a copper foil having a thickness of 350 mm × 250 mm × 12 μm using a coating rod (arithmetic average roughness (Ra): 1.0 to 1.5 μm, 3EC-III (commodity made by Mitsui Metals Mining Corporation) Name)) was heated and dried at 130 ° C. for 5 minutes to obtain a copper foil with an insulating resin layer having an insulating resin layer having a thickness of 40 μm.

A 12 μm-thick copper foil (3EC-III (trade name) manufactured by Mitsui Metals Mining Co., Ltd.) was placed on the insulating resin layer side of the obtained copper foil with an insulating resin layer so as to contact the felted surface, and Forming was performed at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes, thereby obtaining a metal foil-clad laminate. The obtained metal-clad laminate was evaluated, and the results are shown in Table 1. The SEM image of the surface of the opening is shown in FIG. 2.

[Example 2]
The milled fiber (EFDE50-31 (trade name) manufactured by Central Glass (trade name), average fiber length: 50 μm, fiber diameter: 6 μm) was changed from 21 parts by mass to 63 parts by mass, and the examples were also used. 1 In the same manner, a copper foil with an insulating resin layer having a thickness of 40 μm of the insulating resin layer was obtained. Then, it carried out similarly to Example 1, and obtained the metal foil-clad laminated board. Evaluation was performed on the obtained metal-clad laminate, and the results are shown in Table 1.

[Example 3]
The milled fiber (EFDE50-31 (trade name) manufactured by Central Glass (stock), average fiber length: 50 μm, fiber diameter: 6 μm) was changed from 21 parts by mass to 100 parts by mass, and the examples were also used. 1 In the same manner, a copper foil with an insulating resin layer having a thickness of 40 μm of the insulating resin layer was obtained. Then, it carried out similarly to Example 1, and obtained the metal foil-clad laminated board. Evaluation was performed on the obtained metal-clad laminate, and the results are shown in Table 1.

[Example 4]
The milled fiber (EFDE50-31 (trade name), manufactured by Central Glass (stock), average fiber length: 50 μm, fiber diameter: 6 μm) was changed from 21 parts by mass to 300 parts by mass, and the examples were also used. 1 In the same manner, a copper foil with an insulating resin layer having a thickness of 40 μm of the insulating resin layer was obtained. Then, it carried out similarly to Example 1, and obtained the metal foil-clad laminated board. Evaluation was performed on the obtained metal-clad laminate, and the results are shown in Table 1.

[Example 5]
Except changing the thickness of the insulating resin layer from 40 μm to 15 μm, the same procedure as in Example 1 was performed to obtain a copper foil with an insulating resin layer having a thickness of 15 μm of the insulating resin layer. Then, it carried out similarly to Example 1, and obtained the metal foil-clad laminated board. Evaluation was performed on the obtained metal-clad laminate, and the results are shown in Table 1.
In addition, since the thickness of the insulating resin layer is too thin to etch the metal-clad laminate, the transportability test was not performed.

[Example 6]
The varnish obtained in Example 1 was diluted with methyl ethyl ketone and applied to a copper foil having a thickness of 350 mm × 250 mm × 12 μm using a coating rod (arithmetic average roughness (Ra): 0.5 μm, manufactured by Mitsui Metals Mining Corporation) M2S-VLP (trade name)) was heated and dried at 130 ° C. for 5 minutes to obtain a copper foil with an insulating resin layer having a thickness of 40 μm and an insulating resin layer. Then, it carried out similarly to Example 1, and used the 12 micrometer-thick copper foil (3EC-III (trade name) by Mitsui Metals Mining Co., Ltd.) to obtain a metal foil-clad laminate. Evaluation was performed on the obtained metal-clad laminate, and the results are shown in Table 1.

[Example 7]
Milled fiber (EFH30-01 (trade name), manufactured by Central Glass (stock), average fiber length: 30 μm, fiber diameter: 11 μm) was used instead of milled fiber (EFDE50-31, manufactured by Central Glass (stock)) Name), average fiber length: 50 μm, fiber diameter: 6 μm), except that the same procedure as in Example 1 was performed to obtain a copper foil with an insulating resin layer having an insulating resin layer thickness of 40 μm. Then, it carried out similarly to Example 1, and obtained the metal foil-clad laminated board. Evaluation was performed on the obtained metal-clad laminate, and the results are shown in Table 1.

[Example 8]
Milled fiber (EFH150-31 (trade name), manufactured by Central Glass (stock), average fiber length: 150 μm, fiber diameter: 11 μm) was used instead of milled fiber (EFDE50-31, manufactured by Central Glass (stock)) Name), average fiber length: 50 μm, fiber diameter: 6 μm), except that the same procedure as in Example 1 was performed to obtain a copper foil with an insulating resin layer having an insulating resin layer thickness of 40 μm. Then, it carried out similarly to Example 1, and obtained the metal foil-clad laminated board. Evaluation was performed on the obtained metal-clad laminate, and the results are shown in Table 1.

[Comparative Example 1]
Except that the milled fiber (EFDE50-31 (trade name) manufactured by Central Glass, average fiber length: 50 μm, fiber diameter: 6 μm) was not blended, it was conducted in the same manner as in Example 1 to obtain insulation. The thickness of the insulating resin layer was 40 μm, and the copper foil was provided with an insulating resin layer. Evaluation was performed on the obtained metal-clad laminate, and the results are shown in Table 1. In addition, in the evaluation of laser processability, since the milled fiber was not blended in Comparative Example 1, no glass fiber protruding from the cross section of the opening was observed.

[Comparative Example 2]
The milled fiber (EFDE50-31 (trade name), manufactured by Central Glass (stock), average fiber length: 50 μm, fiber diameter: 6 μm) was changed from 21 parts by mass to 500 parts by mass, and the examples were also used. 1 was performed in the same manner to obtain a varnish. The varnish obtained by diluting with methyl ethyl ketone was applied to a polyethylene terephthalate film (thickness: 38 μm) using a coating rod. However, the varnish could not be applied and an adhesive film could not be obtained.

[Comparative Example 3]
The milled fiber (EFDE50-31 (trade name) manufactured by Central Glass (trade name), average fiber length: 50 μm, fiber diameter: 6 μm) was changed from 21 parts by mass to 63 parts by mass, and the examples were also used. 1 was performed in the same manner to obtain a varnish. This varnish was diluted with methyl ethyl ketone, and applied to a polyethylene terephthalate film (thickness: 38 μm) with a coating rod, and dried by heating at 130 ° C. for 5 minutes, thereby obtaining a thickness of a layer composed of a resin composition as 40 μm adhesive film. A transportability test was performed on the obtained adhesive film, and the results are shown in Table 1.

Next, a copper-clad laminate (CCL (registered trademark)-HL832NSF (trade name), manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used with a CZ-8100 (trade name) manufactured by MEC (stock), and the thickness of the insulating resin layer was 0.1. mm, copper foil thickness: 12 μm) roughened on both sides to obtain a roughened copper foil-clad laminate. The adhesive film obtained above was placed on both sides of the roughened product of the copper-clad laminate so that the layer composed of the resin composition was in contact with the copper foil, and a batch vacuum pressure laminator was used ( CVP-600 (trade name) manufactured by Nichigo-Morton (stock) was laminated to obtain a laminate. The lamination system was carried out by pressing under a vacuum at a temperature of 120 ° C and a pressure of 8 kgf / cm ² . The polyethylene terephthalate film was peeled from both sides of the obtained laminate. Thereafter, a layer made of a resin composition was hardened under a hardening condition at a temperature of 80 ° C. for 30 minutes and then at a temperature of 180 ° C. for 30 minutes to form an insulating resin layer. Laminated substrate of insulating resin layer. A laser processing test was performed on the obtained laminated substrate, and the results are shown in Table 1. The SEM image of the surface of the opening is shown in FIG. 3.

The laminated substrate subjected to the hole-opening processing by laser processing is subjected to a slag removing treatment, and the appearance after the processing is confirmed. The results are shown in Table 1. Since there are no copper foils on both sides, the glass fiber was observed to protrude a lot and the surface was rough.

The obtained laminated substrate after the desmearing treatment was subjected to copper plating to form a copper plating layer having a thickness of 18 μm. The laminated substrate subjected to the plating treatment was used to measure the peel strength. The results are shown in Table 1.

[Comparative Example 4]
Except that the milled fiber was not blended (EFDE50-31 (trade name) manufactured by Central Glass, average fiber length: 50 μm, fiber diameter: 6 μm), the same procedure as in Comparative Example 3 was performed. An adhesive film having a thickness of 40 μm of a layer composed of a resin composition, a laminated substrate having an insulating resin layer on both sides of a copper-clad laminated board, a laminated substrate subjected to hole processing by laser processing, And laminated substrate after deslagging treatment. These were evaluated in the same manner as in Comparative Example 3, and the results are shown in Table 1. In addition, in the evaluation of the laser processability and the appearance after the slag removal treatment, in Comparative Example 4, since the milled fiber was not blended, the glass fiber protruding from the cross section of the opening was not observed, and the surface shape was also not observed. For uniform.

[Comparative Example 5]
On both sides of the prepreg (GHPL-830NSF (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness of the insulating resin layer: 40 μm), a copper foil of 12 μm thickness (3EC-III (manufactured by Mitsui Metals Mining Co., Ltd.) Trade name)), forming at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes, thereby obtaining a metal foil-clad laminate. The evaluation of the transportability test and the laser processing test was performed on the obtained metal-clad laminate, and the results are shown in Table 1.

[Comparative Example 6]
The milled fiber (EFDE50-31 (trade name) manufactured by Central Glass (stock), average fiber length: 50 μm, fiber diameter: 6 μm) was changed from 21 parts by mass to 63 parts by mass, and the spherical fusion A varnish was produced in the same manner as in Example 1 except that silicon oxide (SC2050MB (trade name) manufactured by Admatechs) was used. The varnish obtained by diluting with methyl ethyl ketone was carried out in the same manner as in Example 1. Then, a 350 mm × 250 mm × 12 μm-thick copper foil (3EC-III (trade name) manufactured by Mitsui Metals Mining Co., Ltd.) was coated with a coating rod.化 面面。 Face side. Thereafter, it was heated and dried at 130 ° C. for 5 minutes to manufacture a copper foil with an insulating resin layer, but the insulating resin layer could not be molded, and a copper foil with an insulating resin layer could not be manufactured.

[Comparative Example 7]
The varnish obtained in Example 1 was diluted with methyl ethyl ketone, and applied to a copper foil having a thickness of 350 mm × 250 mm × 12 μm using a coating rod (arithmetic average roughness (Ra): 0.04 μm, GHT5-HA (commercial product made by JX Metal Co., Ltd.) Name)) The heated side of the felt surface was heated and dried at 130 ° C. for 5 minutes to obtain a copper foil with an insulating resin layer having an insulating resin layer thickness of 40 μm. Then, it carried out similarly to Example 1, and used the 12 micrometer-thick copper foil (3EC-III (trade name) by Mitsui Metals Mining Co., Ltd.), and obtained the metal foil-clad laminate. Evaluation was performed on the obtained metal-clad laminate, and the results are shown in Table 1.

[Comparative Example 8]
The varnish obtained in Example 1 was diluted with methyl ethyl ketone and applied to a 350 mm × 250 mm × 70 μm-thick copper foil (arithmetic average roughness (Ra): 4 μm, GY-MP (manufactured by Furukawa Circuit Foil Taiwan (FCFT)) using a coating rod. Product name)) was heated and dried at 130 ° C. for 5 minutes to obtain a copper foil with an insulating resin layer having an insulating resin layer thickness of 40 μm. Then, it carried out similarly to Example 1, and used the 12 micrometer-thick copper foil (3EC-III (trade name) by Mitsui Metals Mining Co., Ltd.), and obtained the metal foil-clad laminate. Evaluation was performed on the obtained metal-clad laminate, and the results are shown in Table 1.

[Table 1]

This application is based on a Japanese patent application filed on December 14, 2017 (Japanese Patent Application No. 2017-239467), and the contents thereof are incorporated herein by reference.
[Industrial availability]

According to the present invention, it is possible to ideally obtain a thin printed wiring board having a high density of fine wirings and a good via hole, and a substrate for mounting a semiconductor element.

10‧‧‧Printed wiring board made by laminating insulating resin on copper-clad laminate (before opening)

11‧‧‧Printed wiring board made by laminating insulating resin on copper-clad laminate (after opening)

20‧‧‧ This is a printed wiring board in which copper foil with an insulating resin layer in this embodiment is laminated on a metal foil laminate (before opening).

21‧‧‧A printed wiring board (after opening) in which a copper foil with an insulating resin layer is laminated on a metal foil laminated board in this embodiment

30‧‧‧ insulating resin layer

31‧‧‧copper foil

32‧‧‧ Glass fiber and other inorganic substances

40‧‧‧ glass fiber protruding part

[Fig. 1] It is a schematic diagram showing a surface state of a via hole when a printed wiring board is drilled using laser processing.

Fig. 2 is a SEM image of the surface of the opening after laser processing (Example 1).

Fig. 3 is a SEM image of the surface of the opening after laser processing (Comparative Example 3).

Claims (9)

A copper foil with an insulating resin layer includes: Copper foil; and An insulating resin layer laminated on the copper foil, The arithmetic mean roughness (Ra) of the copper foil surface in contact with the insulating resin layer is 0.05 to 2 μm, The insulating resin layer is composed of a resin composition containing (A) a thermosetting resin, (B) a spherical filler, and (C) short glass fibers having an average fiber length of 10 to 300 μm. For example, the copper foil provided with an insulating resin layer in the first patent application scope, wherein the thickness of the insulating resin layer is 3 to 50 μm. For example, the copper foil provided with an insulating resin layer in the first patent application scope, wherein the thickness of the copper foil is 1 to 18 μm. For example, the copper foil with an insulating resin layer attached to the first patent application scope has a fiber diameter of 1 to 15 μm. For example, the copper foil provided with an insulating resin layer in the first patent application scope, wherein the content of the short glass fibers is 5 to 450 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. For example, the copper foil provided with an insulating resin layer in the first patent application scope, wherein the short glass fibers are milled fibers. For example, the copper foil with an insulating resin layer in the first patent application scope, wherein the content of the spherical filler is 50 to 500 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. For example, the copper foil provided with an insulating resin layer in the first patent application range, wherein the thermosetting resin contains a material selected from the group consisting of epoxy resin, cyanate compound, maleimide compound, phenol resin, and thermosetting. Modified polyphenylene ether resin, benzopyrene At least one of the group consisting of a compound, an organic-based modified polysiloxane, and a compound having a polymerizable unsaturated group. For example, the copper foil with an insulating resin layer in the scope of patent application No. 1 is used as a stacking material for printed wiring boards or substrates for mounting semiconductor elements.