JP2019127491A - Quartz glass fiber-containing prepreg, quartz glass fiber-containing film and quartz glass fiber-containing substrate - Google Patents

Abstract

To provide a quartz glass fiber-containing prepreg having excellent dielectric properties, and having excellent heat resistance, and a quartz glass fiber-containing film and a quartz glass fiber-containing substrate including the quartz glass fiber-containing prepreg.SOLUTION: A quartz glass fiber-containing prepreg contains (A) a quartz glass fiber and (B) a curable resin composition. In the (A) quartz glass fiber, the number of air bubbles contained therein is 10/mor less per unit area.SELECTED DRAWING: None

Description

  The present invention relates to a quartz glass fiber-containing prepreg, a quartz glass fiber-containing film, and a quartz glass fiber-containing substrate.

  With the development of digital technology, electronic devices such as personal computers and mobile phones are being reduced in size and size, and enhanced in function. For example, high density mounting and reduction in size and thickness on printed circuit boards, which are representative components, are required. It is done. In order to cope with this, there is a strong demand for improving the properties of glass fiber-containing substrates and films.

  In addition, with the progress of high speed and high frequency such as computer, mobile and communication infrastructure, high tensile rigidity for low dielectric material, super thin film substrate and film excellent in transmission loss as characteristic required for printed wiring board Characteristics, uniformity of glass fiber, and thinning are required (Patent Documents 1 and 2).

  Conventionally, cloths woven from E glass fibers and D glass fibers have been used as glass cloths used for prepregs and substrates (Patent Documents 3 to 5). Among glass fibers, quartz glass fibers are attracting attention because of their characteristics such as high heat resistance, low impurities, low dielectric constant, and dielectric loss.

  In addition, since general-purpose glass cloth has holofibers containing bubbles, plating solution, cleaning solution, etching solution, etc. used in the substrate molding process penetrates into the bubbles present in the cloth, and the plating layer does not attach, resulting in poor conduction. Defects such as generation and deterioration of dielectric properties occur. On the other hand, quartz glass cloth has a low content of holofiber, so that there is no problem of conduction failure and deterioration of dielectric characteristics, which are problems with general-purpose glass cloth.

JP 2016-131243 A JP2015-155196A JP-A-9-74255 JP-A-2-61131 Japanese Patent Laid-Open No. 62-169495

  The present invention has been made in view of the above circumstances, and provides a quartz glass fiber-containing prepreg having excellent dielectric characteristics and heat resistance, a quartz glass fiber-containing film and a quartz glass fiber-containing substrate using the quartz glass fiber-containing prepreg. The purpose is to do.

In order to achieve the above object, the present invention provides:
A quartz glass fiber-containing prepreg,
(A) A quartz glass fiber-containing prepreg comprising a quartz glass fiber (B) and a curable resin composition, wherein the (A) quartz glass fiber contains 10 bubbles / m ² or less of bubbles per unit area. I will provide a.

  If it is a quartz glass fiber containing prepreg of this invention, it will become a quartz glass fiber containing prepreg which is excellent in a dielectric characteristic and excellent in heat resistance by using a quartz glass fiber with few bubbles.

  Moreover, it is preferable that the fiber diameter of said (A) quartz glass fiber is 3 micrometers or more and 9 micrometers or less, and fictive temperature is 1,300 to 1500 degreeC.

  Such a quartz glass fiber is a quartz glass fiber-containing prepreg having excellent processability and mass productivity and excellent structural stability.

  In addition, the (B) curable resin composition is a thermosetting resin containing at least one of a curable resin selected from silicone resin, curable polyimide resin, maleimide resin, epoxy resin, cyanate resin, and (meth) acrylic resin. And / or a photocurable resin composition.

  Such a resin composition can be suitably used for the quartz glass fiber-containing prepreg of the present invention.

  Moreover, it is preferable that the said (B) curable resin composition contains an inorganic filler further.

  Thus, if it is a quartz glass fiber containing prepreg containing an inorganic filler, the low thermal expansion characteristic of the resin composition, high elastic modulus, heat resistance, flame retardancy etc. can be improved.

  Moreover, the quartz glass fiber containing film which consists of a hardened | cured material of the said quartz glass fiber containing prepreg 1 sheet is provided.

  Thus, the quartz glass fiber containing prepreg of this invention can be used suitably for a quartz glass fiber containing film.

  In the quartz glass fiber-containing film, the absolute value of the difference between the dielectric loss tangent at 1.0 GHz and the dielectric loss tangent at 10 GHz is preferably 0 or more and 0.01 or less.

  Such a quartz glass fiber-containing film is a material suitable for application to various electronic components utilizing its low dielectric properties.

  Moreover, the quartz glass fiber containing board | substrate which consists of a lamination | stacking hardened | cured material of two or more sheets of the said quartz glass fiber containing prepreg is provided.

  Thus, the quartz glass fiber containing prepreg of this invention can be used suitably for a quartz glass fiber containing board | substrate.

  In the quartz glass fiber-containing substrate, the absolute value of the difference between the dielectric loss tangent at 1.0 GHz and the dielectric loss tangent at 10 GHz is preferably 0 or more and 0.01 or less.

  Such a quartz glass fiber-containing substrate is a material suitable for application to various electronic components utilizing its low dielectric properties.

  The quartz glass fiber-containing prepreg of the present invention is a quartz glass fiber-containing prepreg having excellent dielectric properties, high strength, high tensile rigidity, surface uniformity, thin film formability, and excellent plating properties. And a quartz glass fiber-containing substrate.

The present invention includes the following aspects.
<Quartz glass fiber containing prepreg>
[(A) Quartz glass fiber]
The quartz glass fibers contained in the quartz glass fiber-containing prepreg in the present invention may be fibrous or cloth-like called glass cloth, but it is preferable to use quartz glass cloth because it is easy to handle. The quartz glass cloth is produced using a quartz glass strand and / or a quartz glass yarn. Quartz glass strands and / or quartz glass yarns are bundles of 50 to 500 quartz glass fibers. In the present invention, a bundle of fibers bundled without twisting is referred to as a strand, and a bundle of fibers twisted together is referred to as a yarn.

  The fictive temperature of the quartz glass fiber is preferably in the range of 1,300 ° C. to 1,500 ° C. If the fictive temperature is within the fictive temperature range, the processability and mass productivity are excellent, and the structural stability is excellent. The fiber diameter is preferably 3 μm or more and 9 μm or less.

Further, the quartz glass fiber contained in the quartz glass fiber-containing prepreg of the present invention has an extremely small content of air bubbles, and the number of air bubbles is 10 / m ² or less per unit area, preferably 5 / m ^2. It is below.

  The quartz glass fiber contained in the prepreg containing quartz glass fiber of the present invention preferably has characteristics such as high heat resistance, low impurities, low dielectric constant, and dielectric loss, in addition to the above characteristics. In addition, it is preferable to have high strength and high tensile stiffness characteristics, surface uniformity, and excellent thin film formability. As the quartz glass fiber, quartz glass fiber made from natural quartz glass and / or synthetic quartz glass can be used.

[(B) Curable resin composition]
The curable resin composition is preferably a thermosetting resin composition and / or a photocurable resin composition, and may be in any state of liquid, semi-solid or solid at normal temperature (25 ° C.) Absent. Specific examples of the curable resin contained in the curable resin composition include silicone resin, curable polyimide resin, maleimide resin, epoxy resin, cyanate resin, (meth) acrylic resin and the like, and the quartz of the present invention The glass fiber-containing prepreg, the substrate, and the film preferably contain at least one of curable resins selected therefrom. Among them, silicone resins, curable polyimides, maleimide resins and epoxy resins are preferably used. The curable resin may be used alone or in combination of a plurality of resins.

((B-1) silicone resin)
The silicone resin includes an addition curing type silicone resin and a condensation type silicone resin.
As the addition curing silicone resin, the following components (a) to (c),
(A) Organopolysiloxane represented by the following average composition formula (1) and having at least two alkenyl groups bonded to silicon atoms in one molecule (R ¹ ₃ SiO _1/2 ) _a (R ¹ ₂ SiO _{2 / 2} ) _b (R ¹ SiO _3/2 ) _c (SiO _4/2 ) _d (1)
(Wherein, R ¹ independently represents a hydroxyl group, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 5 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, and carbon A group selected from alkenyl groups of 2 to 10, a, b, c, d are numbers satisfying a ≧ 0, b ≧ 0, c ≧ 0, d ≧ 0, and a + b + c + d = 1.)
(B) Organohydrogenpolysiloxane represented by the following average composition formula (2) and having at least two hydrogen atoms bonded to silicon atoms in one molecule (R ² ₃ SiO _1/2 ) _e (R ² ₂ SiO _2/2 ) _f (R ² SiO _3/2 ) _g (SiO _4/2 ) _h (2)
(Wherein R ² independently represents a hydrogen atom, or a hydroxyl group, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 5 to 10 carbon atoms, an aromatic hydrocarbon having 6 to 10 carbon atoms And e, f, g and h are numbers satisfying e ≧ 0, f ≧ 0, g ≧ 0, h ≧ 0 and e + f + g + h = 1)
The blending ratio of the component (a) to the component (b) is such that the amount of hydrogen atoms bonded to silicon atoms in the component (b) is 0 per mole of alkenyl groups bonded to silicon atoms in the component (a). And an amount of 1 to 5.0 moles, and (c) a silicone resin containing an addition reaction catalyst.

Further, as the condensation type silicone resin, the following component (d),
(D) An organopolysiloxane represented by the following average composition formula (4) and having at least two condensation-reactive groups in one molecule (R ³ ₃ SiO _1/2 ) _i (R ³ ₂ SiO _2/2) ) _J (R ³ SiO _3/2 ) _k (SiO _4/2 ) _l (4)
(Wherein R ³ independently represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 5 to 10 carbon atoms, or 6 to 6 carbon atoms It is a group selected from 10 aromatic hydrocarbon groups, and at least two or more of R ³ in one molecule are a hydroxyl group or a group selected from an alkoxy group having 1 to 6 carbon atoms, i, j, k, l Is a number satisfying i ≧ 0, j ≧ 0, k ≧ 0, l ≧ 0, i + j + k + l = 1.)
And silicone resins containing

  (D) alone is condensed and cured by heating, but a condensation catalyst may be added separately in order to accelerate the curing.

  The silicone resin that can be included in the prepreg containing quartz glass fibers of the present invention is 10 mol% to 99 mol%, preferably 15 mol% to 80 mol%, more preferably 17 mol%, based on all organic groups bonded to silicon atoms. It is preferred to contain an aryl group bonded to a mole percent to 75 mole percent silicon atom.

((B-2) curable polyimide resin, maleimide resin)
Curable polyimide resins are classified according to the chemical nature of their reactive end groups. Among these, the use of a maleimide resin is preferable from the viewpoint of processability and handling. The following describes the maleimide resin.

  The maleimide resin is a compound containing two or more maleimide groups in one molecule and may be a resin that is cured by reaction of the maleimide group by heating. Examples of the maleimide resin include N, N ′-(4,4′-diphenylmethane) bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and the like. A maleimide resin having a hydrogen group is preferable because it has not only excellent heat resistance but also excellent dielectric properties.

  Moreover, in order to accelerate hardening more, you may contain a reaction initiator. Although it does not limit as a reaction initiator, A peroxide etc. are mentioned. Further, a compound having a functional group capable of reacting with a maleimide group may be contained as a curing agent. Examples of the curing agent include alicyclic maleimides, aromatic maleimides, unsaturated hydrocarbons, aromatic amines, aliphatic amines, alicyclic amines, acid anhydrides, isocyanates, and the like. .

((B-3) Epoxy resin)
The epoxy resin should just contain 2 or more of epoxy groups in 1 molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy Naphthalene frame structure type epoxy resin such as resin, phenol aralkyl type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, bifunctional biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, dihydroanthracene Type epoxy resin. Among these, from the viewpoint of dielectric properties and thermal expansion properties, it is preferable to use a naphthalene skeleton-containing epoxy resin or a biphenyl aralkyl epoxy resin. One of these may be used alone, or two or more may be used in combination.

  In addition, a curing agent that reacts with the epoxy resin may be used, and the type is not particularly limited. For example, a phenol type hardening | curing agent, an acid anhydride type hardening | curing agent, an amine type hardening | curing agent, and also a benzoxazine compound are mentioned. These curing agents may be used alone or in combination of two or more. As a compounding ratio of the epoxy resin and the curing agent, a ratio in which the active group capable of reacting with the epoxy group of the curing agent is 1.0 equivalent, and the epoxy group in the epoxy resin is preferably 0.5 to 2.0 equivalent. More preferably, it is 0.6-1.8, More preferably, it is 0.8-1.5. If it is this ratio, it will be excellent in characteristics, such as glass transition temperature after hardening, and will be a highly reliable substrate and film.

  Furthermore, in order to enhance the reactivity of the epoxy resin and the curing agent, a curing accelerator may be added. The curing accelerator is not particularly limited. For example, nitrogen-based curing accelerators such as amines and imidazoles, phosphorus-based curing accelerators such as quaternary phosphonium salts, organometallic salts and derivatives thereof. Is mentioned.

((B-4) cyanate resin)
The cyanate resin is not particularly limited as long as it has two or more cyanate groups in one molecule. For example, a method of reacting a halogenated cyanide compound with phenols or naphthols and heating as necessary Can be obtained by prepolymerization.

  Examples of the cyanate resin include novolac type cyanate resin, bisphenol type cyanate resin, naphthol aralkyl type cyanate resin, dicyclopentadiene type cyanate resin, biphenyl alkyl type cyanate resin and the like. Among these, those having a small cyanate group equivalent have small curing shrinkage, and a cured product having a low thermal expansion coefficient and a high glass transition temperature can be obtained. One of these may be used alone, or two or more may be used in combination.

  Further, a curing agent or a curing catalyst may be included. There are no particular limitations on the type of curing agent or curing catalyst, examples of the curing agent include phenolic curing agents and dihydroxynaphthalene compounds, and examples of the curing accelerator include primary amines and metal complexes.

((B-5) (meth) acrylic resin)
Examples of the (meth) acrylic resin include polymers and copolymers such as (meth) acrylic acid, (meth) acrylonitrile, (meth) acrylic acid ester and (meth) acrylamide, and a (meth) acrylic skeleton. The resin which has is shown. The resin is not limited to a resin that cures with a reactive group such as an acryloyl group or a methacryloyl group.

  In order to adjust the curability, a radical polymerization initiator such as peroxide, a photopolymerization initiator, or a curing accelerator that accelerates the reaction of the reactive group of the (meth) acrylic resin may be added. .

  One of these resins may be used alone, or two or more of these resins may be used in combination. Furthermore, two or more types of resins selected from each resin group may be used in combination. In particular, a mixed composition of a maleimide resin (compound) of (B-2) and a cyanate resin (compound) of (B-4) is known as a BT resin, and is excellent in processability, heat resistance, electrical properties and the like.

(Inorganic filler)
It is preferable that the resin composition of the component (B) further contains an inorganic filler. By arbitrarily containing an appropriate inorganic filler, the low thermal expansion property, high elastic modulus, heat resistance, flame retardancy, and the like of the resin composition can be improved. As the inorganic filler, those usually blended in a thermosetting resin composition such as an epoxy resin composition can be used, and are not particularly limited. For example, silica, cristobalite silica, alumina, titanium oxide, mica , Beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride , Fired clay, talc, aluminum borate, silicon carbide and the like. Above all, it is preferable to blend silica in order to obtain a low thermal expansion coefficient, and in particular, it is more preferred to blend spherical silica in order to achieve high loading.

These may be used alone or in combination of two or more. There is no restriction | limiting in particular also about the shape and particle size of an inorganic filler. The shape of the inorganic filler may be, for example, spherical or crushed, but as described above, it is preferably spherical for high filling. The particle size of the inorganic filler may be, for example, 0.01 to 50 μm, 0.01 to 20 μm, 0.1 to 15 μm, or 0.1 to 10 μm. Here, the particle diameter refers to an average particle diameter, and is a value obtained as a mass average value D ₅₀ (or median diameter) in particle size distribution measurement by a laser light diffraction method.

  The blending ratio of the inorganic filler to the curable resin composition is not particularly limited, but from the viewpoint of the adhesiveness, toughness, heat resistance, chemical resistance, etc. of the curable resin composition, the total amount of the resin composition component is 100 mass The amount is preferably in the range of 1 to 1,000 parts by mass with respect to part, and from the viewpoint of maintaining the toughness after curing while suppressing the thermal expansion of the curable resin composition, 100 to 800 parts by mass is more preferable.

[Other additives]
If necessary, in addition to the above-mentioned curing agent and curing accelerator, various additives such as adhesion assistant, silane coupling agent, titanate coupling agent, thermoplastic resin, pigment, resin particles, etc., containing quartz glass fiber It can mix | blend with any one or both of a prepreg and (B) component. In addition, as an additive, a well-known thing can be used.

(Adhesion aid)
An adhesion assistant (adhesion imparting agent) can be added to impart adhesiveness to the curable resin composition. Examples of the adhesion assistant include a hydrogen atom (Si—H group) bonded to a silicon atom in one molecule, an alkenyl group (for example, Si—CH═CH ₂ group) bonded to a silicon atom, and an alkoxysilyl group (for example, a trimethyl group). Silanes containing, as functional groups, methoxysilyl groups), epoxy groups (eg glycidoxypropyl groups, 3,4-epoxycyclohexylethyl groups), isocyanate groups (eg organooxysilyl-modified isocyanurate compounds and hydrolysis condensates thereof), etc. And siloxane. The adhesion assistant can be used singly or in combination of two or more.

(Coupling agent)
Silane to increase the bond strength between the component (A) quartz glass fiber and the component (B) curable resin composition, or to improve the wettability of the curable resin composition to quartz glass fiber. Coupling agents such as coupling agents and titanate coupling agents can be added. In addition, the surface of the quartz glass fiber may be treated with a coupling agent in advance.

  Examples of coupling agents include epoxy functional alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. Amino-functional alkoxysilanes such as N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; γ-mercaptopropyltri Silane coupling agents such as mercapto functional alkoxysilanes such as methoxysilane, isopropyl triisostearoyl titanate, tetraoctyl bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titaniume A titanate coupling agent such as a salt is used. The amount of coupling agent used for the surface treatment and the surface treatment method are not particularly limited.

(Thermoplastic resin)
Furthermore, a thermoplastic resin may be added as a dielectric property improvement / stress relaxation material to improve the properties. Examples of the thermoplastic resin include a fluororesin, a polyphenylene ether resin, a styrene-ethylene-butylene copolymer, a cycloolefin polymer, and an acrylic block copolymer.

(Pigment, dye)
Pigments and dyes may be added for the purpose of coloring. Examples of the pigment include carbon black, titanium black, kaolin, synthetic iron oxide red, nickel titanium yellow, hydrous chromium oxide, chromium oxide, cobalt aluminate, and inorganic pigments such as synthetic ultramarine blue. Examples of the dye include isoindolinone, isoindoline, quinophthalene, xanthene, diketopyrrolopyrrole, perylene, perinone, anthraquinone, indigoid, oxazine, quinacridone, benzimidazolone, violanthrone, phthalocyanine, and azomethine.

<Quartz glass fiber-containing film and quartz glass fiber-containing substrate>
Further, the present invention is a quartz glass fiber-containing film which is a cured product of a quartz glass fiber-containing prepreg comprising (A) quartz glass fiber and (B) a curable resin composition of the present invention, and quartz glass fiber containing the present invention Provided is a quartz glass fiber-containing substrate comprising a laminated cured product of two or more prepregs. It is preferable that the quartz glass fiber-containing film and the quartz glass fiber-containing substrate of the present invention have excellent dielectric properties, and the difference between the dielectric loss tangent at 1.0 GHz and the dielectric loss tangent at 10 GHz is 0 to 0.01.

<Method for producing quartz glass fiber-containing prepreg, film and substrate>
It does not specifically limit as a manufacturing method of the quartz glass fiber containing prepreg of this invention. A production method such as a general glass fiber-containing prepreg can be applied. For example, it manufactures according to the coating method (coating system) of the cured resin composition to a general glass fiber.

  Typical coating methods include direct gravure coater, chamber doctor coater, offset gravure coater, single roll kiss coater, reverse kiss coater, bar coater, reverse roll coater, slotter die, air doctor coater, positive rotation roll coater, blade coater There are methods using a coating apparatus such as a knife coater, an impregnation coater, an MB coater, and an MB reverse coater.

  In order to improve and secure the coatability, the curable resin composition may be diluted with a solvent. An organic solvent can be used singly or in combination of two or more in view of the dissolution characteristics of the curable resin composition. Examples of organic solvents include alcohols such as methanol, ethanol, isopropanol and n-butanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, glycol ethers such as ethylene glycol and propylene glycol, and fats such as hexane and heptane. And aromatic hydrocarbons such as toluene and xylene, ethers such as diethyl ether, diisopropyl ether and di n-butyl ether.

  Although the conditions differ depending on the curable resin composition to be used, for example, after being applied to quartz glass fiber by the above method, it is dried at 25 to 150 ° C., preferably 50 to 120 ° C., and B-staged. The quartz glass fiber-containing prepreg of the invention can be obtained. By heating and curing the obtained prepreg at 25 to 300 ° C. for 1 minute to 24 hours, a quartz glass fiber-containing film or a quartz glass fiber-containing substrate can be obtained. In the present invention, what is obtained by heat-curing one prepreg is referred to as a film, and what is obtained by laminating two or more prepregs and heat-cured is referred to as a substrate.

  In addition, when producing the said board | substrate, you may pressure-mold simultaneously with heating. It is preferable to form by applying a pressure of 5 to 50 MPa using a hydraulic press, a vacuum press or the like.

  It is preferable that the quartz glass fiber containing film and board | substrate of this invention are excellent in a dielectric characteristic. Specifically, the absolute value of the difference between the dielectric loss tangent at 1.0 GHz and the dielectric loss tangent at 10 GHz is preferably 0 or more and 0.01 or less. If it is in this range, it will become a material suitable for application to various electronic parts utilizing its low dielectric property.

  Since the quartz glass fiber-containing film and substrate produced in this way have a very low bubble content in the quartz glass fiber used, the plating solution, cleaning solution, etching solution, etc. used in the substrate molding process constitute the film or substrate. There is no risk that the plated layer will be lost due to intrusion of bubbles present in the quartz glass cloth. Therefore, it becomes a quartz glass fiber containing film and a substrate without defects such as occurrence of conduction failure and deterioration of dielectric characteristics. In addition, it is high in strength and high in tensile rigidity, excellent in surface uniformity and thin film formability.

  Films and substrates mainly made of quartz glass fiber have very few impurity elements, so they are required for printed wiring boards etc. along with semiconductor applications, especially high speed and high frequency such as computer, mobile and communication infrastructure etc. Excellent in quartz glass fiber-containing film and substrate.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

Glass Cloth A glass cloth having a thickness of 0.1 mm was prepared using the glass shown in Table 1 below. Describe the type and number of bubbles at the same time. In addition, the number of bubbles of the glass of Comparative Examples 1 to 6 was too large and could only be measured up to 200.

Preparation of film Cresol novolac type epoxy resin (trade name: EPICLON N-695, manufactured by DIC Corporation), 10 parts by mass, phenol novolac resin (trade name PEHNOLITE TD-2090, manufactured by DIC Corporation) 5 parts by mass, imidazole 0.1 part by mass of a curing accelerator (trade name: 2E4MZ, manufactured by Shikoku Kasei Co., Ltd.), 85 parts by mass of spherical silica (trade name: SC-2050-SE, manufactured by Admatex Co., Ltd.) and 50 parts of MEK solvent A slurry of a filler-containing epoxy resin composition consisting of parts was prepared.

  After impregnating each glass cloth shown in Table 1 with the above-mentioned filler-containing epoxy resin composition slurry, drying it at 100 ° C. for 10 minutes to prepare a prepreg, and further curing the prepreg at 180 ° C. for 4 hours. A glass cloth-containing film was prepared. In addition, all the adhesion amounts of resin were 55 mass%.

Measure a dielectric loss tangent measurement network analyzer (manufactured by Keysight E5063-2D5) and a stripline (manufactured by Keycom Co., Ltd.) and measure the dielectric loss tangent tan δ1 of the film at a frequency of 1.0 GHz and the dielectric loss tangent tan δ2 at 10 GHz. The value of the formula | tan δ1−tan δ2 | was calculated. The results are shown in Table 2.

Measurement of Permittivity A network analyzer (manufactured by Keysight Co., Ltd. E5063-2D5) and a strip line (manufactured by Keycom Co., Ltd.) were connected, and the dielectric constant of the film at a frequency of 1.0 GHz was measured. The results are shown in Table 2.

Preparation of substrate : Cresol novolac type epoxy resin (trade name: EPICLON N-695, manufactured by DIC Corporation), 10 parts by mass, Phenolic novolac resin (trade name: PEHNOLITE TD-2090, manufactured by DIC Corporation) 5 parts by mass, imidazole 0.1 part by mass of a curing accelerator (trade name: 2E4MZ, manufactured by Shikoku Kasei Co., Ltd.), 85 parts by mass of spherical silica (trade name: SC-2050-SE, manufactured by Admatex Co., Ltd.) and 50 parts of MEK solvent A slurry of a filler-containing epoxy resin composition consisting of parts was prepared.

  Each glass cloth shown in Table 1 was impregnated with the filler-containing epoxy resin composition slurry, and then dried at 100 ° C. for 10 minutes to prepare a prepreg. Five of these prepregs were stacked, and a laminated substrate was prepared under conditions of 180 ° C., 4 hours, and 4.0 MPa.

The laminated substrate prepared just before the heat resistance test was cut into a size of 100 mm × 100 mm. Subsequently, 10 holes were created using a drill with a drill diameter of 5 mm. Thereafter, electroless copper plating was performed, and a reflow process at 260 ° C. was performed five times, after which peeling and swelling of the plating in the holes were confirmed. The case where no blistering or peeling occurred was marked with ○, and the case where even one occurred was marked with ×. The results are shown in Table 2.

  As shown in Table 2, it was found that by using a quartz glass cloth having a small number of bubbles, the dielectric characteristics were good and the plating was not swollen or peeled off. Thus, the present invention has been shown to be useful.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has the substantially same constitution as the technical idea described in the claims of the present invention, and the same effects can be exhibited by any invention. It is included in the technical scope of

Claims (8)

A quartz glass fiber-containing prepreg,
(A) A quartz glass fiber (B) comprising a curable resin composition, wherein the number of bubbles contained in the (A) quartz glass fiber is 10 / m ² or less per unit area. Quartz glass fiber containing prepreg.   The silica glass fiber-containing prepreg according to claim 1, wherein the fiber diameter of the (A) quartz glass fiber is 3 μm to 9 μm, and the fictive temperature is 1,300 ° C. to 1,500 ° C. .   The (B) curable resin composition includes at least one of a curable resin selected from a silicone resin, a curable polyimide resin, a maleimide resin, an epoxy resin, a cyanate resin, and a (meth) acrylic resin. The quartz glass fiber-containing prepreg according to claim 1 or 2, wherein the prepreg is a composition and / or a photocurable resin composition.   The quartz glass fiber-containing prepreg according to any one of claims 1 to 3, wherein the (B) curable resin composition further contains an inorganic filler.   5. A quartz glass fiber-containing film comprising a cured product of one quartz glass fiber-containing prepreg according to claim 1.   The quartz glass fiber-containing film according to claim 5, wherein the absolute value of the difference between the dielectric loss tangent at 1.0 GHz and the dielectric loss tangent at 10 GHz is 0 or more and 0.01 or less. .   A quartz glass fiber-containing substrate comprising a laminated cured product of two or more quartz glass fiber-containing prepregs according to any one of claims 1 to 4.   The quartz glass fiber-containing substrate according to claim 7, wherein the quartz glass fiber-containing substrate has an absolute value of a difference between a dielectric loss tangent at 1.0 GHz and a dielectric loss tangent at 10 GHz of not less than 0 and not more than 0.01. .