Organosilicon compound, article including substrate surface-treated with organosilicon compound, prepreg, printed wiring board, and glass cloth treatment liquid

Abstract

Provided is an organosilicon compound represented by formula (1) and an article including a substrate surface-treated with the organosilicon compound. (In the formula, Me represents a methyl group; each R1 independently represents a hydrogen atom or an alkyl group having 1-10 carbon atoms; R2 represents a hydrogen atom, an alkyl group having 1-10 carbon atoms, or an aryl group having 6-20 carbon atoms; R3 represents a hydrogen atom or a methyl group; X represents a p+q+1-valent hydrocarbon group having 3-20 carbon atoms and containing a branched structure or a ring structure; m represents an integer of 1-3; n represents an integer of 1-12; p represents 0 or 1; q represents an integer of 1-3; and p+q represents an integer of 1-4.)

Description

Organosilicon compounds, articles containing substrates surface-treated with organosilicon compounds, prepregs, printed wiring boards, and glass cloth treatment liquids

[0001] The present invention relates to an organosilicon compound, an article including a substrate surface-treated with an organosilicon compound, a prepreg, a printed wiring board, and a glass cloth treatment liquid containing an organosilicon compound.

[0002] As electronic devices, such as tablets and smartphones, become more powerful and offer faster communication speeds, the printed wiring boards used in these devices are becoming increasingly denser and thinner, while also exhibiting lower dielectric constants and lower dielectric loss tangents. A widely used insulating material for these printed wiring boards is a laminated board made by laminating prepregs containing inorganic fillers and glass cloth as reinforcing materials for thermosetting resins (hereinafter referred to as "matrix resins"), such as epoxy resins and thermosetting polyphenylene ether resins, followed by heat and pressure curing. The reinforcing materials used in these applications are surface-treated with a silane coupling agent, which reacts with the organic functional groups of the matrix resin to improve adhesion between the reinforcing material, such as glass cloth, and the matrix resin.

[0003] Typical silane coupling agents used in the surface treatment of glass cloth include those having an unsaturated double bond, such as 3-methacryloxypropyltrimethoxysilane or N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride (Patent Documents 1 and 2). Inorganic fillers surface-treated with silane coupling agents having a vinyl group have also been proposed, and it has been reported that resins containing such inorganic fillers have improved dielectric properties, heat resistance, and moist heat resistance (Patent Document 3). However, there is still room for improvement in the dielectric properties of materials used in printed wiring boards, and further performance improvements are desired.

[0004] International Publication No. 2020 / 194772 Japanese Patent Application Laid-Open No. 2018-127747 Japanese Patent No. 6684822

[0005] The present invention has been made in view of the above circumstances, and aims to provide an organosilicon compound that can provide an article with excellent mechanical and dielectric properties by surface treating the substrate of the article, and an article, prepreg, or printed wiring board that includes a substrate that has been surface treated with this organosilicon compound.

[0006] The present inventors have conducted extensive research to solve the above problems and have found that when an organosilicon compound having a specific structure is used to treat the surface of a substrate of an article, it provides an article that has excellent adhesion to the matrix resin used in prepregs and printed wiring boards, in particular, and therefore can improve the mechanical and dielectric properties of the prepregs and printed wiring boards, thereby completing the present invention.

[0007] That is, the present invention provides: 1. an organosilicon compound represented by the following formula (1): (wherein Me represents a methyl group, R 1 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R 2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R 3 represents a hydrogen atom or a methyl group, X represents a hydrocarbon group having 3 to 20 carbon atoms and a valence of (p+q+1), which has a branched structure or a ring structure, m represents an integer of 1 to 3, n represents an integer of 1 to 12, p is 0 or 1, q represents an integer of 1 to 3, and p+q represents an integer of 1 to 4. 2. An organosilicon compound according to 1, which is represented by the following formula (2) or (3): (In the formula, Me, R 1 , R 2 , m and n are the same as above, and R 4 represents a hydrogen atom, a methyl group, or an allyloxy group. 1 is a hydrogen atom, a methyl group, or an ethyl group, and R 2is a hydrogen atom and n is 3; 4. An article comprising a substrate surface-treated with the organosilicon compound according to any one of 1 to 3; 5. The article according to 4, wherein the substrate is an inorganic material; 6. The article according to 5, wherein the inorganic material is silica particles or glass fibers; 7. A prepreg comprising the article according to any one of 4 to 6 and a matrix resin; 8. A printed wiring board comprising the prepreg according to 7; and 9. A glass cloth treatment liquid in which the organosilicon compound according to any one of 1 to 3 is dissolved in a solvent containing water.

[0008] The organosilicon compounds of the present invention can be used to surface treat the substrate of an article, thereby providing the article with excellent adhesion to resins and dielectric properties. Therefore, the compounds can be suitably used as a treating agent for inorganic fillers, glass cloth, etc., and the use of these articles makes it possible to obtain prepregs, printed wiring boards, etc. that have excellent mechanical properties and dielectric properties.

[0009] The present invention will be described in detail below. [Organosilicon Compound] The organosilicon compound of the present invention is an organosilicon compound represented by the following formula (1) (hereinafter, sometimes referred to as compound (1)).

[0010]

[0011] In the formula, Me represents a methyl group, and R 1 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R 2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R 3 represents a hydrogen atom or a methyl group; X represents a (p+q+1)-valent hydrocarbon group having 3 to 20 carbon atoms, which has a branched structure or a ring structure; m represents an integer of 1 to 3; n represents an integer of 1 to 12; p is 0 or 1; q represents an integer of 1 to 3; and p+q represents an integer of 1 to 4.

[0012] R 1The alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. 1 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, with a methyl group and an ethyl group being even more preferred, and a methyl group being even more preferred.

[0013] R 2 Examples of the alkyl group having 1 to 10 carbon atoms include R 1 Examples of the aryl group having 6 to 20 carbon atoms include the same groups as those exemplified in R, and are preferably alkyl groups having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl, α-naphthyl, and β-naphthyl groups, and are preferably aryl groups having 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms. 2 R is preferably a hydrogen atom, a methyl group, or a phenyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom. 3 represents a hydrogen atom or a methyl group, with a methyl group being preferred.

[0014] X represents a p+q+1 valent hydrocarbon group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, containing a branched or cyclic structure, and more preferably a p+q+1 valent saturated hydrocarbon group having 3 to 6 carbon atoms and containing a branched structure. Specific examples of X include, but are not limited to, groups represented by the following formulas: In the following formulas, the wavy line represents -NR 2 It represents the bonding site to the oxygen atom of (C═O)O—, and the asterisk represents the bonding site to the allyloxy group, methyl group, or ethyl group.

[0015]

[0016] m represents an integer of 1 to 3, preferably 2 or 3, and more preferably 3. n represents an integer of 1 to 12, but from the viewpoint of raw material procurement, an integer of 1 to 8 is preferred, an integer of 1 to 4 is more preferred, and 3 is even more preferred. p is 0 or 1. q represents an integer of 1 to 3, but from the viewpoint of adhesion to resin, 2 or 3 is preferred. p+q represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2 or 3.

[0017] The organosilicon compound of the present invention is preferably one represented by the following formula (2) or (3).

[0018]

[0019] In the above formula, Me, R 1 , R 2 , m and n are the same as above, and R 4 represents a hydrogen atom, a methyl group, or an allyloxy group.

[0020] Specific examples of the compound represented by formula (2) include, but are not limited to, those represented by the following formulas:

[0021] (In the formula, Me represents a methyl group, and Et represents an ethyl group.)

[0022] (In the formula, Me represents a methyl group, and Et represents an ethyl group.)

[0023] Specific examples of the compound represented by formula (3) include, but are not limited to, those represented by the following formulas:

[0024] (In the formula, Me represents a methyl group, and Et represents an ethyl group.)

[0025] The organosilicon compound of the present invention can be produced, for example, by reacting an alkoxysilane having an isocyanato group (hereinafter sometimes referred to as "isocyanate silane") with an alcohol having an allyl group in the presence of a catalyst, but the production method is not limited to this.

[0026] Specific examples of isocyanate silanes include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropylethyldimethoxysilane, 3-isocyanatopropylethyldiethoxysilane, etc. Specific examples of alcohols having an allyl group include trimethylolpropane diallyl ether, pentaerythritol triallyl ether, glycerin diallyl ether, etc.

[0027] The reaction ratio of the isocyanate silane and the alcohol having an allyl group is preferably 0.90 moles or more but less than 1.2 moles, more preferably 0.95 moles or more but less than 1.05 moles, of the alcohol having an allyl group per mole of the isocyanate silane.

[0028] The catalyst used in the above reaction is not particularly limited, and may be a commonly used isocyanate reaction catalyst, such as a tertiary amine compound, an organotin compound, an aluminum complex, or a zirconium complex, with organotin compounds being preferred. Among these, tin(II) carboxylate compounds are more preferred in terms of catalytic activity. The amount of catalyst used is preferably 0.00001 to 1 mol, more preferably 0.0001 to 0.01 mol, per mol of isocyanate silane. If more than 1 mol is used, the effect may saturate, making the process uneconomical. If the amount is less than 0.00001 mol, the catalytic effect may be insufficient, the reaction rate may be slow, and productivity may decrease.

[0029] When a catalyst is used in the above reaction, a step of removing or reducing the catalyst may be carried out. The removal method is not particularly limited, but examples thereof include a method of distillation under reduced pressure in the case of a low-boiling tertiary amine compound, and a method of adsorption and removal using an inorganic oxide such as silicon oxide, magnesium oxide, or aluminum oxide in the case of an organotin compound. When the adsorption and removal step using an inorganic oxide is carried out, the inorganic oxide can be removed by filtration in a subsequent step.

[0030] In the production of the organosilicon compound of the present invention, a solvent may be used if necessary. There are no particular limitations on the solvent as long as it is non-reactive with the starting isocyanate silane and allyl group-containing alcohol, but specific examples include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and decane; ether solvents such as diethyl ether, tetrahydrofuran, and 1,4-dioxane; amide solvents such as formamide, dimethylformamide, and N-methylpyrrolidone; and aromatic hydrocarbon solvents such as benzene, toluene, and xylene.

[0031] In the production of the organosilicon compound of the present invention, the reaction is an exothermic reaction, and from the viewpoints of productivity and suppression of side reactions, the reaction temperature is preferably 20 to 150° C., more preferably 30 to 130° C., and even more preferably 40 to 110° C. The reaction time is not particularly limited, but is preferably 10 minutes to 24 hours, and more preferably about 1 hour to 10 hours.

[0032] [Article] The article of the present invention comprises a substrate surface-treated with the above-described organosilicon compound. (1) Organosilicon Compound The organosilicon compound used in the article of the present invention is represented by the above formula (1). Specific examples and preferred examples of the organosilicon compound are as described above. By applying the organosilicon compound of the present invention to the surface of a substrate and drying it by heating, a substrate surface-treated with the organosilicon compound of the present invention can be obtained.

[0033] (2) Substrate The substrate is not particularly limited, but inorganic materials are preferred, and specific examples thereof include inorganic particles (inorganic fillers) such as silica, titania, zirconia, calcium carbonate, magnesium carbonate, alumina, magnesium oxide, aluminum hydroxide, magnesium hydroxide, talc, clay, and mica; glass fibers such as monofilaments, glass strands, glass yarns, glass rovings, twisted and twisted yarns, bulky processed yarns, chopped strands, milled fibers, staple fibers, glass cloths, nonwoven fabrics, tapes, and nets; ceramics such as porcelain, cement, enamel, and fine ceramics; and metals such as iron, aluminum, copper, silver, gold, and magnesium. Among these, silica particles or glass fibers are particularly preferred from the viewpoint of the reactivity of the alkoxysilyl group.

[0034] (2-1) Silica Particles The silica particles are not particularly limited, and examples thereof include colloidal silica, fumed silica, crystalline silica, and fused silica. In the case of colloidal silica, the silica particles are preferably colloidally dispersed in a medium such as water or an organic solvent, and commercially available water-dispersed or organic-dispersed types can be used. The shape of the silica particles is not particularly limited, and examples include spherical and irregular shapes, with spherical shapes being preferred. The average particle size is also not particularly limited, but a median diameter of 1 to 100 nm measured by dynamic light scattering is preferred. Commercially available silica particles can be used, and examples of such silica particles include Snowtex O, OS, O40, OL, methanol silica sol, IPA-ST, IBA-ST, PMA-ST, and MEK-ST, all manufactured by Nissan Chemical Industries, Ltd. Of these, Snowtex O is preferred.

[0035] (2-2) Glass Fibers Glass cloth is preferred as the glass fiber. The glass yarns constituting the glass cloth that serves as the substrate before surface treatment are not particularly limited, and glass fibers of conventionally known glass compositions can be used. Specific examples include E glass, L glass, L2 glass, NE glass, NE2 glass, S glass, T glass, UT glass, LU glass, D glass, and silica glass. Depending on the intended use, one or more glass cloths selected from the group consisting of these glasses are used. Among these, glass cloths selected from L glass, L2 glass, NE glass, NE2 glass, LU glass, and silica glass are preferred in terms of dielectric properties. In the present invention, the dielectric loss tangent at 10 GHz refers to a value measured using the method described in JIS R 1641:2007 (Method for measuring microwave dielectric properties of fine ceramic substrates).

[0036] It is preferable to remove organic substances such as sizing agents adhering to the surface of the glass cloth before surface treatment with the organosilicon compound, since this allows the surface of the glass cloth to be treated evenly with the organosilicon compound. Methods for removing the organic substances include heat cleaning, corona treatment, and hot water washing.

[0037] The thickness of the glass cloth is preferably 6 to 200 μm, more preferably 10 to 100 μm, and the mass per unit area is preferably 5 to 200 g / m ２ and 10 to 100 g / m ２ The glass cloth is more preferable.

[0038] (3) Method for Manufacturing an Article The article of the present invention includes a surface-treated substrate as described above. However, it is preferable that the surface-treated substrate itself is used as the article. In this case, the method for manufacturing the article of the present invention is not particularly limited, and the article of the present invention can be manufactured by appropriately selecting a surface treatment method for the substrate depending on the type, shape, etc. of the substrate.

[0039] (3-1) Method for Producing Surface-Treated Silica Particles When silica particles are used as the substrate, for example, a method of surface-treating in a solvent is applicable. When a resin is used in a subsequent process, a kneading treatment in which compound (1) is added to and mixed with a compound consisting of untreated silica particles and a resin dispersion medium is also applicable, but a method of surface-treating in a solvent is preferred. The solvent may be one that is generally easily available, such as water; alcohol-based solvents such as methanol, ethanol, and isopropyl alcohol; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; hydrocarbon-based solvents such as hexane, toluene, and xylene; ether-based solvents such as diethyl ether, tetrahydrofuran, and dioxane; and ester-based solvents such as ethyl acetate and butyl acetate. One type may be used alone, or two or more types may be mixed and used.

[0040] In the present invention, it is preferable to use a colloidal silica dispersion in which silica particles are dispersed in the above-mentioned solvent, and the surface treatment can be carried out by adding compound (1) to this dispersion and mixing and stirring. The treatment conditions are not particularly limited, but can be, for example, preferably 20 to 150°C, more preferably 25 to 120°C, and preferably 1 to 10 hours, more preferably 1 to 6 hours.

[0041] The amount of compound (1) added is preferably 1 to 50 parts by mass, more preferably 5 to 20 parts by mass, relative to 100 parts by mass of silica particles. Compound (1) can be used alone or in combination of two or more.

[0042] In the surface treatment of silica particles, organosilicon compounds other than compound (1), such as alkoxy group-containing organosilicon compounds and silazane structure-containing compounds, may be used in combination. Specific examples of the alkoxy group-containing organosilicon compounds include 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, and 8-methacryloxyoctyltrimethoxysilane. Specific examples of the silazane structure-containing compounds include low-molecular-weight silazane compounds such as 1,1,3,3-tetramethyldisilazane, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, octamethyltrisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, and 1,1,3,3,5,5-trimethyltrivinylcyclotrisilazane. These compounds may be used alone or in combination of two or more.

[0043] When an organosilicon compound other than compound (1) is used, it may be added simultaneously with compound (1), or it may be added before or after the surface treatment with compound (1), but it is preferable to add it after the surface treatment with compound (1). Furthermore, when an organosilicon compound other than compound (1) is used, the amount added is preferably 1 to 50 parts by mass, more preferably 5 to 20 parts by mass, in total, per 100 parts by mass of silica particles.

[0044] After the surface treatment, the solvent is removed by separation means such as filtration or liquid separation, followed by washing and drying to obtain surface-treated silica particles. The drying conditions are not particularly limited, but are, for example, preferably 60 to 180°C, more preferably 80 to 150°C, and preferably 5 minutes to 2 hours, more preferably 10 minutes to 1 hour. The above production method can also be applied to inorganic particles and inorganic fillers other than silica particles.

[0045] (3-2) Method for Producing Surface-Treated Glass Fibers When glass fiber is used as the substrate, glass cloth is particularly preferred. When surface-treating glass cloth, it can be treated using a glass cloth treatment solution in which the organosilicon compound of the present invention is dissolved in a solvent containing water. The surface treatment method for glass cloth is not particularly limited, but specific examples include flow coating (immersion method) and spin coating, which are methods for directly treating the substrate. Other known methods, such as spray coating, dip coating, roller coating, brush coating, and bar coating, can also be appropriately selected and used. A heating and drying treatment is then preferably performed. Typical treatment conditions include, for example, heating and drying at 60 to 180°C, preferably 80 to 150°C, for 5 minutes to 2 hours, to remove the solvent and simultaneously chemically react the organosilicon compound in the solution with the substrate surface. The above-described production method can also be applied to substrates other than glass cloth.

[0046] [Glass Cloth Treatment Liquid] The glass cloth treatment liquid of the present invention (hereinafter sometimes referred to as "treatment liquid") contains the organosilicon compound of the present invention and water, and the organosilicon compound of the present invention is dissolved in a solvent containing water. From the viewpoint of storage stability and productivity of the treatment liquid, the content of the organosilicon compound is preferably 0.001 to 10.0 mass %, more preferably 0.05 to 5.0 mass %, and still more preferably 0.05 to 2.0 mass %, in terms of solids content, based on the total treatment liquid.

[0047] The method for producing the glass cloth treatment liquid of the present invention is not particularly limited, and the glass cloth treatment liquid can be produced by adding and dissolving the organosilicon compound of the present invention in a solvent containing water. The temperature when adding the organosilicon compound to the solvent is preferably 10 to 50°C, more preferably 15 to 40°C.

[0048] In addition to the organosilicon compound and water of the present invention, the glass cloth treatment solution of the present invention may contain an organic solvent to the extent that the effects of the present invention are not impaired. The organic solvent is not particularly limited, but organic solvents with excellent compatibility with water are preferred. Examples include alcohols such as methanol, ethanol, and isopropanol; ethers such as diethyl ether, tetrahydrofuran, and 1,4-dioxane; esters such as ethyl acetate; and ketones such as acetone and methyl ethyl ketone. These organic solvents may be used alone or in combination of two or more. When an organic solvent is used, its amount is not particularly limited, but is preferably 10 to 70% by mass, and more preferably 20 to 60% by mass, of the total treatment solution.

[0049] From the viewpoint of storage stability, the water contained in the glass cloth treatment liquid of the present invention is preferably water adjusted to be acidic. Examples of acids used to adjust the acidity include organic acids such as formic acid, acetic acid, and citric acid, and inorganic acids such as hydrochloric acid. When an acid is used, the amount added is preferably 0.001 to 0.5 mass %, more preferably 0.01 to 0.1 mass %, of the total treatment liquid. When an acid is used, water adjusted to be acidic by mixing the acid and water in advance may be used, or the acid may be added to a glass cloth treatment liquid containing compound (1) to adjust the acidity.

[0050] To the glass cloth treatment solution of the present invention, if necessary, an alkoxy group-containing organosilicon compound, a silazane compound, or the like other than the organosilicon compound of the present invention can be added to improve adhesion and bonding to the glass cloth, as long as the effects of the present invention are not impaired. Specific examples of alkoxy group-containing organosilicon compounds and silazane compounds include those exemplified in the method for producing surface-treated silica particles. Furthermore, to the glass cloth treatment solution of the present invention, if necessary, other additives can be added, as long as the effects of the present invention are not impaired. Specific examples of other additives include water-soluble resins, curing catalysts, physical property adjusters for adjusting the tensile properties of the resulting cured coating, storage stability improvers, surfactants, metal deactivators, antiozonants, lubricants, pigments, etc.

[0051] [Prepreg] The prepreg of the present invention comprises the above-described article and a matrix resin. An article comprising a substrate surface-treated with the organosilicon compound of the present invention can be made into a prepreg by mixing it with a matrix resin. In particular, when the substrate (article) is surface-treated silica particles or surface-treated glass cloth, the resulting prepreg has excellent strength and can be suitably used, for example, for printed wiring boards.

[0052] (1) Articles The articles contained in the prepreg are not particularly limited as long as they contain a substrate that has been surface-treated with the organosilicon compound of the present invention. However, it is preferable that the surface-treated substrate itself, such as surface-treated silica particles or surface-treated glass cloth, is used as the article.

[0053] (2) Matrix Resin The matrix resin used in the prepreg of the present invention is not particularly limited and can be appropriately selected from conventionally known resins. Examples include thermosetting silicone resins, polyimide resins, maleimide resins, epoxy resins, cyanate resins, (meth)acrylic resins, polyphenylene ether resins, and polytetrafluoroethylene resins. Of these, polyphenylene ether resins are preferred.

[0054] Other components can be added to the matrix resin in the present invention in order to accelerate curing of the resin, increase its strength, etc. Specific examples of other components include inorganic fillers, flame retardants, additives, reaction initiators, crosslinking agents, curing agents, and organic resins other than the matrix resin. When other components are blended, the amount added is preferably 1 to 900 parts by mass, more preferably 10 to 500 parts by mass, and even more preferably 10 to 100 parts by mass, per 100 parts by mass of the matrix resin.

[0055] (3) Method for Producing Prepreg There are no particular limitations on the method for producing the prepreg of the present invention, and general methods for producing glass cloth-containing substrates, films, prepregs, etc. can be applied. For example, a method in which a molten matrix resin or a solution containing a matrix resin is mixed with a surface-treated inorganic filler, and the obtained resin is applied to a glass cloth to impregnate it, or a method in which a matrix resin is applied to a surface-treated glass cloth to impregnate it, can be used.

[0056] (3-1) Method for producing prepreg containing surface-treated silica particles When surface-treated silica particles are used as the article, a matrix resin, surface-treated silica particles, and other components as necessary are mixed, and the resulting resin or solution is applied to and impregnated into glass cloth, thereby obtaining a prepreg containing surface-treated silica particles.

[0057] The matrix resin may be diluted with a solvent to improve or ensure coatability. Depending on the solubility characteristics of the matrix resin, one organic solvent may be used alone or two or more organic solvents may be used in combination. 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; aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; and alkyl ethers such as diethyl ether, diisopropyl ether, and dibutyl ether.

[0058] The method for mixing the matrix resin and the surface-treated silica particles is not particularly limited, and examples thereof include a method in which the matrix resin or a solution containing the matrix resin, the surface-treated silica particles, and, if necessary, other components are mixed by a conventionally known method, and the mixture is stirred for about 10 minutes to 1 hour.

[0059] The amount of the surface-treated silica particles added is preferably 10 to 300 parts by mass, more preferably 50 to 200 parts by mass, and even more preferably 60 to 150 parts by mass, per 100 parts by mass of the matrix resin (the amount of the matrix resin contained in the case of a solution). The glass cloth may be surface-untreated or surface-treated, and one type may be used alone or two or more types may be used in combination.

[0060] Next, the matrix resin containing the surface-treated silica particles is applied to the glass cloth to allow it to be impregnated. The prepreg of the present invention can be produced, for example, according to a general method for applying a curable resin composition to glass cloth fibers (coating method). Typical coating methods include a direct gravure coater, a chamber doctor coater, an offset gravure coater, a single-roll kiss coater, a reverse kiss coater, a bar coater, a reverse roll coater, a slotter die coater, an air doctor coater, a positive rotation roll coater, a blade coater, a knife coater, an impregnation coater, a MB coater, and an MB reverse coater.

[0061] The amount of matrix resin attached to the glass cloth is preferably 10 to 80% by mass, more preferably 20 to 70% by mass. Within this range, the amount of matrix resin attached to the glass cloth is appropriate, and is effective in improving adhesion and bonding with the matrix resin and the strength of the wiring board. If the amount is 10% by mass or more, when laminating prepreg and copper foil to produce a board, the amount of matrix resin adhering to the copper foil is not too small, and sufficient peel strength with the copper foil is obtained. Furthermore, if the amount is 80% by mass or less, the amount of matrix resin is not too large, and resin flow during pressing is unlikely to occur, which is preferable. The amount of matrix resin attached here refers to the mass % of the matrix resin relative to the total mass of the prepreg.

[0062] The conditions vary depending on the matrix resin used, but for example, after application, the resin can be dried and then heated at 50 to 300° C. for 1 minute to 24 hours for curing.

[0063] (3-2) Manufacturing method of prepreg containing surface-treated glass cloth When a surface-treated glass cloth is used as the article, a matrix resin or a solution containing the matrix resin, and other components as necessary, are mixed, and the surface-treated glass cloth is impregnated with the resulting resin or solution to obtain a prepreg containing the surface-treated glass cloth. The specific manufacturing method is the same as when surface-treated silica particles are used. Note that surface-treated silica particles may be added to the matrix resin, and in that case, the amount added is the same as above.

[0064] The thickness of the prepreg of the present invention is not particularly limited, but is preferably 10 to 400 μm, more preferably 30 to 300 μm, and even more preferably 40 to 200 μm. Within this range, for example, when the prepreg of the present invention is used for a printed wiring board, a substrate such as a copper-clad laminate can be successfully prepared. The prepreg of the present invention may be semi-cured (B-staged) in advance by heating. The method for B-staging is not particularly limited, but for example, B-staging can be achieved by dissolving the matrix resin in a solvent, impregnating glass cloth with the solution, drying, and then heating at a temperature of 80 to 200°C for 1 to 30 minutes.

[0065] [Printed Wiring Board] The printed wiring board of the present invention is obtained using a prepreg containing the article of the present invention. The method for producing the printed wiring board of the present invention is not particularly limited, and a general method for producing a printed wiring board can be applied. Specific examples include a method in which the prepreg of the present invention and copper foil are stacked and pressed, followed by heat curing, to produce a copper-clad laminate. The method for producing a copper-clad laminate is not particularly limited, but it can be produced, for example, by using 1 to 20 sheets, preferably 2 to 10 sheets, of the above prepreg, placing copper foil on one or both sides of the prepreg, pressing, and heat curing.

[0066] The thickness of the copper foil is not particularly limited, but is preferably 3 to 70 μm, more preferably 10 to 50 μm, and even more preferably 15 to 40 μm. Within this range, a multilayer copper-clad laminate with high reliability can be formed. The molding conditions for the copper-clad laminate are not particularly limited, but for example, molding can be performed using a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, or the like, at a temperature of 100 to 400°C, a pressure of 1 to 100 MPa, and a heating time of 0.1 to 4 hours. Alternatively, a copper-clad laminate can be formed by combining and molding the prepreg of the present invention, copper foil, and an inner layer wiring board.

[0067] The method of circuit processing is not particularly limited, and examples thereof include circuit formation processing methods such as drilling, metal plating, etching of metal foil, etc. Furthermore, a printed wiring board may be produced by a build-up method in which a composition containing a matrix resin or the prepreg of the present invention and copper foil are sequentially laminated.

[0068] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following formulas, Me represents a methyl group and Et represents an ethyl group. In the following examples, the kinematic viscosity, specific gravity, and refractive index are values ​​measured at 25°C, and parts are parts by mass. In this case, the kinematic viscosity was measured in accordance with JIS Z 8803. The specific gravity was measured in accordance with JIS Z 8804. The refractive index was measured in accordance with JIS K 0062. Nuclear magnetic resonance spectrum ( 1 H-NMR measurements were performed in deuterated chloroform using an AVANCE III / ULTRASHIELD 400 manufactured by BRUKER. Infrared absorption (IR) measurements were performed using a Nicolet 6700 Fourier transform infrared spectrophotometer manufactured by Thermo Fisher Scientific.

[0069] [1] Synthesis of Organosilicon Compound [Example 1-1] 100.0 g of Neoallyl T-20 (trimethylolpropane diallyl ether, manufactured by Osaka Soda Co., Ltd.) (hydroxyl value: 265 mg KOH / g) and 0.11 g of dioctyltin oxide were placed in a 300 mL separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, and 3-isocyanatopropyltrimethoxysilane was added dropwise over 1 hour at an internal temperature of 80 to 90°C. The amount of 3-isocyanatopropyltrimethoxysilane was 1.0 mole relative to the molar amount of hydroxyl groups calculated from the hydroxyl value of Neoallyl T-20. The mixture was then stirred at 85°C for 3 hours, and the reaction was terminated when IR measurement confirmed that the absorption peaks derived from the isocyanato groups of the raw material had completely disappeared. Thereafter, 7.9 g of Silica Gel 60N (manufactured by Kanto Chemical Co., Inc.) was added, and the mixture was stirred at room temperature for 3 hours. Thereafter, the silica gel 60N was filtered off, and the resulting product had a kinematic viscosity of 65.5 mm ２ / s, specific gravity 1.06, refractive index 1.458, it is a pale yellow transparent liquid, １ It was confirmed by H-NMR that the compound was the organosilicon compound represented by the above formula (2-1). １ H-NMR (CDCl ３ , 400MHz) δ: 0.56-0.67 (m, 2H), 0.80-0.92 (m, 3H), 1.30-1.52 (d, 2H), 1.53-1.70 (m, 2H), 3.00-3.23 (m, 2H), 3.25-3 .35 (m, 2H), 3.53 (s, 9H), 3.92-3.97 (d, 2H), 4.00 (s, 2H), 4.78-4.95 (s, 1H), 5.05-5.30'' (m, 4H), 5.77-5.95 (m, 2H)

[0070] Example 1-2: A 300 mL separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 100.0 g (hydroxyl value 237 mg KOH / g) of Neoallyl P-30 (pentaerythritol triallyl ether, manufactured by Osaka Soda Co., Ltd.) and 0.11 g of dioctyltin oxide, and 3-isocyanatopropyltrimethoxysilane was added dropwise over 1 hour at an internal temperature of 80 to 90°C. The amount of 3-isocyanatopropyltrimethoxysilane was 1.0 mole relative to the molar amount of hydroxyl groups calculated from the hydroxyl value of Neoallyl P-30. The mixture was then stirred at 85°C for 3 hours, and the reaction was terminated when IR measurement confirmed that the absorption peaks derived from the isocyanato groups of the raw material had completely disappeared. Thereafter, 7.5 g of silica gel 60N (manufactured by Kanto Chemical Co., Inc.) was added, and the mixture was stirred at room temperature for 3 hours. Thereafter, the silica gel 60N was filtered off, and the resulting product had a kinematic viscosity of 78.2 mm ２ / s, specific gravity 1.07, refractive index 1.462, it is a pale yellow transparent liquid, １ It was confirmed by H-NMR that the compound was the organosilicon compound represented by the above formula (2-2). １ H-NMR (CDCl ３ , 400MHz) δ: 0.56-0.70 (m, 2H), 1.52-1.70 (m, 2H), 3.18 (s, 2H), 3.36-3.51 (m, 6H), 3.55 (s, 9 H), 3.90-4.00 (d, 6H), 4.15 (s, 2H), 4.75-4.95 (s, 1H), 5.05-5.30'' (m, 6H), 5.77-5.95 (m, 3H)

[0071] Example 1-3: 100.0 g (hydroxyl value 237 mg KOH / g) of Neoallyl P-30 (pentaerythritol triallyl ether, manufactured by Osaka Soda Co., Ltd.) and 0.11 g of dioctyltin oxide were placed in a 300 mL separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, and 3-isocyanatopropyltriethoxysilane was added dropwise over 1 hour at an internal temperature of 80 to 90°C. The amount of 3-isocyanatopropyltriethoxysilane was 1.0 mole relative to the molar amount of hydroxyl groups calculated from the hydroxyl value of Neoallyl P-30. The mixture was then stirred at 85°C for 3 hours, and the reaction was terminated when IR measurement confirmed that the absorption peaks derived from the isocyanato groups of the raw material had completely disappeared. Thereafter, 8.2 g of silica gel 60N (manufactured by Kanto Chemical Co., Inc.) was added, and the mixture was stirred at room temperature for 3 hours. Thereafter, the silica gel 60N was filtered off, and the resulting product had a kinematic viscosity of 55.5 mm ２ / s, specific gravity 1.03, refractive index 1.457, pale yellow transparent liquid, １ It was confirmed by H-NMR that the compound was the organosilicon compound represented by the above formula (2-3). １ H-NMR (CDCl ３ , 400MHz) δ: 0.56-0.70 (m, 2H), 1.17-1.28 (m, 9H), 1.52-1.70 (m, 2H), 3.18 (s, 2H), 3.36-3.51 (m, 6H), 3.7 8-3.89 (m, 6H), 3.90-4.00 (d, 6H), 4.15 (s, 2H), 4.75-4.95 (s, 1H), 5.05-5.30'' (m, 6H), 5.77-5.95 (m, 3H)

[0072] [Example 1-4] 100.0 g (0.581 mol) of Neoallyl E-20 (glycerin diallyl ether, manufactured by Osaka Soda Co., Ltd.) and 0.13 g of dioctyltin oxide were placed in a 500 mL separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, and 119.2 g (0.581 mol) of 3-isocyanatopropyltrimethoxysilane was added dropwise over 1 hour at an internal temperature of 80 to 90°C. The mixture was then stirred at 85°C for 3 hours, and the reaction was terminated when IR measurement confirmed that the absorption peak derived from the isocyanato group of the raw material had completely disappeared. 8.8 g of Silica Gel 60N (manufactured by Kanto Chemical Co., Inc.) was then added, and the mixture was stirred at room temperature for 3 hours. The silica gel 60N was then filtered off, and the resulting product had a kinematic viscosity of 32.0 mm ２ / s, specific gravity 1.08, refractive index 1.455, it is a pale yellow transparent liquid, １ It was confirmed by H-NMR that the compound was the organosilicon compound represented by the above formula (3-1). １ H-NMR (CDCl ３ , 400MHz) δ: 0.56-0.67 (m, 2H), 1.52-1.70 (m, 2H), 3.08-3.23 (m, 2H), 3.54 (s, 9H), 3.60- 3.70 (m, 4H), 3.95-4.08 (m, 4H), 4.90-4.95 (s, 1H), 4.97-5.05 (m, 1H), 5.10-5.33 (m, 4H) , 5.82-5.96 (m, 2H)

[0073] [2] Production of Surface-Treated Silica Particles [Example 2-1] 625 g of silica sol obtained by concentrating a commercially available acidic aqueous silica sol (trade name: Snowtex O, manufactured by Nissan Chemical Industries, Ltd.) to a silica concentration of 40% by mass, and 1,125 g of isopropyl alcohol were added to a 2-liter glass separable flask equipped with a stirrer, a dropping funnel, a condenser, and a thermometer, and the mixture was stirred at 25 ° C. while bubbling air. 30 g of the organosilicon compound (2-1) obtained in Example 1-1 was added dropwise thereto, and the temperature was raised to 78 ° C., and stirring was continued for 4 hours to perform a hydrophobic treatment of the silica sol. Thereafter, the internal temperature was lowered to 70 ° C., and 34 g of hexamethyldisilazane (trade name: HMDS, manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise, and stirring was continued for 2 hours. The solid was collected by filtration, washed with methanol, and then dried under reduced pressure at 110 ° C. for 1 hour to obtain surface-treated silica particles (A).

[0074] [Example 2-2] Surface-treated silica particles (B) were obtained by the same procedure as in Example 2-1, except that the organosilicon compound (2-1) in Example 2-1 was changed to the organosilicon compound (2-2) obtained in Example 1-2.

[0075] [Example 2-3] Surface-treated silica particles (C) were obtained by the same procedure as in Example 2-1, except that the organosilicon compound (2-1) in Example 2-1 was changed to the organosilicon compound (3-1) obtained in Example 1-4.

[0076] Comparative Example 2-1 Surface-treated silica particles (D) were obtained by the same procedure as in Example 2-1, except that the organosilicon compound (2-1) was changed to 28 g of organosilicon compound (4) (vinyltrimethoxysilane, trade name: KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0077] [3] Production of prepregs and substrates using surface-treated silica particles [Examples 3-1 to 3-4, Comparative Examples 3-1 to 3-3] A polyphenylene ether resin containing methacryloxy groups as polymerizable reactive groups (Noryl (registered trademark) SA9000 manufactured by SHPP Japan LLC, hereinafter referred to as PPE) and toluene were mixed in a mass ratio of 1:1, and the mixed solution was heated and stirred at 80 ° C. for 1 hour to completely dissolve the PPE in toluene, and then cooled to 25 ° C. to obtain a 50 mass% toluene solution of PPE. Next, according to the blending ratios (parts by mass) listed in Table 1, the 50 mass% toluene solution of PPE (non-volatile content equivalent), crosslinker, organic resin, surface-treated silica particles, and curing agent were mixed and stirred for 30 minutes to completely dissolve, obtaining a varnish-like curable composition (resin varnish).

[0078] Next, the obtained resin varnish was impregnated into a glass cloth (manufactured by Nitto Boseki Co., Ltd., #1078 type, WEA1078) and then heated and dried at 120°C for 3 minutes to obtain a prepreg. At this time, the thickness after curing was adjusted to about 60 μm. Both sides of one of the obtained prepregs were sandwiched between copper foils (manufactured by Furukawa Electric Co., Ltd., GT-MP, thickness 12 μm), and laminated, and the laminate was then heated under vacuum conditions at 190°C for 90 minutes at a pressure of 40 kgf / cm. ２ The cured product, evaluation substrate 1, was obtained by heating and pressing under the conditions of 12. Twelve prepregs obtained above were stacked, sandwiched between copper foils (GT-MP manufactured by Furukawa Electric Co., Ltd., thickness 12 μm), and laminated under vacuum conditions at 220°C for 90 minutes under a pressure of 40 kgf / cm. ２ By applying heat and pressure under the conditions above, an evaluation substrate 2 was obtained.

[0079] The evaluation substrates 1 and 2 prepared by the above procedure were evaluated by the following methods. The results are also shown in Table 1 below. [Dielectric Properties] For each evaluation substrate 2 prepared above, from which the copper foil had been removed, the relative permittivity and dielectric loss tangent at 10 GHz were measured using a network analyzer (Keysight: E5063-2D5) by the cavity resonator perturbation method. [Copper Foil Adhesion Strength] The copper foil peel strength (copper foil adhesion strength) of each evaluation substrate 1 prepared above was measured using a method in accordance with JIS C 6481. A 10 mm wide and 100 mm long pattern was formed on a 20 mm wide and 100 mm long test piece, and the copper foil was peeled off at a rate of 50 mm / min using a tensile tester. The peel strength (kN / m) at this time was evaluated as the copper foil adhesion strength.

[0080]

[0081] Each component shown in Table 1 will be explained below. PPE: PPO Noryl (registered trademark) SA9000 (polyphenylene ether resin containing methacryloxy groups as polymerizable reactive groups) manufactured by SABIC Innovative Plastics Corporation (SHPP Japan LLC) Crosslinker 1: TAIC (trademark) (triallyl isocyanurate) manufactured by Nippon Kasei Chemical Co., Ltd. Crosslinker 2: DCP (tricyclodecane dimethanol dimethacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. Organic resin: Ricon 100 (styrene butadiene random copolymer) manufactured by Cray Valley Curing agent: Perbutyl P (1,3-bis(butylperoxyisopropyl)benzene, peroxide) manufactured by NOF Corporation

[0082] As shown in Table 1, the printed wiring boards provided with prepregs using silica particles surface-treated with organosilicon compounds obtained in Examples 1-1, 1-2 and 1-4 have excellent dielectric properties and copper foil adhesion strength.

[0083] [4] Production of Surface-Treated Glass Cloth [Examples 4-1 to 4-3, Comparative Examples 4-1 to 4-5] A glass cloth treatment solution was prepared according to the following procedure, and glass cloth was subjected to a surface treatment. To a solvent prepared by mixing a 0.1 mass % aqueous acetic acid solution and methanol in a mass ratio of 50:50, the organosilicon compounds (2-1), (2-2), and (3-1) obtained in Examples 1-1, 1-2, and 1-4 above, and the following organosilicon compounds (4) to (6), were added to a solids concentration of 0.2 mass % and stirred, to prepare a glass cloth treatment solution. Furthermore, the following organosilicon compound (7) was added to ion-exchanged water to a concentration of 0.2 mass %, followed by stirring, to prepare a glass cloth treatment solution containing the following organosilicon compound (7). A silica glass cloth (thickness: 95 μm, mass per unit area: 93 g / m) was added to the obtained glass cloth treatment solution. ２ ) and then heated and dried at 110°C for 10 minutes to produce a surface-treated glass cloth.

[0084] Organosilicon compound (4): vinyltrimethoxysilane (trade name: vinyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) Organosilicon compound (5): 3-(methacryloyloxy)propyltrimethoxysilane (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) Organosilicon compound (6): N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride (trade name: KBM-575, manufactured by Shin-Etsu Chemical Co., Ltd.) Organosilicon compound (7): 3-aminopropyltrimethoxysilane (trade name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0085] The surface-treated glass cloth thus obtained was evaluated by the following methods, and the results are shown in Table 2 below.

[0086] [Dielectric Properties] A rectangular molded piece having a thickness of 0.30 mm and a size of 5 cm x 5 cm was prepared. A network analyzer (manufactured by Keysight Corporation: E5063-2D5) was connected to a strip line (manufactured by Keycom Corporation) to measure the dielectric constant and dielectric loss tangent of the molded piece at a frequency of 10 GHz. The measurement results for a glass cloth that had not been subjected to a surface treatment (Comparative Example 4-1) were converted to 100, and evaluation was performed.

[0087] [5] Manufacturing of Prepregs and Substrates Using Surface-Treated Glass Cloth [Examples 5-1 to 5-3, Comparative Examples 5-1 to 5-5] The surface-treated glass cloth obtained in Examples 4-1 to 4-3 and Comparative Examples 4-2 to 4-5 was impregnated with matrix resin (M-1) and heated and dried at 100°C for 10 minutes to remove the solvent, resulting in a prepreg. Next, one prepreg was heat-cured at 180°C for 60 minutes using a vacuum press under a pressure of 5 MPa to produce evaluation substrate 3. In Comparative Example 5-1, evaluation substrate 3 was produced in the same manner as in the other Examples and Comparative Examples, except that untreated silica glass cloth was used. Here, matrix resin (M-1) was a mixture of the above-mentioned PPE, crosslinker 1, organic resin, dicumyl peroxide, and toluene in a mass ratio of 75:12.5:12.5:1:70.

[0088] [Dielectric Properties] As in the case of the surface-treated glass cloth described above, the relative permittivity and dielectric loss tangent of each evaluation substrate 3 were measured, and the measurement results of a printed wiring board (Comparative Example 5-1) using a glass cloth that had not been surface-treated (Comparative Example 4-1) were converted to 100 and evaluated.

[0089] [Tensile Strength] The tensile strength of the evaluation substrate 3 was measured in accordance with JIS K 6251:2010 using an EZ TEST (EZ-L, manufactured by Shimadzu Corporation) under conditions of a test speed of 500 mm / min, a gripping distance of 80 mm, and a gauge length of 40 mm.

[0090] [Solder Heat Resistance Test] Three sheets of the prepreg obtained above were stacked and heat-cured using a vacuum press at 180°C for 60 minutes under a pressure of 5 MPa to produce evaluation board 4. Each evaluation board 4 obtained was boiled in ion-exchanged water for one hour and then immersed in a solder bath at 260°C for 30 seconds. The appearance of the board was visually observed, and those that did not blister were rated as "O" and those that blistered were rated as "X". The evaluation results for evaluation boards 3 and 4 are shown in Table 2.

[0091]

[0092] As shown in Table 2, the glass cloths treated with the organosilicon compounds obtained in Examples 1-1, 1-2, and 1-4 and their cured products (substrates) had low dielectric dissipation factors and excellent tensile strength. On the other hand, the substrate (Comparative Example 5-2) using the glass cloth treated with vinyltrimethoxysilane (Comparative Example 4-2) exhibited poor tensile strength and heat resistance. This is thought to be due to the organosilicon compound having a low carbon number and poor compatibility with the matrix resin. Furthermore, the surface-treated glass cloths of Comparative Examples 4-3 and 4-4 did not have sufficiently low dielectric dissipation factors, while the surface-treated glass cloth of Comparative Example 4-5 had a high dielectric dissipation factor, resulting in poor heat resistance for the substrates using it (Comparative Example 5-5).

Claims

1. An organosilicon compound represented by the following formula (1): (In the formula, Me represents a methyl group, R 1 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R 2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R 3 represents a hydrogen atom or a methyl group, X represents a p+q+1 valent hydrocarbon group having 3 to 20 carbon atoms, including a branched structure or a ring structure, m represents an integer of 1 to 3, n represents an integer of 1 to 12, p is 0 or 1, q represents an integer of 1 to 3, and p+q represents an integer of 1 to 4.

2. The organosilicon compound according to claim 1, which is represented by the following formula (2) or (3): (In the formula, Me, R 1 , R 2 , m and n are the same as above, and R 4 represents a hydrogen atom, a methyl group, or an allyloxy group.

3. R 1 is a hydrogen atom, a methyl group, or an ethyl group, and R 2 3. The organosilicon compound according to claim 1, wherein is a hydrogen atom and n is 3.

4. An article comprising a substrate surface-treated with the organosilicon compound according to any one of claims 1 to 3.

5. The article of claim 4, wherein the substrate is an inorganic material.

6. The article according to claim 5, wherein the inorganic material is silica particles or glass fibers.

7. A prepreg comprising the article according to any one of claims 4 to 6 and a matrix resin.

8. A printed wiring board comprising the prepreg according to claim 7.

9. A glass cloth treatment liquid comprising the organosilicon compound according to any one of claims 1 to 3 dissolved in a solvent containing water.

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