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

Abstract

Provided is an article including a substrate surface-treated with an organosilicon compound represented by formula (1). (In the formula, Me is a methyl group, R1s each independently represent a hydrogen atom, a C1-C10 alkyl group, or a C6-C20 aryl group, R2 is a hydrogen atom or a methyl group, and m is an integer of 1-3.)

Description

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

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

[0002] As electronic devices, such as tablets and smartphones, become more powerful and faster, the printed wiring boards used in these devices are becoming increasingly dense and thin, while also exhibiting lower dielectric constants and lower dielectric loss tangents. The insulating material used in these printed wiring boards is a laminated board made by laminating prepregs containing inorganic fillers and glass cloth as reinforcements 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 reinforcements used in these applications are surface-treated with silane coupling agents, which react with the organic functional groups of the matrix resin to improve adhesion between the reinforcement material, such as glass cloth, and the matrix resin. Surface treatment can involve coating the substrate with the silane coupling agent itself, or it can be performed in solution to achieve uniform treatment. When using solutions, the ability to handle them as an aqueous solution without using solvents such as methanol is also important, particularly from the perspective of reducing environmental impact.

[0003] A typical silane coupling agent used in glass cloth treatment solutions is 3-methacryloyloxypropyltrimethoxysilane, as reported in Patent Document 1. However, laminates using glass cloth surface-treated with 3-methacryloxypropyltrimethoxysilane have poor solder heat resistance and alkali resistance, and have had reliability issues.

[0004] On the other hand, Patent Documents 2 and 3 report that the dielectric properties, heat resistance, and moist heat resistance of resins can be improved by using fillers treated with alkenyl group-containing silane coupling agents. However, there is still room for improvement. In particular, long-chain alkenylsilanes with 6 or 8 carbon atoms have low hydrophilicity, which means that alcohol must be used in combination when forming an aqueous solution, and the storage stability of the aqueous solution is low.

[0005] International Publication No. 2020 / 194772 Patent No. 6684822 Publication No. 2019 / 103082

[0006] The present invention has been made in view of the above problems, and has as its object to provide an article that can provide a prepreg or printed wiring board having excellent durability and dielectric properties.

[0007]

[0006] The present inventors have conducted extensive research to solve the above problems and have found that when a substrate containing an article surface-treated with an organosilicon compound in which a (meth)acryloyloxy group is bonded to a silicon atom via an isobutylene linking chain is used in a prepreg or printed wiring board, the dielectric properties of the substrate can be improved. They have also found that a solution of the organosilicon compound in a solvent containing water gives a surface-treated glass cloth that can be used to form a highly reliable laminate, and is therefore suitable as a glass cloth treatment liquid.

[0007] In this invention, the term "(meth)acryloyloxy group" refers to a methacryloyloxy group or an acryloyloxy group.

[0008] That is, the present invention provides: 1. an article comprising a substrate surface-treated with an organosilicon compound represented by the following formula (1); (wherein Me is a methyl group, R 1 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R 2 is a hydrogen atom or a methyl group, and m is an integer of 1 to 3. 1are each independently a hydrogen atom, a methyl group, or an ethyl group, 3. The article according to 1 or 2, wherein the substrate is an inorganic material, 4. The article according to 3, wherein the inorganic material is silica particles or glass fibers, 5. A prepreg comprising the article according to any one of 1 to 4 and a matrix resin, 6. A printed wiring board comprising the prepreg according to 5, 7. A solution in which an organosilicon compound represented by the following formula (1) is dissolved in a solvent containing water, (wherein Me is a methyl group, R 1 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R 2 is a hydrogen atom or a methyl group, and m is an integer of 1 to 3.) 8. R 1 are each independently a hydrogen atom, a methyl group or an ethyl group; 9. A glass cloth treatment liquid comprising the solution according to 7 or 8.

[0009] The article of the present invention has excellent adhesion to resins and dielectric properties, and can therefore be suitably used as a reinforcing material for prepregs, printed wiring boards, and the like. By using the article, it is possible to obtain prepregs, printed wiring boards, and the like that are excellent in durability and dielectric properties.

[0010] The present invention will be described in detail below. [Article] The article of the present invention comprises a substrate surface-treated with an organosilicon compound represented by the following formula (1) (hereinafter, sometimes referred to as compound (1)). (1) Organosilicon Compound The organosilicon compound used in the present invention is represented by the following formula (1). A substrate surface-treated with this organosilicon compound can be obtained by applying the organosilicon compound represented by the following formula (1) to the surface of a substrate and drying it by heating.

[0011]

[0012] In the above formula, Me is a methyl group, and R 1 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R 2 is a hydrogen atom or a methyl group.

[0013] R 1 The 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 Specific examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and a tolyl group. 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.

[0014] R 2 is a hydrogen atom or a methyl group, and is preferably a methyl group from the viewpoint of compatibility with the matrix resin and dispersion medium when applied to a substrate.

[0015] m represents an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0016] The compound (1) used in the present invention is preferably one represented by the following formulas (2) to (13), and one in which some or all of the alkoxy groups have been converted to hydroxyl groups by hydrolysis. (In the formula, Me represents a methyl group, and Et represents an ethyl group.)

[0017] The method for producing compound (1) is not particularly limited, and conventionally known production methods can be used. For example, as described in JP-A-2000-159780, compound (1) can be produced by the potassium dechlorination reaction of 3-chloroisobutylalkoxysilane and potassium methacrylate. The reaction ratio of 3-chloroisobutylalkoxysilane and potassium methacrylate is not particularly limited, but for example, 0.8 to 1.5 moles of potassium methacrylate per mole of 3-chloroisobutylalkoxysilane is preferred, and 0.8 to 1.2 moles is more preferred.

[0018] The reaction proceeds without a solvent, but a solvent can also be used. Specific examples of usable solvents include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene, and xylene; ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; ester solvents such as ethyl acetate and butyl acetate; aprotic polar solvents such as N,N-dimethylformamide; and chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents may be used alone or in combination of two or more.

[0019] In the above reaction, if necessary, a polymerization inhibitor for the radical polymerizable monomer can be used. Examples include phenolic inhibitors such as hydroquinone, methylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, p-methoxyphenol, 2,6-di-t-butyl-p-cresol, 6-t-butyl-2,4-xylenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methoxyphenol, and 2,2'-methylenebis(4-methyl-6-t-butylphenol); organic acid copper salts; and phenothiazine. Among these, phenolic inhibitors are preferred in terms of low coloration and polymerization inhibition ability, and p-methoxyphenol, 2,6-di-t-butyl-p-cresol, 6-t-butyl-2,4-xylenol, and 2,6-di-t-butylphenol are particularly preferred in terms of availability and economy. These polymerization inhibitors may be used alone or in combination of two or more.

[0020] When a polymerization inhibitor is used, the amount to be added is not particularly limited, but is about 100 to 100,000 ppm based on the mass of the metal salt compound such as potassium methacrylate.

[0021] In the above reaction, a catalyst such as a phase transfer catalyst may be used as necessary. Specific examples of the phase transfer catalyst include quaternary phosphonium salts and quaternary ammonium salts. Examples of the quaternary phosphonium salts include tetraethylphosphonium chloride, tetraethylphosphonium bromide, tetraethylphosphonium iodide, tetrabutylphosphonium bromide, triphenylbenzylphosphonium bromide, and tetraphenylphosphonium bromide. Examples of quaternary ammonium salts include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylbenzylammonium hydroxide, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, trimethylbenzylammonium bromide, triethylbenzylammonium bromide, trimethylphenylammonium bromide, triethylbenzylammonium chloride, tetramethylammonium chloride, trioctylmethylammonium chloride, tributylbenzylammonium chloride, trimethylbenzylammonium chloride, N-laurylpyridinium chloride, N-benzylpicolinium chloride, N-lauryl 4-picolinium chloride, N-laurylpicolinium chloride, tricaprylmethylammonium chloride, tetramethylammonium iodide, tetra-n-butylammonium iodide, and tetrabutylammonium hydrogen sulfate.

[0022] When a catalyst is used, the amount used is not particularly limited, but from the standpoints of reactivity and productivity, the amount of catalyst is preferably 0.1 to 10.0 mass%, more preferably 1.0 to 5.0 mass%, and even more preferably 2.0 to 4.0 mass%, relative to the halogen group-containing organosilicon compound such as 3-chloroisobutylalkoxysilane.

[0023] The reaction temperature in the above reaction is not particularly limited, but is preferably 0 to 200° C., and from the viewpoints of productivity and suppression of side reactions, is more preferably 0 to 100° C., and even more preferably 10 to 100° C. The reaction time is also not particularly limited, but is preferably 10 minutes to 60 hours, more preferably 1 to 30 hours, and even more preferably 1 to 20 hours.

[0024] (2) Substrate The substrate in the article of the present invention is not particularly limited, but is preferably an inorganic material, 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, ply-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.

[0025] (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.

[0026] (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).

[0027] 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.

[0028] 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.

[0029] (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.

[0030] (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 step, 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 solvent may be used alone, or two or more solvents may be used in combination.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] (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, the treatment can be performed using a 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.

[0037] [Solution / Glass Cloth Treatment Liquid] The solution of the present invention is a solution in which the organosilicon compound of the present invention is dissolved in a solvent containing water, and it is preferable to use the solution of the present invention as a glass cloth treatment liquid (hereinafter sometimes referred to as "treatment liquid") used to surface treat glass cloth as described above. From the viewpoints of storage stability and productivity, the content of the organosilicon compound in the treatment liquid of the present invention is preferably 0.001 to 10.0 mass %, more preferably 0.05 to 5.0 mass %, and even more preferably 0.05 to 2.0 mass %, in terms of solids content, relative to the entire treatment liquid.

[0038] 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 the organosilicon compound is added to the solvent is preferably 10 to 50°C, more preferably 15 to 40°C.

[0039] 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.

[0040] From the viewpoint of storage stability, the water contained in the glass cloth treatment liquid of the present invention is preferably water adjusted to an acidic state. Examples of acids used to adjust the acidic state 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 an acidic state by mixing the acid and water in advance may be used, or the acid may be added to the glass cloth treatment liquid containing the organosilicon compound of the present invention to adjust the acidic state.

[0041] The glass cloth treatment liquid of the present invention is preferably an aqueous solution in which the organosilicon compound of the present invention is dissolved in water, and more preferably an aqueous solution in which the organosilicon compound of the present invention is dissolved in water adjusted to be acidic.

[0042] 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.

[0043] [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.

[0044] (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 preferred that the surface-treated substrate itself, such as surface-treated silica particles or surface-treated glass cloth, be used as the article.

[0045] (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 and maleimide resins are preferred.

[0046] 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.

[0047] (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.

[0048] (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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] (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.

[0056] 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.

[0057] [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.

[0058] 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.

[0059] 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. In addition, 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.

[0060] The present invention will be described in more detail below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to these examples. In the following formula, Me represents a methyl group, and Et represents an ethyl group. Gas chromatography was carried out under the following measurement conditions. GC apparatus: 8890 manufactured by Agilent Technologies Detector: Hydrogen ionization detector (FID) Column: HP-5 J-413 (length 30 m x inner diameter 0.32 mm, film thickness 0.25 μm) Column temperature: 50°C → 300°C (heating rate 10°C / min, total measurement time 35.0 min) Injection port temperature: 250°C Detector temperature: 300°C Carrier gas: He Carrier gas flow rate: 1.0 mL / min

[0061] [1] Synthesis of Organosilicon Compounds [Synthesis Example 1] A 500 mL separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 80.0 g (1.40 mol) of potassium methacrylate (Tokyo Chemical Industry Co., Ltd.), 100 g of toluene, 0.4 g of 2,6-di-tert-butyl-p-cresol, and 4.0 g of tetrabutylammonium bromide. 300 g (1.4 mol) of 3-chloro-2-methylpropyltrimethoxysilane was added dropwise over 1 hour using a dropping funnel at an internal temperature of 80 to 90 ° C. The mixture was then stirred at 80 ° C. for 30 hours, and analyzed by gas chromatography. The disappearance of 3-chloro-2-methylpropyltrimethoxysilane was confirmed. The reaction solution and the duplicated potassium chloride were separated by pressure filtration (filter plate NA-100, manufactured by ADVANTEC), and the reaction solution was distilled at 105 ° C. and 6 Torr to obtain compound (2) represented by the following formula:

[0062]

[0063] Synthesis Example 2 The same procedure as in Synthesis Example 1 was carried out, except that 3-chloro-2-methylpropyltrimethoxysilane in Synthesis Example 1 was changed to 3-chloro-2-methylpropylmethyldimethoxysilane (1.41 mol), to obtain compound (3) represented by the following formula:

[0064]

[0065] Synthesis Example 3 The same operation as in Synthesis Example 1 was carried out, except that 3-chloro-2-methylpropyltrimethoxysilane in Synthesis Example 1 was changed to 3-chloro-2-methylpropyldimethylmethoxysilane (1.41 mol), to obtain compound (4) represented by the following formula.

[0066]

[0067] Synthesis Example 4 The same operation as in Synthesis Example 1 was carried out, except that 3-chloro-2-methylpropyltrimethoxysilane in Synthesis Example 1 was changed to 3-chloro-2-methylpropyltriethoxysilane (1.41 mol), to obtain compound (5) represented by the following formula.

[0068]

[0069] Synthesis Example 5 The same procedure as in Synthesis Example 1 was carried out, except that potassium methacrylate in Synthesis Example 1 was changed to potassium acrylate (1.48 mol), to obtain a compound (8) represented by the following formula.

[0070]

[0071] [2] Preparation of Aqueous Solutions [Examples 1-1 to 1-5, Comparative Examples 1-1 to 1-3] 99.5 parts by mass of ion-exchanged water and 0.05 parts by mass of acetic acid were mixed and stirred at 25°C, and 0.5 parts by mass of each of the organosilicon compounds obtained in Synthesis Examples 1 to 5 above or organosilicon compounds A to C below was added dropwise to prepare aqueous solutions. The resulting aqueous solutions were evaluated as follows. The results are shown in Table 1.

[0072] Organosilicon compound A: 3-methacryloyloxypropyltrimethoxysilane (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) Organosilicon compound B: 8-methacryloyloxyoctyltrimethoxysilane (trade name: KBM-5083, manufactured by Shin-Etsu Chemical Co., Ltd.) Organosilicon compound C: 7-octenyltrimethoxysilane (trade name: KBM-1083, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0073] [Stability of Aqueous Solution] The appearance of the obtained aqueous solution was visually inspected after leaving it to stand in an environment of 25°C for 1 hour and 3 days, and evaluated according to the following criteria: ◯: Completely dissolved, forming a homogeneous aqueous solution; ×: Insoluble matter precipitated.

[0074]

[0075] As shown in Table 1, the aqueous solutions of Examples 1-1 to 1-5 had excellent storage stability. The aqueous solution of Comparative Example 1-1 in which 3-methacryloyloxypropyltrimethoxysilane was dissolved had low storage stability, and it was difficult to prepare aqueous solutions of the silane coupling agents with long alkylene chains shown in Comparative Examples 1-2 and 1-3.

[0076] [3] Preparation of Surface-Treated Silica Particles [Examples 2-1 to 2-5, Comparative 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 placed in a 2-L glass separable flask equipped with a stirrer, dropping funnel, condenser, and thermometer, and stirred at 25°C while bubbling air. 30 g of each of the organosilicon compounds obtained in Synthesis Examples 1 to 5 above or the organosilicon compound A above was added dropwise thereto, and the temperature was raised to 78°C, and stirring was continued for 4 hours to hydrophobize 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, followed by stirring 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 (i) to (vi) shown in Table 2.

[0077]

[0078] [4] Production of prepregs and substrates using surface-treated silica particles [Examples 3-1 to 3-6, 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 3, 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).

[0079] 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.

[0080] Each of the evaluation substrates 1 and 2 prepared by the above procedure was evaluated by the following method. The results are also shown in Table 3 below. [Dielectric Properties] For each of the evaluation substrates 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 of the evaluation substrates 1 prepared above was measured by a method conforming to JIS C 6481. A pattern with a width of 10 mm and a length of 100 mm was formed on a test piece with a width of 20 mm and a length of 100 mm, 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.

[0081]

[0082] Each component shown in Table 3 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: DCP (tricyclodecane dimethanol dimethacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. Crosslinker 2: TAIC (trademark) (triallyl isocyanurate) manufactured by Nippon Kasei Chemical Co., Ltd. Organic resin: Ricon 156 (polybutadiene) manufactured by Cray Valley Curing agent: Perbutyl P (1,3-bis(butylperoxyisopropyl)benzene, peroxide) manufactured by NOF Corporation

[0083] As shown in Table 3, the printed wiring boards of Examples 3-1 to 3-6, which are provided with prepregs using the surface-treated silica particles of Examples 2-1 to 2-5, are excellent in dielectric properties and copper foil adhesion strength.

[0084] [5] Production of Surface-Treated Glass Cloth [Examples 4-1 to 4-5, Comparative Examples 4-1 and 4-2] A glass cloth treatment liquid was prepared according to the following procedure, and the surface of glass cloth was treated with the liquid. The organosilicon compounds (2), (3), (4), (5), and (8) obtained in Synthesis Examples 1 to 5 above, or the organosilicon compound A described above, were added to an aqueous acetic acid solution having a concentration of 0.1% by mass, and the mixture was stirred to give a solids concentration of 0.2% by mass, to prepare a glass cloth treatment liquid. Furthermore, the organosilicon compound D described below was added to ion-exchanged water to give a concentration of 0.2% by mass, and the mixture was stirred to prepare a glass cloth treatment liquid. A silica glass cloth (thickness: 95 μm, mass per unit area: 93 g / m) was added to the obtained glass cloth treatment liquid. 2 ) and then heated and dried at 110°C for 10 minutes to produce a surface-treated glass cloth.

[0085] Organosilicon compound D: 3-aminopropyltrimethoxysilane (trade name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0086] The obtained surface-treated glass cloth was evaluated by the following methods, and the results are shown in Table 4 below.

[0087] [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 result of Comparative Example 4-1 was converted to 100, and evaluation was performed.

[0088] [6] Prepreg and Substrate Production Using Surface-Treated Glass Cloth [Examples 5-1 to 5-5, Comparative Examples 5-1 and 5-2] The surface-treated glass cloth obtained in Examples 4-1 to 4-5 and Comparative Examples 4-1 and 4-2 was impregnated with matrix resin (M-1), heated and dried at 100 ° C. for 10 minutes to remove the solvent, and a prepreg was obtained. Next, one prepreg was heated and cured at 180 ° C. for 60 minutes under a pressure of 5 MPa using a vacuum press to produce an evaluation substrate 3. Here, the matrix resin (M-1) was prepared by adding 122 parts by weight of toluene to 100 parts by weight of a bismaleimide compound (trade name: BMI-5000P, manufactured by Designer Molecules Inc.), adjusting the resin concentration to 45% by weight, and then adding 2 parts by weight of dicumyl peroxide as a curing catalyst.

[0089] [Solder Heat Resistance Test] Each evaluation board 3 obtained was cut into a 5 cm square, boiled in ion-exchanged water for 2 hours, and then immersed in a solder bath at 260°C for 30 seconds. The appearance of the board was visually observed, and boards that did not blister were evaluated as "Good", and boards that blistered were evaluated as "Poor". The results are shown in Table 4.

[0090] [Alkali Immersion Test] Each of the obtained evaluation substrates 3 was cut into a 5 cm square and immersed in a 1 N aqueous sodium hydroxide solution for 24 hours. The appearance of the cured product was visually observed and evaluated according to the following criteria. The results are shown in Table 4. ◯: No whitening or slight whitening at the edges. Δ: Whitening extended to near the center. ×: Whitening occurred all over the surface.

[0091]

[0092] As shown in Table 4, the surface-treated glass cloths of Examples 4-1 to 4-5 had low dielectric dissipation factors, and the printed wiring boards of Examples 5-1 to 5-5, which were provided with prepregs using these surface-treated glass cloths, exhibited excellent solder heat resistance and alkali resistance. On the other hand, the surface-treated glass cloths of Comparative Examples 4-1 and 4-2 had high dielectric dissipation factors, and the substrates of Comparative Examples 5-1 and 5-2 using them also had low alkali resistance.

Claims

1. An article comprising a substrate surface-treated with an organosilicon compound represented by the following formula (1): (wherein Me is a methyl group, R 1 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R 2 is a hydrogen atom or a methyl group, and m is an integer of 1 to 3.

2. R 1 2. The article of claim 1, wherein each independently represents a hydrogen atom, a methyl group, or an ethyl group.

3. The article according to claim 1 or 2, wherein the substrate is an inorganic material.

4. The article according to claim 3, wherein the inorganic material is silica particles or glass fibers.

5. A prepreg comprising the article according to any one of claims 1 to 4 and a matrix resin.

6. A printed wiring board comprising the prepreg according to claim 5.

7. A solution in which an organosilicon compound represented by the following formula (1) is dissolved in a solvent containing water. (wherein Me is a methyl group, R 1 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R 2 is a hydrogen atom or a methyl group, and m is an integer of 1 to 3.

8. R 1 The solution according to claim 7, wherein each of is independently a hydrogen atom, a methyl group, or an ethyl group.

9. A glass cloth treatment solution comprising the solution according to claim 7 or 8.

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