Aqueous composition and article treated with aqueous composition

Abstract

Disclosed is an aqueous composition comprising (A) an organosilicon compound represented by formula (1): (RO)3-n(CH3)nSi-Z (R represents a hydrogen atom or a C1-10 alkyl group, Z represents a group having an ethylenically unsaturated bond, and n represents 0, 1, or 2), (B) a nonionic surfactant, (C) an acid, and (D) water, wherein the amount of component (B) is 0.0005-0.05 mass% with respect to the total mass of the aqueous composition, and component (A) has a G value of 1.5 or more as calculated using equation (2): G=M / 20S, where M is the amount (parts by mass) of methanol added dropwise to a liquid until the liquid is compatibilized while stirring S parts by mass of the organosilicon compound and 19×S parts by mass of ion-exchanged water at 25°C. The aqueous composition contains a highly hydrophobic silane coupling agent. When the aqueous composition is applied to a substrate, an article having excellent dielectric properties and high reliability in high-temperature or high-humidity environments is provided.

Description

Aqueous composition and articles treated with said aqueous composition

[0001] The present invention relates to an aqueous composition and an article treated with the aqueous composition, and more specifically to an aqueous composition containing a highly hydrophobic silane coupling agent and an article treated with the aqueous composition.

[0002] Silane coupling agents are compounds that possess both a moiety (a hydrolyzable group bonded to a silicon atom) that is reactive toward inorganic substances and a moiety that can impart various functions, such as reactivity toward organic substances, solubility, and radical polymerization, within a single molecule. They function as adhesion promoters at the interface between inorganic and organic substances and as resin modifiers for inorganic-organic composite materials, and are therefore widely used as composite resin modifiers. In recent years, silane coupling agents have been used for the surface treatment of inorganic fillers such as silica and glass fiber products such as glass cloth, and by incorporating the surface-treated articles into resins, various properties have been improved. Surface treatment can involve coating the substrate with the silane coupling agent itself, but it can also be done in solution to achieve uniform treatment. When using a solution, it is important to note that it can be handled as an aqueous solution without using solvents such as methanol, particularly from the perspective of reducing environmental impact.

[0003] Meanwhile, advances in digital technology are driving the development of lighter, thinner, smaller, and more functional electronic devices, such as tablets and smartphones. For example, printed wiring boards, which are key components of these devices, are required to be more compact and lighter, with higher mounting density. To meet these demands, there is a strong demand for improved properties in inorganic fillers and glass cloth, which are essential components used as reinforcement materials for printed wiring boards. Furthermore, as computers, mobile devices, and communications infrastructure become faster and faster, the inorganic fillers and glass cloth used in printed wiring boards are required to have dielectric properties to improve transmission loss and reliability in high-temperature or high-humidity environments.

[0004] A typical silane coupling agent used in glass cloth treatment liquids is 3-methacryloyloxypropyltrimethoxysilane, as reported in Patent Document 1. In this case, the glass cloth treatment liquid is prepared by dissolving 3-methacryloyloxypropyltrimethoxysilane in weakly acidic water.

[0005] Furthermore, Patent Documents 2 and 3 report that the dielectric properties, heat resistance, and moist heat resistance of a resin can be improved by using a filler treated with an alkenyl group-containing silane coupling agent that does not contain polar atoms such as N atoms or O atoms, but there is still room for improvement.

[0006] On the other hand, in order to improve the heat resistance and low moisture absorption of laminates, it is possible to treat glass cloth or copper foil with a more hydrophobic silane coupling agent, but highly hydrophobic silane coupling agents have issues such as difficulty in preparing an aqueous solution, the silane coupling agent being insoluble in water, and the precipitation of condensation products of the silane coupling agent.When using highly hydrophobic silane coupling agents, alcohol is generally used in combination as a solvent, but this is not desirable in terms of the risk of fire and the health risks to workers in the working environment.

[0007] International Publication No. 2020 / 194772 Patent No. 6684822 International Publication No. 2019-103082

[0008] The present invention has been made in consideration of the above problems, and aims to provide an aqueous composition containing a highly hydrophobic silane coupling agent, which, when applied to a substrate, provides an article having excellent dielectric properties and reliability in high-temperature or high-humidity environments.

[0009] As a result of extensive research to solve the above problems, the present inventors have discovered that an aqueous composition containing a specific organosilicon compound, a specific amount of a nonionic surfactant, an acid, and water, when applied to a substrate, provides an article that has excellent dielectric properties and reliability in high-temperature or high-humidity environments, and have completed the present invention.

[0010] That is, the present invention provides: 1. (A) an organosilicon compound represented by the following formula (1): (RO) 3-n (CH3)n 1. An aqueous composition comprising: Si-Z (1) (wherein each R independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Z represents a group having an ethylenically unsaturated bond, and n represents 0, 1, or 2), (B) a nonionic surfactant, (C) an acid, and (D) water, wherein the amount of the (B) nonionic surfactant is 0.0005 to 0.05 mass% relative to the total mass of the aqueous composition, and the (A) organosilicon compound has a value of G calculated by the following formula (2) of 1.5 or more, when S parts by mass of the organosilicon compound and 19 x S parts by mass of ion-exchanged water are stirred at 25°C and methanol is added dropwise until the liquids become compatible, and the amount of methanol is M parts by mass: G = M / 20S (2) 2. The aqueous composition is p H 2p -Ar-CH=CH2, -C q H 2q -CH=CH2, -C q H 2q -OC(=O)-C(CH3)=CH2, -C q H 2q -OC(=O)-CH=CH2, -C r H 2r -NHC(=O)-O-CX3, or -C r H 2r2. The aqueous composition of 1, wherein Ar is an arylene group having 6 to 20 carbon atoms, and each X is independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an allyloxymethyl group, an acryloyloxymethyl group, or a methacryloyloxymethyl group, and at least one of X is an allyloxymethyl group, an acryloyloxymethyl group, or a methacryloyloxymethyl group, and p is an integer of 0 to 3, q ​​is an integer of 4 to 12, and r is an integer of 1 to 4. 3. The aqueous composition of 1, wherein the (B) nonionic surfactant is one or more selected from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbit fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, polyoxyethylene-modified organopolysiloxanes, and polyoxyethylene polyoxypropylene-modified organopolysiloxanes; 4. The aqueous composition of 1, wherein the (C) acid is one or more selected from hydrochloric acid, formic acid, acetic acid, propionic acid, citric acid, and oxalic acid; The present invention provides the aqueous composition of item 1, in which the amount of the (A) organosilicon compound is 0.1 to 5.0% by mass, and the amount of the (C) acid is 0.0001 to 5.0% by mass, based on the total mass of the aqueous composition; 6. an article comprising a substrate surface-treated with any of the aqueous compositions of items 1 to 5; 7. the article of item 6, in which the substrate is silica particles or glass fiber; 8. a prepreg comprising the article of item 6 and a matrix resin; and 9. a printed wiring board comprising the prepreg of item 8.

[0011] According to the present invention, by using a nonionic surfactant, it is possible to prepare an aqueous composition of a highly hydrophobic organosilicon compound without using an organic solvent such as methanol. Articles such as inorganic fillers and glass cloth treated with this aqueous composition have improved resin properties, and can be endowed with excellent dielectric properties and durability, particularly when prepregged with a matrix resin.

[0012] The present invention will be described in detail below. [Aqueous Composition] The aqueous composition of the present invention contains (A) an organosilicon compound, (B) a nonionic surfactant, (C) an acid, and (D) water.

[0013] (A) Organosilicon Compound Component (A) is an organosilicon compound represented by the following formula (1): (RO) 3-n (CH3) n Si-Z (1)

[0014] In formula (1), each R independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Z represents a group having an ethylenically unsaturated bond, and n represents 0, 1, or 2, preferably 0. The alkyl group having 1 to 10 carbon atoms represented by R 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. Among these, R is more preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0015] Examples of the group having an ethylenically unsaturated bond for Z include —C p H 2p -Ar-CH=CH2, -C q H 2q -CH=CH2, -C q H 2q -OC(=O)-C(CH3)=CH2, -C q H 2q -OC(=O)-CH=CH2, -Cr H 2r -NHC(=O)-O-CX3, or -C r H 2r A group represented by --NHC(.dbd.O)--O--CH2--CX3 is preferred.

[0016] Ar represents an arylene group having 6 to 20 carbon atoms, preferably a phenylene group. Each X is independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an allyloxymethyl group, an acryloyloxymethyl group, or a methacryloyloxymethyl group, and at least one of X is an allyloxymethyl group, an acryloyloxymethyl group, or a methacryloyloxymethyl group.

[0017] p is an integer of 0 to 3, and preferably an integer of 0 to 2. q is an integer of 4 to 12, and preferably an integer of 4 to 8. r is an integer of 1 to 4, and preferably 3.

[0018] The organosilicon compound (A) is one in which the value of G calculated by the following formula (2) is 1.5 or more when S parts by mass of the organosilicon compound and 19×S parts by mass of ion-exchanged water are stirred at 25° C. and methanol is added dropwise until the liquids are compatible, where M parts by mass is the amount of methanol: G=M / 20S (2)

[0019] As a specific example, 19 g of ion-exchanged water is weighed into a glass bottle in a thermostatic chamber at 25°C. 1 g of 7-octenyltrimethoxysilane (KBM-1083; manufactured by Shin-Etsu Chemical Co., Ltd.) is added thereto, and after stirring for 10 seconds, methanol is added dropwise while stirring. Immediately after the start of the methanol addition, the highly hydrophobic 7-octenyltrimethoxysilane cannot dissolve in water, so the appearance of the liquid is non-uniform and cloudy. However, after 50 g has been added dropwise, the appearance of the liquid becomes uniform and transparent. At this time, G calculated from 50 / (20*1) is 2.5. There is no particular upper limit for G, but it is preferably 4.0 or less.

[0020] Specific examples of the component (A) include, but are not limited to, compounds represented by the following formulas (1-1) to (1-16).

[0021]

[0022] The component (A) may be commercially available or may be produced by a known method. For example, the organosilicon compounds having an alkyl linking chain and an alkenyl group represented by the above formulas (1-2) to (1-5) can be produced by reacting a diene compound with trimethoxysilane in the presence of a platinum catalyst. The organosilicon compounds represented by the above formulas (1-8) to (1-16) can be produced by reacting an alkoxysilane having an isocyanate group with an alcohol compound having an allyl group or a (meth)acryloyloxy group in the presence of a catalyst, but the production method is not limited to these.

[0023] From the viewpoints of stability and cost of the aqueous composition, the amount of component (A) is preferably 0.1 to 5.0 mass %, more preferably 0.2 to 3.0 mass %, based on the total mass of the aqueous composition.

[0024] (B) Nonionic surfactant The nonionic surfactant of component (B) is a component that functions as a dispersant for component (A), and can be appropriately selected from known surfactants, but in the present invention, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, polyoxyethylene modified organopolysiloxane, polyoxyethylene polyoxypropylene modified organopolysiloxane etc. are preferably used.These surfactants can be used alone or in combination of two or more.

[0025] Commercially available nonionic surfactants may also be used, and examples of commercially available nonionic surfactants include the Pronon series, Nonion series, Uniol series, and Unilube series manufactured by NOF Corp. More specific examples include Pronon 102, 201, 202, and 204, Nonion HT-505, HT-510, Uniol TG-330, and Unilube DGP-700.

[0026] The amount of component (B) is 0.0005 to 0.05% by mass, preferably 0.001 to 0.03% by mass, based on the total mass of the aqueous composition. If the amount is less than the lower limit, the stability of the composition may be insufficient, and if the amount is more than the upper limit, the dielectric properties and moist heat resistance of the treated article may be reduced.

[0027] (C) Acid Examples of the acid of component (C) include organic acids such as formic acid, acetic acid, propionic acid, citric acid, and oxalic acid; and inorganic acids such as hydrochloric acid. Among these, organic acids are preferred, and formic acid and acetic acid are more preferred. From the viewpoint of stability of the aqueous composition, the amount of component (C) is preferably 0.0001 to 5.0 mass%, and more preferably 0.0002 to 1.0 mass%, relative to the total mass of the aqueous composition.

[0028] The method for preparing the aqueous composition of the present invention is not particularly limited, and it can be prepared by mixing the above-mentioned components (A), (B), (C), and (D). In this case, a method in which component (A) is added to an aqueous solution in which components (B), (C), and (D) have been mixed in advance is preferred, and a method in which component (A) is added dropwise to the aqueous solution is more preferred. The temperature during mixing is preferably 10 to 50°C, more preferably 15 to 40°C.

[0029] To the aqueous composition of the present invention, an alkoxy group-containing organosilicon compound or a silazane structure-containing compound other than component (A) can be added as needed to improve adhesion and bonding to the substrate, as long as the effects of the present invention are not impaired. Specific examples of alkoxy group-containing organosilicon compounds and silazane structure-containing compounds include those exemplified in the method for producing surface-treated silica particles. When an alkoxy group-containing organosilicon compound or a silazane structure-containing compound is used, the amount added is preferably 0.01 to 0.2 mol per 1 mol of the total of component (A).

[0030] Furthermore, various additives may be added to the aqueous composition of the present invention as needed, provided that the effects of the present invention are not impaired. Specific examples of additives include water-soluble resins, curing catalysts, property adjusters for adjusting the tensile properties of the resulting cured coating, storage stability improvers, metal deactivators, antiozonants, lubricants, pigments, etc.

[0031] The aqueous composition of the present invention is preferably substantially free of organic solvents. Here, "substantially" means that the organic solvent content in the aqueous composition is 1% by mass or less, particularly 0.1% by mass or less.

[0032] [Article] The article according to the present invention includes a substrate surface-treated with the aqueous composition. The substrate used in the article according to 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 preferred from the viewpoint of the reactivity of the alkoxysilyl group.

[0033] 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 measured by dynamic light scattering is preferably 1 to 100 nm. Commercially available products such as these silica particles can be used, and examples 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., with Snowtex O being preferred.

[0034] 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. The dielectric loss tangent in the present invention refers to the value at 10 GHz measured by the method described in JIS R 1641:2007 (Method for measuring microwave dielectric properties of fine ceramic substrates).

[0035] 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 washing with hot water.

[0036] 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 more preferably 10 to 100 g / m 2 is.

[0037] [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.

[0038] The surface treatment method is not particularly limited, but specific examples include flow coating (dipping method), spin coating, etc. Typical curing conditions include heating and drying, and after treatment, the composition is preferably heated and dried at 60 to 180°C, preferably 80 to 150°C, for 5 minutes to 2 hours to remove water and simultaneously cause a chemical reaction between component (A) and the substrate surface.

[0039] [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 aqueous composition of the present invention can be prepregized by mixing 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.

[0040] (1) Articles The articles contained in the prepreg are not particularly limited as long as they include a substrate that has been surface-treated with the aqueous composition of the present invention. However, it is preferable that the surface-treated substrate itself, such as the surface-treated silica particles or surface-treated glass cloth, be used as the article.

[0041] (2) Matrix Resin The matrix resin in the present invention is impregnated into the glass cloth to form a prepreg, and either a thermosetting resin or a thermoplastic resin can be used. Resins with low dielectric properties are particularly preferred, and one or more resins selected from epoxy resins, silicone resins, polyimide resins, bismaleimide resins, polyphenylene ether resins, and polytetrafluoroethylene resins are more preferred. The matrix resin may be used alone or in combination with multiple resins. Resins other than the matrix resin can also be used, but resins with excellent dielectric properties are preferred. To produce a prepreg for a high-frequency substrate with excellent dielectric properties, it is preferable that the matrix resin also have excellent dielectric properties, and polyphenylene ether resins are particularly preferred.

[0042] 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, organic resins other than the matrix resin, etc. 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.

[0043] (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.

[0044] (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 is applied to and impregnated into glass cloth, thereby obtaining a prepreg containing surface-treated silica particles.

[0045] 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. Specific 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.

[0046] 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.

[0047] 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.

[0048] 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, an air doctor coater, a forward rotation roll coater, a blade coater, a knife coater, an impregnation coater, a MB coater, and an MB reverse coater.

[0049] 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. That is, if the amount of matrix resin attached 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. On the other hand, if the amount of matrix resin attached is 80% by mass or less, the amount of matrix resin is not too large, and resin flow during pressing is unlikely to occur. Note that the amount of matrix resin attached here refers to the mass % of the matrix resin relative to the total mass of the prepreg.

[0050] 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.

[0051] (3-2) Method for Producing Prepreg Comprising Surface-Treated Glass Cloth The glass cloth surface-treated with the aqueous solution of the present invention is preferably used to produce a prepreg by impregnating it with a matrix resin. When using a surface-treated glass cloth as an article, a matrix resin or a solution containing the matrix resin is mixed with other components as necessary, and the resulting resin or solution is impregnated into the surface-treated glass cloth to produce a prepreg comprising the surface-treated glass cloth. The specific production 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.

[0052] 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.

[0053] [Printed Wiring Board] The printed wiring board of the present invention comprises the prepreg described above. The method for producing the printed wiring board of the present invention is not particularly limited, and general methods for producing printed wiring boards can be applied. Specific examples include a method of heat-curing a laminate of one or more, preferably 2 to 20, sheets of the prepreg described above. Alternatively, the prepreg of the present invention can be superimposed on copper foil, pressed, and heat-cured 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 laminating prepregs in the same manner as described above, placing copper foil on one or both sides of the laminate, pressing, and heat-curing.

[0054] 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.

[0055] The copper foil may have a roughened layer and / or a heat-resistant layer and / or a rust-proofing layer and / or a chromate-treated layer and / or a plating layer and / or a silane coupling treatment layer. The roughened layer is not particularly limited, and any roughened layer or known roughened layer can be applied. The heat-resistant layer is not particularly limited, and any heat-resistant layer or known heat-proofing layer can be applied. The rust-proofing layer is not particularly limited, and any rust-proofing layer or known rust-proofing layer can be applied. The plating layer is not particularly limited, and any plating layer or known plating layer can be applied. The chromate layer is not particularly limited, and any chromate layer or known chromate layer can be applied.

[0056] Furthermore, after forming roughening particles from copper or a copper alloy, a roughening treatment can be performed in which secondary particles or tertiary particles are provided from nickel, cobalt, copper, zinc, or an alloy thereof. A heat-resistant or rust-proofing layer can then be formed from nickel, cobalt, copper, zinc, or an alloy thereof, and the surface can be further treated with chromate treatment, silane coupling treatment, or the like. Alternatively, a heat-resistant or rust-proofing layer can be formed from nickel, cobalt, copper, zinc, or an alloy thereof without performing a roughening treatment, and the surface can be further treated with chromate treatment, silane coupling treatment, or the like.

[0057] The silane coupling treatment layer can be formed by any known method, such as spraying a silane coupling agent solution, applying it with a coater, immersing it, pouring it, etc. Specific examples of the silane coupling agent that can be used include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane. However, as mentioned above, there is a demand for the use of silane coupling agents with higher hydrophobicity, and the water-soluble composition of the present invention can be applied to these.

[0058] The method for circuit processing of the copper-clad laminate 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.

[0059] 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 formulas, Me represents a methyl group.

[0060] (A) The parameter G of the organosilicon compound was measured by the following method. In a 25°C thermostatic chamber, S (g) of each organosilicon compound and 19 x S (g) of ion-exchanged water were weighed into a 100 mL glass bottle equipped with a Teflon (registered trademark) stirrer, and methanol was added dropwise while stirring. Methanol was added dropwise until the liquid changed from a non-uniform, cloudy appearance to a uniform, transparent appearance, and the parameter G was calculated based on the amount of methanol M (g) at that time using the following formula (2): G = M / 20S (2), where S is the amount of organosilicon compound (1 g in this example), and M is the amount of methanol at which the liquid becomes uniformly transparent.

[0061] Synthesis Example 1 100.0 g of glycerin dimethacrylate (NOF Corporation, Blemmer GMR-M) and 0.1 g of dioctyltin oxide were placed in a 300 mL separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, and 3-isocyanatepropyltrimethoxysilane was added dropwise over 1 hour at an internal temperature of 80 to 90°C. The amount of 3-isocyanatepropyltrimethoxysilane was 1.0 mole relative to the molar amount of hydroxyl groups calculated from the hydroxyl value of Blemmer GMR-M. The mixture was then stirred at 85°C for 3 hours to obtain organosilicon compound (A-5) represented by the following structural formula (1-12).

[0062]

[0063] Synthesis Example 2 100.0 g of trimethylolpropane diallyl ether (Neoallyl T-20, manufactured by Osaka Soda Co., Ltd.) and 0.1 g of dioctyltin oxide were placed in a 300 mL separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, and 3-isocyanatepropyltrimethoxysilane was added dropwise over 1 hour at an internal temperature of 80 to 90°C. The amount of 3-isocyanatepropyltrimethoxysilane used 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 to obtain organosilicon compound (A-6) represented by the following structural formula (1-9).

[0064]

[0065] Synthesis Example 3 100.0 g of pentaerythritol triallyl ether (Neoallyl P-30, manufactured by Osaka Soda Co., Ltd.) and 0.1 g of dioctyltin oxide were placed in a 300 mL separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, and 3-isocyanatepropyltrimethoxysilane was added dropwise over 1 hour at an internal temperature of 80 to 90°C. The amount of 3-isocyanatepropyltrimethoxysilane 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 to obtain organosilicon compound (A-7) represented by the following structural formula (1-10).

[0066]

[0067] [Examples 1 to 18, Comparative Examples 1 and 2] According to the blending amounts (parts by mass) shown in Tables 1, 2, and 3, (B) a nonionic surfactant was added to a mixed solution of (D) ion-exchanged water and (C) acetic acid, followed by stirring, and then (A) an organosilicon compound was added and stirred to prepare aqueous compositions. A silica glass cloth (thickness: 95 μm, mass per unit area: 93 g / m) was applied to the obtained aqueous composition. 2 ) and then heated and dried at 110°C for 10 minutes to produce a surface-treated glass cloth.

[0068] Comparative Example 3 An aqueous composition was prepared by adding an organosilicon compound (A-8) to a mixed solution of (D) ion-exchanged water and a nonionic surfactant (B-1) in the amounts (parts by mass) shown in Table 3 and stirring the mixture. A silica glass cloth (thickness: 95 μm, mass per unit area: 93 g / m) was added to the obtained aqueous composition. 2 ) and then heated and dried at 110°C for 10 minutes to produce a surface-treated glass cloth.

[0069] Comparative Example 4 An aqueous composition was prepared by adding organosilicon compound (A-7) to a mixed solution of (D) ion-exchanged water and (C) acetic acid in the amounts (parts by mass) shown in Table 3 and stirring. A silica glass cloth (thickness: 95 μm, mass per unit area: 93 g / m) was added to the obtained aqueous composition. 2 ) and then heated and dried at 110°C for 10 minutes to produce a surface-treated glass cloth.

[0070] Comparative Example 5 An aqueous composition was prepared by adding organosilicon compound (A-8) to (D) ion-exchanged water and stirring the mixture in the amounts (parts by mass) shown in Table 3. The obtained aqueous composition was coated with silica glass cloth (thickness: 95 μm, mass per unit area: 93 g / m 2 ) and then heated and dried at 110°C for 10 minutes to produce a surface-treated glass cloth.

[0071] [Comparative Example 6] When organosilicon compound (A-1) was added to a mixed solution of (D) ion-exchanged water and (C) acetic acid in the amounts (parts by mass) shown in Table 3 and stirred, the treatment solution did not become uniform and a large amount of insoluble matter was produced, making it impossible to perform glass cloth treatment.

[0072] (A) Organosilicon Compounds (A-1): 7-octenyltrimethoxysilane (trade name: KBM-1083, manufactured by Shin-Etsu Chemical Co., Ltd.) (A-2): 5-hexenyltrimethoxysilane (trade name: KBM-1063, manufactured by Shin-Etsu Chemical Co., Ltd.) (A-3): 8-methacryloyloxyoctyltrimethoxysilane (trade name: KBM-5083, manufactured by Shin-Etsu Chemical Co., Ltd.) (A-4): p-styryltrimethoxysilane (trade name: KBM-1403, manufactured by Shin-Etsu Chemical Co., Ltd.) (A-5): Organosilicon compound represented by the above formula (1-12) obtained in Synthesis Example 1 (A-6): Organosilicon compound represented by the above formula (1-9) obtained in Synthesis Example 2 (A-7): Organosilicon compound represented by the above formula (1-10) obtained in Synthesis Example 3 (A-8): 3-methacryloyloxypropyltrimethoxysilane (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) (A-9): 3-aminopropyltrimethoxysilane (trade name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0073] (B) Nonionic surfactants (B-1) Pronon 201 (manufactured by NOF Corporation) (B-2) Pronon 102 (manufactured by NOF Corporation) (B-3) Pronon 202 (manufactured by NOF Corporation) (B-4) Pronon 204 (manufactured by NOF Corporation) (B-5) Nonion HT-505 (manufactured by NOF Corporation) (B-6) Nonion HT-510 (manufactured by NOF Corporation) (B-7) Uniol TG-330 (manufactured by NOF Corporation) (B-8) Unilube DGP-700 (manufactured by NOF Corporation)

[0074] The obtained surface-treated glass cloth was evaluated by the following methods, and the results are shown in Tables 1, 2 and 3 below.

[0075] [Dielectric Properties] A rectangular molded piece of 5 cm x 5 cm was prepared from the obtained surface-treated glass cloth. A network analyzer (Keysight: E5063-2D5) was connected to a strip line (Keycom Co., Ltd.) to measure the relative permittivity and dielectric loss tangent at a frequency of 10 GHz.

[0076] The obtained surface-treated glass cloth was impregnated with matrix resin (M-1), heated and dried at 100 ° C. for 10 minutes to remove the solvent and form a prepreg. One prepreg was then heated and cured at 180 ° C. for 60 minutes using a vacuum press under a pressure of 2 MPa to produce a cured prepreg. Here, the matrix resin (M-1) was a mixture of 60 parts by mass of methacryloxy group-containing polyphenylene ether resin (trade name: SA-9000, manufactured by SHPP Japan LLC), 15 parts triallyl isocyanurate, and 25 parts of polybutadiene (trade name: RICON 100, manufactured by Cray Valley Corporation) to which toluene was added so that the resin concentration was 55% by mass, followed by the addition of 1 part dicumyl peroxide as a curing catalyst.

[0077] The cured prepregs obtained were evaluated by the following methods, and the results are shown in Tables 1, 2 and 3.

[0078] [Dielectric properties] The relative permittivity and dielectric loss tangent of the cured product of each prepreg were measured in the same manner as for the surface-treated glass cloth. [Wet heat resistance] The obtained cured prepreg was cut into a 5 cm square, and the cut-out cured product was 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 cured product was observed and evaluated according to the following criteria. ◯: No blistering occurred. ×: Blistering occurred.

[0079]

[0080]

[0081]

[0082] As shown in Tables 1 and 2, glass cloth treated with the aqueous composition of the present invention and cured prepregs using the same have low dielectric loss tangents and high moist heat resistance. On the other hand, as shown in Table 3, in Comparative Example 1, in which an excessive amount of nonionic surfactant was used, the resulting glass cloth and cured prepreg had high dielectric constants and dielectric loss tangents, and also had poor moist heat resistance. Furthermore, in Comparative Examples 2 to 5, in which an organosilicon compound with a small G value was used, the resulting glass cloth and cured prepreg had high dielectric loss tangents and tended to have poor moist heat resistance.

Claims

1. (A) An organosilicon compound represented by the following formula (1): (RO) 3-n (CH3) n Si-Z (1) (wherein R each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Z represents a group having an ethylenically unsaturated bond, and n represents 0, 1, or 2.) An aqueous composition comprising: (B) a nonionic surfactant; (C) an acid; and (D) water, wherein the amount of the (B) nonionic surfactant is 0.0005 to 0.05% by mass relative to the total mass of the aqueous composition; and the (A) organosilicon compound has a G value calculated by the following formula (2) of 1.5 or greater, when S parts by mass of the organosilicon compound and 19 x S parts by mass of ion-exchanged water are stirred at 25°C and methanol is added dropwise until the liquids become compatible, where M parts by mass is the amount of methanol. G = M / 20S (2) 2. The Z is -C p H 2p -Ar-CH=CH2, -C q H 2q -CH=CH2, -C q H 2q -OC(=O)-C(CH3)=CH2, -C q H 2q -OC(=O)-CH=CH2, -C r H 2r -NHC(=O)-O-CX3, or -C r H 2r 2. The aqueous composition according to claim 1, which is a group represented by the formula: -NHC(=O)-O-CH2-CX3 (wherein Ar represents an arylene group having 6 to 20 carbon atoms; each X is independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an allyloxymethyl group, an acryloyloxymethyl group, or a methacryloyloxymethyl group, and at least one of X is an allyloxymethyl group, an acryloyloxymethyl group, or a methacryloyloxymethyl group; p is an integer of 0 to 3; q is an integer of 4 to 12; and r is an integer of 1 to 4).

3. The aqueous composition according to claim 1, wherein the (B) nonionic surfactant is one or more selected from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbit fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, polyoxyethylene-modified organopolysiloxanes, and polyoxyethylene polyoxypropylene-modified organopolysiloxanes.

4. The aqueous composition according to claim 1, wherein the acid (C) is one or more selected from the group consisting of hydrochloric acid, formic acid, acetic acid, propionic acid, citric acid and oxalic acid.

5. The aqueous composition according to claim 1, wherein the amount of said (A) organosilicon compound is 0.1 to 5.0 mass % and the amount of said (C) acid is 0.0001 to 5.0 mass % based on the total mass of the aqueous composition.

6. An article comprising a substrate whose surface has been treated with the aqueous composition according to any one of claims 1 to 5.

7. The article of claim 6, wherein said substrate is silica particles or glass fibers.

8. A prepreg comprising the article of claim 6 and a matrix resin.

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

Images