Surface-treated glass cloth, prepreg, printed wiring board, and glass cloth surface treatment agent

Abstract

Provided are: a surface-treated glass cloth that has a hard texture, i.e., high flexural rigidity, can suppress wrinkle formation during roll-to-roll transport, is unlikely to cause voids to be left in a printed wiring board, and can improve insulation reliability; a prepreg; a printed wiring board; and a glass cloth surface treatment agent. This surface-treated glass cloth comprises a surface-treated layer on the surface of a glass cloth formed from glass yarns composed of a plurality of glass filaments as warps and wefts. The surface-treated layer is treated with an amino group-containing organosilicon compound or a mixture of salts thereof, said compound being represented by general formula (1) (in formula (1), R1 represents an arylene group or a C1-C10 cyclic or acyclic divalent hydrocarbon group, R2 and R3 each independently represent a group selected from the group consisting of hydrogen and C1-C10 monovalent hydrocarbon groups, R4 represents an arylene group or a C1-C10 cyclic or acyclic divalent hydrocarbon group, n represents an integer of 0, 1, or 2, and Q1, Q2, and Q3 each independently represent a functional group selected from the group consisting of hydrogen atoms, benzyl groups, and vinylbenzyl groups). The benzyl group content of 1 mole of the amino group-containing organosilicon compound represented by general formula (1) or salts thereof is 0.1-0.8 mol.

Description

Surface-treated glass cloth, prepreg, printed wiring board, and glass cloth surface treatment agent

[0001] The present invention relates to a surface-treated glass cloth, a prepreg, a printed wiring board, and a glass cloth surface treatment agent.

[0002] Currently, the performance of information terminals such as smartphones is being improved, and high-speed communication represented by 5G communication is progressing. Along with such a background, not only an improvement in heat resistance that has been conventionally required for printed wiring boards for high-speed communication, but also a further improvement in the dielectric properties of the insulating material (for example, lowering the dielectric tangent) is desired. Similarly, there is a background in which an improvement in dielectric properties is desired for prepregs used as insulating materials for printed wiring boards, glass fibers contained in the prepregs, and glass cloths.

[0003] In order to reduce the dielectric constant of an insulating material, a method of forming an insulating material using a prepreg in which a glass cloth is impregnated with a low-dielectric resin (hereinafter referred to as a "matrix resin") that is thermally cured by a radical reaction such as a terminal-modified polyphenylene ether (terminal-modified PPE) is known (Patent Document 1). Further, for the purpose of improving the adhesion to the resin by a crosslinking reaction with the matrix resin, a method of surface-treating the glass cloth used in the prepreg with a silane coupling agent having an acryloxy group or a methacryloxy group is known (Patent Document 2).

[0004] However, the glass cloth treated with the silane coupling agent having an acryloxy group or a methacryloxy group described in Patent Document 2 has a soft texture, that is, low flexural rigidity, so that wrinkles are likely to occur during roll-to-roll conveyance, resulting in poor appearance and a decrease in yield.

[0005] In addition, as a required characteristic of the glass cloth used for a printed wiring board, reducing the number of remaining voids is mentioned. As a mechanism for remaining voids, voids remaining in a prepreg obtained by impregnating a glass cloth with a matrix resin and semi-curing it remain even after passing through a press molding process. For the glass cloth, a glass cloth having excellent impregnation properties with respect to a wide range of matrix resins and hardly remaining voids, as described in Patent Document 1, has been strongly demanded.

[0006] International Publication No. 2014 / 203511 International Publication No. 2019 / 167391

[0007] The present invention has been made to solve the above-described problems of the prior art, and provides a surface-treated glass cloth, prepreg, printed wiring board, and glass cloth surface treatment agent that have a hard texture, that is, high flexural rigidity, can suppress the occurrence of wrinkles during roll-to-roll conveyance, hardly leave voids in the printed wiring board, and can improve insulation reliability.

[0008] As a result of intensive studies on the above problems, the present inventors have reached the present invention. That is, in order to solve the above problems, one aspect of the present invention includes the following aspects.

[0009] [1] A surface-treated glass cloth having a surface treatment layer on the surface of a glass cloth composed of a plurality of glass filaments as warp and weft, wherein the surface treatment layer has the following general formula (1):

[0010]

[0011] [In formula (1), R １ represents an arylene group or a cyclic or acyclic divalent hydrocarbon group of C １ to C １０ R ２ and R ３ each independently represent a group selected from the group consisting of hydrogen and a monovalent hydrocarbon group of C １ to C １０ R ４ represents an arylene group or a C １ to C １０Q represents a cyclic or acyclic divalent hydrocarbon group, where n represents an integer of 0, 1, or 2. １ Q ２ , and Q ３ Each of these independently represents a functional group selected from the group consisting of a hydrogen atom, a benzyl group, and a vinylbenzyl group.

[0012] A surface-treated glass cloth, comprising a layer treated with a mixture of an amino group-containing organosilicon compound represented by the general formula (1) or a salt thereof, wherein the content of benzyl groups in 1 mole of the amino group-containing organosilicon compound represented by the general formula (1) or a salt thereof is 0.1 moles or more and 0.8 moles or less.

[0013] [2] The surface-treated glass cloth according to [1], wherein the content of vinylbenzyl groups in 1 mole of an amino group-containing organosilicon compound represented by the general formula (1) or a salt thereof is 1.1 moles or more and 2.5 moles or less.

[0014] [3] The surface-treated glass cloth according to [1] or [2], wherein the surface-treated layer is a layer further treated with an organosilicon compound containing a carbon-carbon unsaturated double bond group.

[0015] [4] The surface-treated glass cloth according to [3], characterized in that the organosilicon compound containing the carbon-carbon unsaturated double bond group contains a (meth)acryloyl group.

[0016] [5] The surface-treated glass cloth according to [4], wherein the organosilicon compound containing the carbon-carbon unsaturated double bond group is at least one selected from the group consisting of 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, and 3-acryloxypropyltriethoxysilane.

[0017] A prepreg comprising a surface-treated glass cloth according to any one of items [6] [1] to [5] and a matrix resin composition impregnated into the glass cloth.

[0018] [7] The prepreg according to [6], wherein the matrix resin composition comprises a polyphenylene ether resin.

[0019] A printed circuit board comprising a surface-treated glass cloth according to any one of items [8] [1] to [5], and a cured product of a matrix resin composition impregnated into the glass cloth.

[0020] [9] The printed circuit board according to [8], wherein the matrix resin composition comprises a polyphenylene ether resin.

[0021]

[10] The following general formula (1):

[0022]

[0023] [In formula (1), R １ is an allerene group or C １ ~C １０ R represents a cyclic or acyclic divalent hydrocarbon group. ２ and R ３ These are, independently, hydrogen and C １ ~C １０ R represents a group selected from the group consisting of monovalent hydrocarbon groups. ４ is an allerene group or C １ ~C １０ Q represents a cyclic or acyclic divalent hydrocarbon group, where n represents an integer of 0, 1, or 2. １ Q ２ , and Q ３ A glass cloth surface treatment agent comprising a mixture of an amino group-containing organosilicon compound or a salt thereof represented by [where each independently represents a functional group selected from the group consisting of a hydrogen atom, a benzyl group, and a vinylbenzyl group], wherein the content of benzyl groups in 1 mole of the amino group-containing organosilicon compound or salt thereof represented by the general formula (1) is 0.1 moles or more and 0.8 moles or less.

[0024]

[11] The glass cloth surface treatment agent according to

[10] , further comprising a surfactant.

[0025]

[12] The glass cloth surface treatment agent according to

[10] or

[11] , wherein the content of vinylbenzyl groups in 1 mole of an amino group-containing organosilicon compound represented by the general formula (1) or a salt thereof is 1.1 moles or more and 2.5 moles or less.

[0026]

[13] A glass cloth surface treatment agent according to any one of

[10] to

[12] , wherein the residual amounts of benzyl halide and vinyl benzyl halide, which are reaction raw materials, are 0.02 moles or less per mole of an amino group-containing organosilicon compound represented by the general formula (1) or a salt thereof.

[0027]

[14] A glass cloth surface treatment agent according to any one of

[10] to

[13] , further comprising an organosilicon compound containing a carbon-carbon unsaturated double bond group.

[0028]

[15] The glass cloth surface treatment agent according to

[14] , wherein the organosilicon compound containing the carbon-carbon unsaturated double bond group contains a (meth)acryloyl group.

[0029]

[16] The glass cloth surface treatment agent according to

[15] , wherein the organosilicon compound containing the carbon-carbon unsaturated double bond group is at least one selected from the group consisting of 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, and 3-acryloxypropyltriethoxysilane.

[0030]

[17] The glass cloth surface treatment agent according to any one of

[14] to

[16] , wherein the molar concentration of a mixture of an amino group-containing organosilicon compound represented by the general formula (1) or a salt thereof, relative to the total amount of organosilicon compounds, is 1 to 100%.

[0031] A surface-treated glass cloth treated with any one of the glass cloth surface treatment agents described in

[18] ,

[10] , to

[17] .

[0032] A prepreg comprising the surface-treated glass cloth described in

[19] and

[18] , and a matrix resin composition impregnated into the glass cloth.

[0033]

[20] The prepreg according to

[19] , wherein the matrix resin composition comprises a polyphenylene ether resin.

[0034] A printed circuit board comprising a surface-treated glass cloth as described in

[21] and

[18] , and a cured product of a matrix resin composition impregnated into the glass cloth.

[0035]

[22] The printed circuit board according to

[21] , wherein the matrix resin composition comprises a polyphenylene ether resin.

[0036] According to the present invention, it is possible to provide a surface-treated glass cloth, prepreg, printed circuit board, and glass cloth surface treatment agent that have a hard texture, i.e., high bending rigidity, can suppress the occurrence of wrinkles during roll-to-roll transport, and can improve insulation reliability by preventing voids from remaining in the printed circuit board.

[0037] The embodiments of this disclosure (hereinafter referred to as "these embodiments") will be described below. However, the present invention is not limited to these embodiments, and various modifications are possible without departing from the spirit of the invention.

[0038] In this specification, if there are multiple structures represented by the same reference numeral in the same formula, unless otherwise specified, these structures may be selected independently and may be identical or different from one another. Similarly, if there are multiple structures represented by the same reference numeral in different formulas, unless otherwise specified, these structures may be selected independently and may be identical or different from one another. In this specification, various measurements are performed according to the methods described in the examples unless otherwise specified. In this specification, upper or lower limits in stepped numerical ranges may be replaced by upper or lower limits in corresponding other stepped numerical ranges, and further, by corresponding values ​​described in the examples.

[0039] The surface-treated glass cloth of the present invention is a glass cloth composed of glass threads made of multiple glass filaments as warp and weft threads, and is provided with a surface treatment layer on its surface, characterized in that the surface treatment layer is formed by treatment with a mixture of an amino group-containing organosilicon compound having a specific structure described later or a salt thereof (preferably a hydrochloride salt).

[0040] [Surface-treated glass cloth] The surface-treated glass cloth according to the present invention is a surface-treated glass cloth that is woven using glass yarn containing a plurality of glass filaments as warp and weft threads, and is surface-treated with a glass cloth surface treatment agent. As the glass fibers (glass filaments) constituting the glass cloth, generally, low dielectric constant glass such as E glass (alkali-free glass) used for printed circuit board applications; D glass, L glass, NE glass, L2 glass, silica glass, and quartz glass; high-strength glass such as S glass and T glass; and high dielectric constant glass such as H glass can be used. The glass fibers may consist of one type of glass material, or they may be a combination of two or more types of glass fibers made of different glass materials.

[0041] [Weaving structure of glass cloth] In one embodiment, the weaving structure of the glass cloth can be, for example, plain weave, twill weave, satin weave, etc. Among these, the plain weave structure is preferred.

[0042] [Density] In one embodiment, the density of the warp and weft threads constituting the glass cloth is preferably 10 to 120 threads / inch (= 10 to 120 threads / 25 mm), more preferably 40 to 100 threads / inch. The effects of the present invention are easily obtained when the density is within the above range. The density of the warp and weft threads may be different from each other.

[0043] [Basis Weight] In one embodiment, the basis weight (mass of the glass cloth) of the glass cloth is preferably 8 to 250 g / m². ２ More preferably 8 to 100 g / m ２ More preferably 8 to 80 g / m ２ Particularly preferred is 8 to 50 g / m２ Therefore, if the basis weight of the glass cloth is within the above range, the effects of the present invention are more easily obtained.

[0044] [Thickness] In one embodiment, the thickness of the glass cloth is preferably 5 μm to 100 μm, more preferably 20 μm to 100 μm, and even more preferably 30 to 90 μm. The effects of the present invention are easily obtained when the thickness of the glass cloth is within the above range.

[0045] [Bending Stiffness] In one embodiment, the texture of the glass cloth, i.e., the value of the bending stiffness of the glass cloth, is determined by dividing the value of the bending stiffness in the warp direction obtained by measurement by the weight of the glass cloth. The value of bending stiffness per weight is preferably 0.0007 to 0.0030, more preferably 0.0008 to 0.0020, and even more preferably 0.0010 to 0.0020. If the bending stiffness per weight is less than 0.0007, the texture is too soft, and wrinkles tend to form in the glass cloth. In this embodiment, the unit of bending stiffness of the glass cloth is (gf・cm). ２ / cm / (g / m) ２ ))

[0046] [Surface Treatment] In one embodiment, the glass threads (including glass filaments) of the glass cloth are surface-treated with a glass cloth surface treatment agent containing an organosilicon compound having a specific chemical structure represented by general formula (1). This improves the reactivity with the matrix resin.

[0047] [Mixture of amino group-containing organosilicon compounds or salts thereof] In the mixture of amino group-containing organosilicon compounds or salts thereof for treating the surface-treated glass cloth of the present invention, the amino group-containing organosilicon compound is of the following general formula (1):

[0048]

[0049] [In formula (1), R １ is an allerene group or C １ ~C １０ R represents a cyclic or acyclic divalent hydrocarbon group. ２ and R ３These are, independently, hydrogen and C １ ~C １０ R represents a group selected from the group consisting of monovalent hydrocarbon groups. ４ is an allerene group or C １ ~C １０ Q represents a cyclic or acyclic divalent hydrocarbon group, where n represents an integer of 0, 1, or 2. １ Q ２ , and Q ３ Each of these independently represents a functional group selected from the group consisting of a hydrogen atom, a benzyl group, and a vinylbenzyl group. When it is a salt, it is a salt using a monovalent or greater anion. The type of anion is not particularly limited, but it may be any monovalent anion, preferably a halide anion selected from fluorine, chlorine, bromine, and iodine, and a salt with a bromide ion or chloride ion as a counteranion is preferred. Industrially, the salt of the amino group-containing organosilicon compound according to the present invention is particularly preferably in the form of a hydrochloride salt using a chloride ion.

[0050] In one embodiment, R １ The arylene group is a substituted or unsubstituted divalent aromatic group, which may be selected from the group consisting of benzene, toluene, xylene, ethylbenzene, cumene, phenol, benzyl alcohol, anisole, acetophenone, cresol, catechol, resorcinol, hydroquinone, benzophenone, naphthalene, biphenyl, anthracene, phenanthrene, terphenyl, triphenylmethane, pyrene, and tetracene, and is preferably phenyl, biphenyl, or terphenyl. If the aromatic group is substituted, it may be substituted with a hydroxyl group, halogen, alkyl group, or alkoxy group. The arylene group may preferably be selected from the group consisting of phenylene, methylphenylene, ethylphenylene, naphthylene, biphenylylene, terphenylene, anthrylene, and phenanthrylene. The number of carbon atoms in the arylene group is preferably 5 to 30, and more preferably 6 to 20.

[0051] In one embodiment, R １ C １~C １０ The cyclic or acyclic divalent hydrocarbon groups are, but are not limited to, alkylene groups, cycloalkylene groups, arylene groups, and aralkylene groups; or groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as chlorine, bromine, and fluorine. Examples of alkylene groups include methylene groups, ethylene groups, propylene groups, butylene groups, pentylene groups, and hexylene groups. Examples of cycloalkylene groups include cyclopropylene groups, cyclobutylene groups, cyclopentylene groups, cyclohexylene groups, 1-methylcyclopropylene groups, 2-methylcyclopropylene groups, and 2,2-dimethylcyclopropylene groups. An example of an arylene group is phenylene. An example of an aralkylene group is benzylene. The number of carbon atoms in the divalent hydrocarbon group is preferably 1 to 8, and more preferably 1 to 6.

[0052] In one embodiment, R ２ and R ３ C １ ~C １０ The monovalent hydrocarbon groups are not limited to these, but include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups; or groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as chlorine, bromine, and fluorine. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-methylcyclopropyl, 2-methylcyclopropyl, and 2,2-dimethylcyclopropyl groups. An example of an aryl group is the phenyl group. An example of an aralkyl group is the benzyl group. The number of carbon atoms in the monovalent hydrocarbon group is preferably 1 to 8, and more preferably 1 to 6.

[0053] In one embodiment, R ４ The arylene group and C １ ~C １０ The cyclic or acyclic divalent hydrocarbon group is R １ It is a similar base.

[0054] In one embodiment, n is an integer of 0, 1, or 2, preferably 0 or 1. In formula (1), OR ３ The group is hydrolyzable and decomposes to form a bond with the glass cloth.

[0055] Q １ Q ２ , and Q ３ Each of these independently represents a functional group selected from the group consisting of a hydrogen atom, a benzyl group, and a vinylbenzyl group, of which the vinylbenzyl group is the group that forms a bond with the matrix resin impregnated into the glass cloth.

[0056] In one embodiment, the benzyl group content in one mole of the amino group-containing organosilicon compound represented by general formula (1) or its salt is 0.1 moles or more and 0.8 moles or less, preferably 0.2 moles or more and 0.8 moles or less. By setting the benzyl group content within the above range, it is possible to provide a glass cloth with excellent compatibility with the matrix resin and a laminate with a low number of voids. If the benzyl group content is less than 0.1 moles, it is thought that the wettability to the matrix resin decreases, making it difficult for the resin to spread uniformly. If the benzyl group content exceeds 0.8 moles, it is thought that the chemical bond formation reaction between the matrix resin and the organosilicon compound tends to become non-uniform, thereby promoting the formation of voids.

[0057] In one embodiment, the content of vinylbenzyl groups in one mole of an amino group-containing organosilicon compound represented by general formula (1) or its salt is 1.1 moles or more and 2.5 moles or less, preferably 1.2 moles or more and 2.3 moles or less, and more preferably 1.2 moles or more and 2.1 moles or less. By setting the content of vinylbenzyl groups within the above range, it is possible to provide glass cloth with excellent compatibility with the matrix resin and laminates with a low number of voids.

[0058] In one embodiment, a mixture of an amino group-containing organosilicon compound represented by general formula (1) or a salt thereof is characterized by a small amount of residual benzyl halide (particularly benzyl bromide or benzyl chloride) and vinyl benzyl halide (particularly vinyl benzyl chloride or vinyl benzyl bromide), which are reaction raw materials. The residual amounts of benzyl halide and vinyl benzyl halide are 0.02 moles or less each per mole of the amino group-containing organosilicon compound represented by general formula (1) or a salt thereof. Preferably, the residual amounts of benzyl chloride and vinyl benzyl chloride are 0.017 moles or less each per mole of the amino group-containing organosilicon compound represented by general formula (1) or a salt thereof. By setting the residual amounts of benzyl chloride and vinyl benzyl chloride within the above range, a glass cloth with excellent compatibility with the matrix resin can be provided, and a laminate with a low void number can be provided.

[0059] [Method for producing a mixture of amino group-containing organosilicon compounds or salts thereof] In one embodiment, a mixture of amino group-containing organosilicon compounds or salts thereof represented by general formula (1) is given by the following general formula (2):

[0060] [In formula (2), R １ is an allerene group or C １ ~C １０ R represents a cyclic or acyclic divalent hydrocarbon group. ２ and R ３ These are, independently, hydrogen and C １ ~C １０ R represents a group selected from the group consisting of monovalent hydrocarbon groups. ４ is an allerene group or C １ ~C １０ [This represents a cyclic or acyclic divalent hydrocarbon group, where n is an integer of 0, 1, or 2]

[0061] The amino group-containing organosilicon compound represented by the following general formula (3):

[0062] [In formula (3), X represents a halogen atom]

[0063] It is produced by a manufacturing method that includes a step of reacting halomethylstyrene represented by [formula]. The benzyl halogen may be benzyl chloride or benzyl bromide.

[0064] In one embodiment, R of general formula (2) １ ~R ４ And n are R as described in general formula (1). １ ~R ４ And are the same base and integer as n.

[0065] In one embodiment, it is preferable that the amino group-containing organosilicon compound represented by general formula (2) is one or more selected from the group consisting of 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, and 3-(2-aminoethylamino)propyldimethoxymethylsilane.

[0066] In one embodiment, the halogen atom may be fluorine, chlorine, bromine, or iodine, and may be chlorine or bromine in order to give a chloride ion or bromide ion.

[0067] In one embodiment, the halomethylstyrene represented by general formula (3) is preferably fluoromethylstyrene, chloromethylstyrene, or bromomethylstyrene, and is particularly preferably chloromethylstyrene.

[0068] [Glass Cloth Surface Treatment Agent] The present invention also relates to a glass cloth surface treatment agent comprising a mixture of an amino group-containing organosilicon compound represented by the general formula (1) of the present invention or a salt thereof (preferably a hydrochloride salt).

[0069] The glass cloth surface treatment agent of the present invention may contain solvents such as water, alcohols, ethers, and ketones. The solvent contained in the glass cloth surface treatment agent is for dissolving a mixture of an amino group-containing organosilicon compound represented by general formula (1) or a salt thereof, and a water-soluble solvent is preferred.

[0070] In one embodiment, examples of solvents for alcohols include methanol, ethanol, propanol, ethylene glycol, propanediol, butanediol, and glycerin. Examples of solvents for ethers include diethyl ether, dioxane, trioxane, tetrahydrofuran, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether. Examples of solvents for ketones include acetone and methyl ethyl ketone. In addition, solvents having both a hydroxyl group and an ether group in the same molecule, such as 2-methoxyethanol and tetrahydrofurfuryl alcohol, can also be used.

[0071] In one embodiment, the glass cloth surface treatment agent of the present invention is preferably acidic in order to enhance the dispersibility and stability of the mixture of an amino group-containing organosilicon compound represented by general formula (1) or a salt thereof. Examples of acids for making the glass cloth surface treatment agent acidic include organic acids such as formic acid, acetic acid, citric acid, and propionic acid, as well as inorganic acids such as hydrochloric acid, with acetic acid being preferred.

[0072] The solvent in the glass cloth surface treatment agent of the present invention can be used alone, or two or more solvents can be used in combination.

[0073] In one embodiment, the glass cloth surface treatment agent of the present invention may contain an organosilicon compound having a carbon-carbon unsaturated double bond group, other than a mixture of an amino group-containing organosilicon compound represented by the general formula (1) of the present invention or a salt thereof. This makes it easier to improve reactivity with the matrix resin. Furthermore, it makes it less likely for hydrophilic functional groups to be formed after reaction with the matrix resin, and thus easier to improve insulation reliability. The organosilicon compound having a carbon-carbon unsaturated double bond group preferably contains a (meth)acryloyl group. Examples of organosilicon compounds having a carbon-carbon unsaturated double bond group include vinyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropyltriethoxysilane, 5-hexenyltrimethoxysilane, and p-styryltrimethoxysilane. From the viewpoint of reactivity with the matrix resin, it is preferable to use 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, or 3-acryloxypropyltriethoxysilane.

[0074] Organosilicon compounds containing carbon-carbon unsaturated double bond groups can be used individually, or in combination of two or more.

[0075] In one embodiment, the molar concentration of the mixture of amino group-containing organosilicon compounds represented by general formula (1) or their salts, relative to the total amount of organosilicon compounds, is preferably 1 to 100%. This enhances the impregnation of the glass cloth into the matrix resin. The molar concentration of the mixture of amino group-containing organosilicon compounds represented by general formula (1) or their salts is preferably 3 to 100%, and more preferably 5 to 100%.

[0076] In one embodiment, the glass cloth surface treatment agent of the present invention may contain a surfactant to improve dispersibility and stability. As the surfactant, any of anionic surfactants, cationic surfactants, or nonionic surfactants may be used. From the viewpoint of improving the insulation reliability of printed circuit boards, it is preferable to use a nonionic surfactant. Examples of anionic surfactants include fatty acid monocarboxylates, polyoxyethylene alkyl ether carboxylates, N-acyl sarcosine salts, N-acyl glutamate salts, dialkyl sulfosuccinates, alkane sulfonates, alpha-olefin sulfonates, linear alkylbenzene sulfonates, alkylbenzene sulfonates, naphthalene sulfonate-formaldehyde condensates, alkyl naphthalene sulfonates, N-methyl-N-acyl taurate salts, alkyl sulfates, polyoxyethylene alkyl ether sulfates, oil and fat sulfate esters, alkyl phosphates, polyoxyethylene alkyl ether phosphates, and polyoxyethylene alkylphenyl ether phosphates. Cationic surfactants include monoalkylamine salts, dialkylamine salts, trialkylamine salts, alkyltrimethylammonium chloride, and alkylbenzalkonium chloride. Nonionic surfactants include glycerin fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polyoxypropylene glycol, fatty acid polyethylene glycol, fatty acid polyoxyethylene sorbitan, and fatty acid alkanolamides.

[0077] The concentration of the surfactant in the glass cloth surface treatment agent is preferably 1% by mass or less, and more preferably 0.1% by mass or less from the viewpoint of improving the insulation reliability of the printed circuit board.

[0078] In one embodiment, the concentration of the mixture of an amino group-containing organosilicon compound represented by general formula (1) or a salt thereof contained in the glass cloth surface treatment agent of the present invention is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and most preferably 0.1 to 5% by mass, relative to the glass cloth surface treatment agent.

[0079] [Method for producing the glass cloth surface treatment agent] The method for producing the glass cloth surface treatment agent of the present invention is to directly add a mixture of an amino group-containing organosilicon compound represented by general formula (1) or a salt thereof (preferably a hydrochloride salt) to a solvent, or to dissolve a mixture of an amino group-containing organosilicon compound represented by general formula (1) or a salt thereof in a water-soluble organic solvent to make an organic solvent solution, and then add the organic solvent solution to water.

[0080] [Method for Surface Treatment of Glass Cloth] Possible methods for applying the glass cloth surface treatment agent to the glass cloth include: (a) a method in which the glass cloth surface treatment agent is placed in a bath and the glass cloth is immersed and passed through it (hereinafter referred to as the "immersion method"), and (b) a method in which the glass cloth surface treatment agent is directly applied to the glass cloth using a roll coater, die coater, or gravure coater. When applying by the immersion method described in (a) above, it is preferable to select an immersion time of the glass cloth in the glass cloth surface treatment agent of 0.5 seconds or more and 1 minute or less.

[0081] [Opening the Fibers of Glass Cloth] The method for manufacturing glass cloth may further include a step of opening the fibers of the surface-treated glass cloth. The method of opening the fibers is not particularly limited, but examples include spray water (high-pressure water opening), vibro-washer, ultrasonic water, mangle, etc. In terms of adjusting the weight loss coefficient to the specific range of this disclosure and obtaining good fluff quality, spray water (high-pressure water opening) is preferred. The water pressure of the high-pressure water spray for high-pressure water opening is preferably 1.0 kg / cm² or more and 15.0 kg / cm² or less, more preferably 1.0 kg / cm² or more and 10.0 kg / cm² or less, and even more preferably 1.0 kg / cm² or more and 5.0 kg / cm² or less.

[0082] Furthermore, known methods such as hot air and electromagnetic waves can be used to heat and dry the solvent after applying a glass cloth surface treatment agent to the glass cloth.

[0083] The heating and drying temperature is preferably 90°C or higher, and more preferably 100°C or higher, so that the reaction between the organosilicon compound and the glass can proceed sufficiently. Furthermore, the heating and drying temperature is preferably 300°C or lower, and more preferably 200°C or lower, in order to prevent deterioration of the organic functional groups of the organosilicon compound.

[0084] [Prepreg] The prepreg of the present invention comprises the above-mentioned glass cloth and a matrix resin composition impregnated into the glass cloth. This makes it possible to provide a prepreg in which voids are less likely to remain and insulation reliability is improved.

[0085] In one embodiment, the prepreg can be manufactured according to a conventional method. For example, it can be manufactured by impregnating the glass cloth of the present invention with a varnish in which the matrix resin is diluted with an organic solvent, then evaporating the organic solvent in a drying oven to cure the thermosetting resin to a B-stage state (semi-cured state).

[0086] Both thermosetting resins and thermoplastic resins can be used as the matrix resin. The thermosetting resin is not particularly limited, but examples include: a) an epoxy resin cured by reacting a compound having an epoxy group with a compound having at least one of the following groups that react with the epoxy group: an amino group, a phenol group, an acid anhydride group, a hydrazide group, an isocyanate group, a cyanate group, and a hydroxyl group, either without a catalyst or with the addition of a catalyst having catalytic activity such as an imidazole compound, a tertiary amine compound, a urea compound, or a phosphorus compound; b) a radical polymerization-type curing resin cured by using a thermal decomposition-type catalyst or a photodecomposition-type catalyst as a reaction initiator with a compound having at least one of the following groups: an allyl group, a methacrylic group, and an acrylic group; c) a maleimidotriazine resin cured by reacting a compound having a cyanate group with a compound having a maleimide group; d) a thermosetting polyimide resin cured by reacting a maleimide compound with an amine compound; and e) a benzoxazine resin cured by crosslinking a compound having a benzoxazine ring by heat polymerization.

[0087] Furthermore, while the thermoplastic resin is not particularly limited, examples include polyphenylene ether, modified polyphenylene ether, polyphenylene sulfide, polysulfone, polyethersulfone, polyarylate, aromatic polyamide, polyetheretherketone, thermoplastic polyimide, insoluble polyimide, polyamideimide, and fluororesin. Additionally, a thermosetting resin and a thermoplastic resin may be used in combination.

[0088] When using terminal-modified polyphenylene ether as the matrix resin and combining it with divinylbenzene as the crosslinking agent, the extremely high reactivity of divinylbenzene causes the matrix resin to harden due to the crosslinking reaction faster than the air contained between the single fibers of the glass cloth in the prepreg can be sufficiently removed during the press molding process where heat curing takes place. This results in a problem where voids tend to remain in the printed circuit board after heat curing.

[0089] However, when using the surface-treated glass cloth of the present invention, even when polyphenylene ether resin is used as the matrix resin and divinylbenzene as the curing agent, voids are less likely to remain in the printed circuit board after heat curing, and polyphenylene ether can be preferably used as the matrix resin.

[0090] The printed circuit board of the present invention comprises the above-mentioned surface-treated glass cloth and a cured product of a matrix resin composition impregnated into the glass cloth. This makes it possible to provide a printed circuit board with fewer residual voids and improved insulation reliability.

[0091] The present invention will be described in more detail below using examples and comparative examples, but the present invention is not limited in any way by the following examples.

[0092] [Preparation of mixtures of amino group-containing organosilicon compounds represented by general formula (1) or their hydrochloride salts] (Synthesis example) Methanol (Tokyo Chemical Industries, 539 g), 3-(2-aminoethylamino)propyltrimethoxysilane (product name: Dowsil OFS-6094SILANE, 222.4 g, 1.0 mol), and 4-tert-butylcatechol (Tokyo Chemical Industries, 0.5 g) were added to a four-necked flask equipped with a magnetic stirrer, an In-Situ FT-IR analyzer (React IR425, Mettler Toledo), a thermometer, a Dieblot condenser, and a dropping funnel. When the temperature in the flask stabilized at 40°C, benzyl chloride (Tokyo Chemical Industries, 25.3 g, 0.2 mol) was added dropwise from the dropping funnel. Immediately after the addition of benzyl chloride was complete, the mixture was heated and reacted under reflux of methanol for 2 hours to complete the reaction. Next, chloromethylstyrene (Tokyo Chemical Industries, 145.0 g, 0.95 mol) was added dropwise from a dropping funnel, and after the addition was complete, the mixture was reacted at a liquid temperature of 67°C for 8 hours. Then, diethylhydroxylamine (Tokyo Chemical Industries, 1.0 g) and sodium methoxide (28% methanol solution, equivalent to 1.15 mol of sodium methoxide from Tokyo Chemical Industries) were added to the flask and reacted at 67°C for 3 hours. Then, chloromethylstyrene (145.0 g, 0.95 mol) and 4-tert-butylcatechol (0.5 g) were added dropwise from a dropping funnel, and the mixture was aged at 67°C for 10 hours to complete the reaction. The by-product salt was filtered off by vacuum filtration using an Advantec GC90 filter to obtain the target amino group-containing organosilicon compound.

[0093] The progress of the reaction is determined by the chlorine concentration obtained by silver nitrate titration and the 700 cm³ observed by ReactIR. －１ The signal intensity of carbon-chlorine stretching oscillations observed in the vicinity was monitored.

[0094]

[0095] [Evaluation of Bending Stiffness of Glass Cloth] The bending stiffness of glass cloth was measured five times using a pure bending tester (Kato Tech Co., Ltd., KES-FB2-A) under the following measurement conditions. The bending characteristics in the warp direction were determined using the average value of the five measured values. The bending characteristics were measured using the value obtained during the first bending test, and the sample was replaced each time for a total of five measurements. Here, the glass cloth was bent so that the warp threads in the sample achieved the maximum curvature shown below. In addition, the glass cloth was sampled without unnecessarily bending or otherwise deforming it, as this would affect the measurement results.

[0096] <Measurement Conditions> Sample width: 7 cm Maximum curvature: ±2.5 (1 / cm) Bending speed: 0.500 ([1 / cm] / sec) Curvature range for calculating bending characteristics: +0.5 to +1.5 Bending stiffness and bending hysteresis are calculated from the average values ​​of front and back bending.

[0097] <Measurement Method> (1) The glass cloth was "bent from the front" so that the curvature was "0" → "+2.5" → "0", and the bending stiffness B-1 was calculated between +0.5 and +1.5. (2) Next, the glass cloth was "bent from the back" so that the curvature was "0" → "-2.5" → "0", and the bending stiffness B-2 was calculated between "-0.5" and "-1.5". (3) The average value Bavg of B-1 and B-2 was calculated. (4) The sample was changed. (5) Steps (1) to (4) above were repeated a total of 5 times. (6) The further average of the average Bavg of the 5 times was taken as the "bending stiffness B in the warp direction".

[0098] [Bending stiffness per unit weight in the warp direction of glass cloth] Using the weight of the glass cloth and the bending stiffness in the warp direction, the following formula (A) is given: Bending stiffness B in the warp direction of glass cloth (gf・cm) ２ (g / m²) / Weight of glass cloth ２ ) ... (A) was used to determine the bending stiffness per unit weight in the warp direction of the glass cloth.

[0099] [Visual Inspection Method for Glass Cloth] The glass cloths of the examples and comparative examples were visually inspected 1 meter at a time on a roll-to-roll inspection table, under tension of 100 N / 1300 mm and illuminated with a halogen lamp, to check for wrinkles, scratches, or tears on the glass cloth. The number of defective products was counted as follows: the number of products with one or more defects per meter was counted as the defective quantity, and the number of products with no defects per meter was counted as the good quantity. The number of defective products per 2000 meters was then counted. Based on the inspection results, the glass cloths of the examples and comparative examples were graded according to the following indicators.

[0100] Wrinkles A: Total length of wrinkled product area is less than 20m (= Defect rate is less than 1%) B: Total length of wrinkled product area is 20m or more but less than 60m (= Defect rate is 1% or more but less than 3%) C: Total length of wrinkled product area is 60m or more (= Defect rate is 3% or more)

[0101] [Method for Measuring the Number of Voids in Laminates] Laminates were cut to a size of 50 mm x 50 mm or larger. The cut laminates were evaluated by counting the number of voids when impregnated with linseed oil (Hayashi Pure Chemical Industries, Ltd., product number: YK014500) at a liquid temperature range of 24.0 to 26.0°C. A high-precision camera (frame size: 5120 x 5120 pixels) was placed perpendicular to the laminate, and an LED light (Power Flash bar-type lighting manufactured by CCS Corporation) was used as a light source, illuminating the laminate from both sides, 15 cm away from the laminate and positioned directly to the side, sandwiching the laminate. The number of voids with a length of 160 μm or more present between the glass filaments in the laminate was counted within a 32 mm x 32 mm field of view. The average value of the number of voids counted at any three locations on the laminate was defined as the void count. Voids correspond to the unimpregnated portions of the glass cloth in the matrix resin. Therefore, a low void number means that the glass cloth has excellent impregnation properties into the matrix resin.

[0102] [Manufacturing of L2-1078 (raw cloth)] Using an L2 LCD520 (manufactured by AGY Holding Corporation) and an air jet loom, the cloth was woven with a weave density of 54 warp threads / 25 mm and 54 weft threads / 25 mm. The cloth width was woven to 1300 mm. As the warp threads, L2 glass yarn with an average filament diameter of 5.0 μm, 200 filaments, and 1.0 Z twist was used. Similarly, as the weft threads, L2 glass yarn with an average filament diameter of 5.0 μm, 200 filaments, and 1.0 Z twist was used.

[0103] [Manufacturing of L1078 (raw cloth)] Using an LCD510 (manufactured by AGY Holding Corporation) and an air jet loom, the cloth was woven with a weave density of 54 warp threads / 25 mm and 54 weft threads / 25 mm. The cloth width was woven to 1300 mm. For the warp threads, L-glass yarn with an average filament diameter of 5.0 μm, 200 filaments, and 1.0 Z twist was used. Similarly, for the weft threads, L-glass yarn with an average filament diameter of 5.0 μm, 200 filaments, and 1.0 Z twist was used.

[0104] [Preparation of Prepregs] Prepregs were prepared by impregnating the surface-treated glass cloth obtained in the following examples and comparative examples with modified polyphenylene ether resin varnish, scraping off excess varnish by passing it through a slit, and evaporating and removing toluene, which is the varnish solvent, in a hot air dryer. Varnish 1 and Varnish 2 were prepared as the polyphenylene ether resin varnish. Varnish 1 consisted of 44.8% by mass of oligophenylene ether (manufactured by Sabic, trade name: Noryl SA9000) as a low dielectric resin, 3.2% by mass of divinylbenzene (manufactured by Nippon Steel Chemical & Material Co., Ltd., trade name: DVB-960) and 10.3% by mass of liquid polybutadiene (manufactured by Nippon Soda Co., Ltd., trade name: B-1000) as crosslinking agents, 0.2% by mass of α,α'-di(tert-butylperoxy)diisopropylbenzene (manufactured by NOF Corporation, trade name: Perbutyl P) as a reaction initiator, and 41.5% by mass of toluene (manufactured by Sigma-Aldrich) as a solvent. Varnish 2 consisted of 45.9% by mass of oligophenylene ether (manufactured by Sabic, trade name: Noryl SA9000) as a low dielectric resin, 11.5% by mass of triallyl isocyanurate (manufactured by Mitsubishi Chemical Corporation) as a crosslinking agent, 0.6% by mass of α,α'-di(tert-butylperoxy)diisopropylbenzene (manufactured by NOF Corporation, trade name: Perbutyl P) as an initiator, and 42.0% by mass of toluene (manufactured by Sigma-Aldrich) as a solvent.

[0105] The prepreg was cut to a predetermined size, and the mass of the prepreg was compared with the mass of glass cloth of the same size to calculate the solid content (mass%) of the thermosetting composition in the prepreg.

[0106] (Example 1) As an organosilicon compound, a mixture of an amino group-containing organosilicon compound represented by general formula (1) of the synthesis example or its hydrochloride salt (40% methanol solution, 0.2 moles of benzyl group and 1.9 moles of vinylbenzyl group per mole of amino group-containing organosilicon compound) was diluted with water containing acetic acid and a surfactant, so that the amount of organosilicon compound was 0.9% by mass, and the mixture was stirred for 2 hours to prepare a glass cloth surface treatment agent.

[0107] The L2-1078 raw cloth was heat-treated at 400°C for 72 hours to remove oil. Subsequently, the cloth was immersed in the above-mentioned glass cloth surface treatment agent, squeezed with an NBR rubber roll, and then heated and dried in a hot air dryer at 120°C for 20 seconds to chemically bond the organosilicon compound to the glass surface. The dried cloth was then discharged at a pressure of 7.0 kg / cm². ２ After the fibers were opened by spraying with water, a surface-treated glass cloth was obtained by drying it in a hot air dryer.

[0108] Next, a prepreg was prepared using varnish 1 as a modified polyphenylene ether resin varnish on the obtained surface-treated glass cloth.

[0109] The obtained prepreg was cut to 200 mm x 200 mm, and with release film superimposed on both sides, a laminate 1 (thickness approximately 0.1 mm) was obtained by vacuum pressing. The vacuum pressing conditions were a press pressure of 10 kgf / cm². ２ The temperature was raised from room temperature to 200°C at a rate of 4°C / min, and then maintained at 200°C for 60 minutes. After pressing, laminate 1 was removed and allowed to cool completely before being subjected to void number measurement.

[0110] Laminate 2 was obtained by making it exactly the same as laminate 1, except that varnish 2 was used as a modified polyphenylene ether resin varnish.

[0111] (Example 2) The surface treatment agent for the glass cloth was prepared in exactly the same manner as in Example 1, except that the organosilicon compound contained in the glass cloth surface treatment agent was a mixture of an amino group-containing organosilicon compound represented by general formula (1) or its hydrochloride salt (40% methanol solution, 0.2 moles of benzyl group and 1.9 moles of vinylbenzyl group per mole of amino group-containing organosilicon compound) consisting of 26 mol% and 74 mol% 3-methacryloxypropyltrimethoxysilane (manufactured by Dow-Toray Industries, Ltd., trade name: XIAMETER OFS-6030 Silane). Surface-treated glass cloth, prepreg, and laminates 1 and 2 were prepared and subjected to void number measurement.

[0112] (Example 3) Except that the organosilicon compound contained in the glass cloth surface treatment agent was a mixture of 6 mol% of an amino group-containing organosilicon compound represented by general formula (1) or its hydrochloride salt, and 94 mol% of 3-methacryloxypropyltrimethoxysilane, the surface-treated glass cloth, prepreg, and laminates 1 and 2 were prepared in exactly the same manner as in Example 1 and subjected to measurement of the void number.

[0113] (Example 4) Except that the organosilicon compound contained in the glass cloth surface treatment agent was a mixture of 3 mol% of an amino group-containing organosilicon compound represented by general formula (1) or its hydrochloride salt, and 97 mol% of 3-methacryloxypropyltrimethoxysilane, the surface-treated glass cloth, prepreg, and laminates 1 and 2 were prepared in exactly the same manner as in Example 1, and subjected to measurement of the void number.

[0114] (Example 5) Except for using an amino group-containing organosilicon compound represented by general formula (1) or its hydrochloride salt (40% methanol solution, 0.5 moles of benzyl group and 1.5 moles of vinylbenzyl group per mole of amino group-containing organosilicon compound) which was obtained by mixing 80% by weight of the amino group-containing organosilicon compound synthesized in the synthesis example with 20% by weight of Z-6049 SILANE (manufactured by Dow-Toray Industries, Ltd., 40% methanol solution, 1.0 mole of benzyl group and 0 moles of vinylbenzyl group per mole of amino group-containing organosilicon compound) as a glass cloth surface treatment agent, surface-treated glass cloth, prepreg, and laminates 1 and 2 were prepared in exactly the same manner as in Example 1 and subjected to void number measurement.

[0115] (Example 6) Except for using 26 mol% of an amino group-containing organosilicon compound represented by general formula (1) or its hydrochloride salt (40% methanol solution, 0.5 moles of benzyl group and 1.5 moles of vinylbenzyl group per mole of amino group-containing organosilicon compound) and 74 mol% of 3-methacryloxypropyltrimethoxysilane as glass cloth surface treatment agents, surface-treated glass cloth, prepreg, and laminates 1 and 2 were prepared in exactly the same manner as in Example 1 and subjected to void number measurement.

[0116] (Example 7) Surface-treated glass cloth, prepregs, and laminates 1 and 2 were prepared in exactly the same manner as in Example 1, except that 6 mol% of an amino group-containing organosilicon compound represented by general formula (1) or its hydrochloride salt (40% methanol solution, 0.5 moles of benzyl group and 1.5 moles of vinylbenzyl group per mole of amino group-containing organosilicon compound) was used as a glass cloth surface treatment agent, with the exception that 94 mol% of 3-methacryloxypropyltrimethoxysilane was used as a glass cloth surface treatment agent.

[0117] (Example 8) Except for using 3 mol% of an amino group-containing organosilicon compound represented by general formula (1) or its hydrochloride salt (40% methanol solution, 0.5 moles of benzyl group and 1.5 moles of vinylbenzyl group per mole of amino group-containing organosilicon compound) and 97 mol% of 3-methacryloxypropyltrimethoxysilane as glass cloth surface treatment agents, surface-treated glass cloth, prepreg, and laminates 1 and 2 were prepared in exactly the same manner as in Example 1 and subjected to void number measurement.

[0118] (Example 9) Except for using 100 mol% of the amino group-containing organosilicon compound synthesized in the synthesis example, mixed with 40% by weight of Z-6049 SILANE, an amino group-containing organosilicon compound represented by general formula (1) or its hydrochloride salt (40% methanol solution, 0.8 moles of benzyl group and 1.2 moles of vinylbenzyl group per mole of amino group-containing organosilicon compound) as a glass cloth surface treatment agent, surface-treated glass cloth, prepreg, and laminates 1 and 2 were prepared in exactly the same manner as in Example 1 and subjected to void number measurement.

[0119] (Example 10) Except for using 26 mol% of an amino group-containing organosilicon compound represented by general formula (1) or its hydrochloride salt (40% methanol solution, 0.8 moles of benzyl group and 1.2 moles of vinylbenzyl group per mole of amino group-containing organosilicon compound) and 74 mol% of 3-methacryloxypropyltrimethoxysilane as glass cloth surface treatment agents, surface-treated glass cloth, prepreg, and laminates 1 and 2 were prepared in exactly the same manner as in Example 1 and subjected to void number measurement.

[0120] (Example 11) Surface-treated glass cloth, prepreg, and laminates 1 and 2 were prepared in exactly the same manner as in Example 1, except that 6 mol% of an amino group-containing organosilicon compound represented by general formula (1) or its hydrochloride salt (40% methanol solution, 0.8 moles of benzyl group and 1.2 moles of vinylbenzyl group per mole of amino group-containing organosilicon compound) was used as a glass cloth surface treatment agent, which was obtained by mixing 60% by weight of the amino group-containing organosilicon compound synthesized in the synthesis example with 40% by weight of Z-6049 SILANE, and 94 mol% of 3-methacryloxypropyltrimethoxysilane was used as a glass cloth surface treatment agent. These were then subjected to void number measurement.

[0121] (Example 12) Except for using 3 mol% of an amino group-containing organosilicon compound represented by general formula (1) or its hydrochloride salt (40% methanol solution, 0.8 moles of benzyl group and 1.2 moles of vinylbenzyl group per mole of amino group-containing organosilicon compound) and 97 mol% of 3-methacryloxypropyltrimethoxysilane as glass cloth surface treatment agents, surface-treated glass cloth, prepreg, and laminates 1 and 2 were prepared in exactly the same manner as in Example 1 and subjected to void number measurement.

[0122] (Example 13) Surface-treated glass cloth, prepreg, and laminates 1 and 2 were prepared in exactly the same manner as in Example 1, except that L1078 raw cloth was used, and were subjected to void number measurement.

[0123] (Example 14) Surface-treated glass cloth, prepreg, and laminates 1 and 2 were prepared in exactly the same manner as in Example 2, except that L1078 raw cloth was used, and were subjected to void number measurement.

[0124] (Example 15) Surface-treated glass cloth, prepreg, and laminates 1 and 2 were prepared in exactly the same manner as in Example 3, except that L1078 raw cloth was used, and were subjected to void number measurement.

[0125] (Example 16) Surface-treated glass cloth, prepreg, and laminates 1 and 2 were prepared in exactly the same manner as in Example 4, except that L1078 raw cloth was used, and were subjected to void number measurement.

[0126] (Comparative Example 1) Except for using 100 mol% 3-methacryloxypropyltrimethoxysilane as the organosilicon compound in the glass cloth surface treatment agent, surface-treated glass cloth, prepreg, and laminates 1 and 2 were prepared in exactly the same manner as in Example 1 and subjected to void number measurement.

[0127]

[0128] The results in Table 2 show that Examples 1 to 16 of the present invention, in which glass cloth was treated with a glass cloth surface treatment agent containing an amino group-containing organosilicon compound represented by general formula (1) or a mixture thereof, exhibited higher bending rigidity and suppressed wrinkle formation compared to Comparative Example 1, which did not contain an amino group-containing organosilicon compound or a mixture thereof. It was also found that voids in the laminate were less likely to remain.

Claims

1. A surface-treated glass cloth comprising a surface treatment layer on the surface of a glass cloth composed of a plurality of glass filaments as warp and weft, wherein the surface treatment layer is represented by the following general formula (1): [In formula (1), R １ represents an arylene group or a cyclic or acyclic divalent hydrocarbon group of C １ to C １０ ; R ２ and R ３ each independently represent a group selected from the group consisting of hydrogen and a monovalent hydrocarbon group of C １ to C １０ ; R ４ represents an arylene group or a cyclic or acyclic divalent hydrocarbon group of C １ to C １０ ; n represents an integer of 0, 1, or 2; Q １ , Q ２ , and Q ３ each independently represent a functional group selected from the group consisting of a hydrogen atom, a benzyl group, and a vinylbenzyl group], and is a layer treated with a mixture of an amino group-containing organosilicon compound represented by the formula or a salt thereof, and the content of the benzyl group in 1 mol of the amino group-containing organosilicon compound represented by the general formula (1) or a salt thereof is 0.1 mol or more and 0.8 mol or less. A surface-treated glass cloth.

2. The surface-treated glass cloth according to claim 1, wherein the content of vinylbenzyl groups in 1 mole of an amino group-containing organosilicon compound represented by the general formula (1) or a salt thereof is 1.1 moles or more and 2.5 moles or less.

3. The surface-treated glass cloth according to claim 1, wherein the surface-treated layer is a layer further treated with an organosilicon compound containing a carbon-carbon unsaturated double bond group.

4. The surface-treated glass cloth according to claim 3, characterized in that the organosilicon compound containing the carbon-carbon unsaturated double bond group contains a (meth)acryloyl group.

5. The surface-treated glass cloth according to claim 4, wherein the organosilicon compound containing the carbon-carbon unsaturated double bond group is at least one selected from the group consisting of 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, and 3-acryloxypropyltriethoxysilane.

6. A prepreg comprising a surface-treated glass cloth according to any one of claims 1 to 5, and a matrix resin composition impregnated into the glass cloth.

7. The prepreg according to claim 6, wherein the matrix resin composition comprises a polyphenylene ether resin.

8. A printed circuit board comprising a surface-treated glass cloth according to any one of claims 1 to 5, and a cured product of a matrix resin composition impregnated into the glass cloth.

9. The printed circuit board according to claim 8, wherein the matrix resin composition comprises a polyphenylene ether resin.

10. The following general formula (1): [In formula (1), R １ is an allerene group or C １ ~C １０ R represents a cyclic or acyclic divalent hydrocarbon group. ２ and R ３ These are, independently, hydrogen and C １ ~C １０ R represents a group selected from the group consisting of monovalent hydrocarbon groups. ４ is an allerene group or C １ ~C １０ Q represents a cyclic or acyclic divalent hydrocarbon group, where n represents an integer of 0, 1, or 2. １ Q ２ , and Q ３ A glass cloth surface treatment agent comprising a mixture of an amino group-containing organosilicon compound or a salt thereof represented by [where each independently represents a functional group selected from the group consisting of a hydrogen atom, a benzyl group, and a vinylbenzyl group], wherein the content of benzyl groups in 1 mole of the amino group-containing organosilicon compound or salt thereof represented by the general formula (1) is 0.1 moles or more and 0.8 moles or less.

11. The glass cloth surface treatment agent according to claim 10, further comprising a surfactant.

12. The glass cloth surface treatment agent according to claim 10, wherein the content of vinylbenzyl groups in 1 mole of an amino group-containing organosilicon compound represented by the general formula (1) or a salt thereof is 1.1 moles or more and 2.5 moles or less.

13. The glass cloth surface treatment agent according to claim 10, wherein the residual amounts of benzyl halide and vinyl benzyl halide, which are reaction raw materials, are 0.02 moles or less per mole of an amino group-containing organosilicon compound represented by the general formula (1) or a salt thereof.

14. The glass cloth surface treatment agent according to claim 10, further comprising an organosilicon compound containing a carbon-carbon unsaturated double bond group.

15. The glass cloth surface treatment agent according to claim 14, wherein the organosilicon compound containing the carbon-carbon unsaturated double bond group contains a (meth)acryloyl group.

16. The glass cloth surface treatment agent according to claim 15, wherein the organosilicon compound containing the carbon-carbon unsaturated double bond group is at least one selected from the group consisting of 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, and 3-acryloxypropyltriethoxysilane.

17. The glass cloth surface treatment agent according to claim 14, wherein the molar concentration of a mixture of an amino group-containing organosilicon compound represented by the general formula (1) or a salt thereof, relative to the total amount of organosilicon compounds, is 1 to 100%.

18. A surface-treated glass cloth treated with the glass cloth surface treatment agent according to any one of claims 10 to 17.

19. A prepreg comprising a surface-treated glass cloth according to claim 18 and a matrix resin composition impregnated into the glass cloth.

20. The prepreg according to claim 19, wherein the matrix resin composition comprises a polyphenylene ether resin.

21. A printed circuit board comprising a surface-treated glass cloth according to claim 18 and a cured product of a matrix resin composition impregnated into the glass cloth.

22. The printed circuit board according to claim 21, wherein the matrix resin composition comprises a polyphenylene ether resin.

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