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

Abstract

Provided are a surface-treated glass cloth with excellent appearance, a prepreg, a printed wiring board, and a glass cloth surface treatment agent capable of reducing the occurrence of appearance defects by uniform surface treatment. 【Solution means】A surface-treated glass cloth provided with a surface treatment layer on the surface of a glass cloth composed of glass yarns made up of a plurality of glass filaments as warp and weft, wherein the surface treatment layer has the following general formula (1): JPEG2026057161000010.jpg25170 [R 1 is an arylene group or a divalent hydrocarbon group having 1 to C 10 ; R 2 and R 3 are independently selected from H and monovalent hydrocarbon groups having 1 to C 10 ; R 4 is an arylene group or a divalent hydrocarbon group having 1 to C 10 ; n is an integer of 0, 1 or 2; Q 1 to Q 3 are independently selected from the group consisting of H, a benzyl group, a vinylbenzyl group, and a monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a hydroxyl group], and is a surface-treated glass cloth that is a layer treated with a mixture of an amino group-containing organosilicon compound represented by the formula or a salt thereof.

Description

Technical Field

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

Background Art

[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 further improvement in the dielectric properties of the insulating materials (for example, lowering of the dielectric tangent) are desired. Similarly, there is a background in which 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 insulating materials, 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 "matrix resin") that is thermally cured by a radical reaction such as end-modified polyphenylene ether (end-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 for the prepreg with a silane coupling agent is known. Furthermore, it is known that by using a combination of a silane coupling agent having a (meth)acryloyl group and a silane coupling agent having an amino group, the insulation reliability can be improved while maintaining a soft texture (Patent Document 2).

[0004] However, when a silane coupling agent having a (meth)acryloyl group and a silane coupling agent having an amino group described in Patent Document 2 are used in combination, when surface treatment is performed in an aqueous solution form, the dispersibility (solubility) of the silane coupling agent in water is low, so it is likely to gel in an aqueous solvent, the surface treatment is not performed uniformly, and there are problems such as appearance defects such as silane-derived stains and coating unevenness, or poor efficiency of the surface treatment.

Prior Art Documents

[0005] [Patent Document 1] International Publication No. 2014 / 203511 [Patent Document 2] Japanese Patent Publication No. 2023-80023 [Overview of the project] [Problems that the invention aims to solve]

[0006] The present invention was made to solve the problems of the above-mentioned prior art, and aims to provide glass cloth, prepreg, and printed circuit boards with superior appearance, and a glass cloth surface treatment agent that reduces the occurrence of appearance defects through uniform surface treatment. [Means for solving the problem]

[0007] The inventors of the present invention have arrived at this invention as a result of diligent study on the above problems. That is, in order to solve the above problems, one aspect of the present invention includes the following aspects.

[0008] [1] A surface-treated glass cloth comprising a glass thread consisting of multiple glass filaments as warp and weft threads, wherein the glass cloth has a surface treatment layer on its surface, The aforementioned surface treatment layer is defined by the following general formula (1):

[0009] [ka]

[0010] [In formula (1), R 1 is an allerene group or C1~C 10 Represents a cyclic or acyclic divalent hydrocarbon group, R 2 and R 3 These are, independently, hydrogen and C1-C 10represents a group selected from the group consisting of monovalent hydrocarbon groups, R 4 is an arylene group or a cyclic or acyclic divalent hydrocarbon group having 1 to C 10 and represents a cyclic or acyclic divalent hydrocarbon group, n represents an integer of 0, 1 or 2, Q 1 Q 2 and Q 3 are each independently a hydrogen atom, a benzyl group, a vinylbenzyl group, and a C1-C 10 selected from the group consisting of monovalent hydrocarbon groups substituted with one or more hydroxyl groups, provided that Q 1 Q 2 and Q 3 at least one of which is a C1-C 10 monovalent hydrocarbon group substituted with one or more hydroxyl groups, representing a functional group]

[0011] A surface-treated glass cloth which is a layer treated with a mixture of an amino group-containing organosilicon compound represented by or a salt thereof.

[0012] [2] In 1 mol of the amino group-containing organosilicon compound represented by the general formula (1) or a salt thereof, the content of the C1-C 10 monovalent hydrocarbon group substituted with one or more hydroxyl groups is 0.2 or less, satisfying the surface-treated glass cloth according to [1].

[0013] [3] The surface treatment layer is a layer further treated with an organosilicon compound containing a carbon-carbon unsaturated double bond group, the surface-treated glass cloth according to [1] or [2].

[0014] [4] The surface-treated glass cloth according to [3], wherein the organosilicon compound containing a carbon-carbon unsaturated double bond group contains a (meth)acryloyl group.

[0015] [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.

[0016] 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.

[0017] [7] The prepreg according to [6], wherein the matrix resin composition comprises a polyphenylene ether resin.

[0018] 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.

[0019] [9] The printed circuit board according to [8], wherein the matrix resin composition comprises a polyphenylene ether resin.

[0020]

[10] General formula (1):

[0021] [ka]

[0022] [In formula (1), R 1 is an allerene group or C1~C 10 Represents a cyclic or acyclic divalent hydrocarbon group, R 2 and R 3 These are, independently, hydrogen and C1-C10 This represents a group selected from the group consisting of monovalent hydrocarbon groups. R 4 is an allerene group or C1~C 10 Represents a cyclic or acyclic divalent hydrocarbon group, n represents an integer of 0, 1, or 2. Q 1 Q 2 , and Q 3 Each of these is independently a C1-C atom substituted with a hydrogen atom, a benzyl group, a vinylbenzyl group, and one or more hydroxyl groups. 10 Selected from the group consisting of monovalent hydrocarbon groups, where Q 1 Q 2 , and Q 3 At least one of the C1-C atoms is substituted with one or more hydroxyl groups. 10 [A monovalent hydrocarbon group, representing a functional group.] A glass cloth surface treatment agent comprising a mixture of an amino group-containing organosilicon compound represented by or a salt thereof.

[0023]

[11] The glass cloth surface treatment agent according to

[10] , further comprising a surfactant.

[0024]

[12] One mole of the amino group-containing organosilicon compound represented by the general formula (1) or its salt contains one or more C1-C atoms substituted with hydroxyl groups. 10 A glass cloth surface treatment agent according to

[10] or

[11] , wherein the content of monovalent hydrocarbon groups is 0.2 or less.

[0025]

[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 0.01 moles or less per mole of an amino group-containing organosilicon compound represented by the general formula (1) or a salt thereof.

[0026]

[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.

[0027]

[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.

[0028]

[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.

[0029]

[17] A 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 30%.

[0030] Surface-treated glass cloth, treated with any one of the glass cloth surface treatment agents described in

[18] ,

[10] , to

[17] .

[0031] A prepreg comprising a surface-treated glass cloth as described in

[19]

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

[0032]

[20] The prepreg according to

[19] , comprising a matrix resin composition and a polyphenylene ether resin.

[0033] A printed circuit board comprising a surface-treated glass cloth as described in

[21]

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

[0034]

[22] The printed circuit board according to

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

[0035] According to the present invention, it is possible to provide glass cloth, prepregs, and printed circuit boards with excellent appearance, as well as a glass cloth surface treatment agent that reduces the occurrence of appearance defects through uniform surface treatment. [Modes for carrying out the invention]

[0036] 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 thereof.

[0037] 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.

[0038] The surface-treated glass cloth of the present invention is a surface-treated glass cloth having a surface treatment layer on the surface of a glass cloth composed of glass threads made of a plurality of glass filaments as warp and weft threads, 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).

[0039] [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. The glass fibers (glass filaments) constituting the glass cloth can generally be low dielectric constant glass such as E glass (alkali-free glass) used in 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. The glass fibers may consist of one type of glass material, or they may be a combination of two or more glass fibers made of different glass materials.

[0040] [Woven structure of glass cloth] In one embodiment, the weave structure of the glass cloth can be, for example, plain weave, twill weave, satin weave, etc. Among these, the plain weave structure is preferred.

[0041] [Drilling density] In one embodiment, the weft and warp density of 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 weft density is within the above range. The weft and warp densities may be different from each other.

[0042] [Gross weight] In one embodiment, the basis weight (mass) of the glass cloth is preferably 8 to 250 g / m². 2 More preferably 8-100 g / m² 2 More preferably 8-80 g / m 2 Particularly preferred is 8-50 g / m 2 Therefore, if the basis weight of the glass cloth is within the above range, the effects of the present invention are more easily obtained.

[0043] [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.

[0044] [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.

[0045] [A mixture of amino group-containing organosilicon compounds or their salts] In the present invention, a mixture of an amino group-containing organosilicon compound or a salt thereof for treating a surface-treated glass cloth, wherein the amino group-containing organosilicon compound is of the following general formula (1):

[0046] [ka]

[0047] [In formula (1), R 1 is an allerene group or C1~C 10 Represents a cyclic or acyclic divalent hydrocarbon group, R 2 and R 3 These are, independently, hydrogen and C1-C 10 This represents a group selected from the group consisting of monovalent hydrocarbon groups. R 4 is an allerene group or C1~C 10 Represents a cyclic or acyclic divalent hydrocarbon group, n represents an integer of 0, 1, or 2. Q 1 Q 2 , and Q 3 Each of these is independently a C1-C atom substituted with a hydrogen atom, a benzyl group, a vinylbenzyl group, and one or more hydroxyl groups. 10 Selected from the group consisting of monovalent hydrocarbon groups, where Q 1 Q2 , and Q 3 At least one of the C1-C atoms is substituted with one or more hydroxyl groups. 10 [A monovalent hydrocarbon group, representing a functional group.] It is expressed as and, if it is a salt, is a salt using one or more valent anions. 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.

[0048] 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.

[0049] In one embodiment, R 1 C1~C 10The 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, ethylene, propylene, butylene, pentylene, and hexylene groups. Examples of cycloalkylene groups include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, 1-methylcyclopropylene, 2-methylcyclopropylene, and 2,2-dimethylcyclopropylene. 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.

[0050] In one embodiment, R 2 and R 3 C1~C 10 The monovalent hydrocarbon groups are, but are not limited to, 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.

[0051] In one embodiment, R 4 The arylene group and C1~C 10 The cyclic or acyclic divalent hydrocarbon group is R 1 It is a similar base.

[0052] In one embodiment, n is an integer of 0, 1, or 2, preferably 0 or 1. OR in formula (1) 3 The group is hydrolyzable and decomposes to form a bond with the glass cloth.

[0053] Q 1 Q 2 , and Q 3 Each of these is independently a C1-C atom substituted with a hydrogen atom, a benzyl group, a vinylbenzyl group, and one or more hydroxyl groups. 10 Selected from the group consisting of monovalent hydrocarbon groups, where Q 1 Q 2 , and Q 3 At least one of the C1-C atoms is substituted with one or more hydroxyl groups. 10 This represents a monovalent hydrocarbon group, a functional group, and among these, the vinylbenzyl group is a group that forms a bond with the matrix resin impregnated into the glass cloth.

[0054] In one embodiment, the content of benzyl groups in 1 mole of an amino group-containing organosilicon compound represented by general formula (1) or its salt is 0.2 moles or more and 0.8 moles or less, preferably 0.2 moles or more and 0.6 moles or less, and more preferably 0.2 moles or more and 0.5 moles or less. By setting the benzyl group content within the above range, a glass cloth with excellent compatibility with the matrix resin can be provided.

[0055] In one embodiment, the content of vinylbenzyl groups in 1 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 1.3 moles or more and 2.3 moles or less, and more preferably 1.5 moles or more and 2.1 moles or less. By setting the content of vinylbenzyl groups within the above range, a glass cloth with excellent adhesion to the matrix resin can be provided.

[0056] 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 low residual amount of the reaction raw materials, benzyl halide (particularly benzyl bromide or benzyl chloride) and vinyl benzyl halide (particularly vinyl benzyl chloride or vinyl benzyl bromide). The residual amounts of benzyl halide and vinyl benzyl halide are 0.01 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 0.009 moles or less each per mole of the amino group-containing organosilicon compound represented by general formula (1) or its hydrochloride salt. 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.

[0057] [Method for producing a mixture of amino group-containing organosilicon compounds or their salts] In one embodiment, a mixture of an amino group-containing organosilicon compound represented by general formula (1) or a salt thereof is defined as follows:

[0058] [ka] [In formula (2), R 1 is an allerene group or C1~C 10 Represents a cyclic or acyclic divalent hydrocarbon group, R 2 and R 3 These are, independently, hydrogen and C1-C 10 This represents a group selected from the group consisting of monovalent hydrocarbon groups. R 4 is an allerene group or C1~C 10 Represents a cyclic or acyclic divalent hydrocarbon group, n represents an integer of 0, 1, or 2.

[0059] For an amino group-containing organosilicon compound represented by the following general formula (3): [ka] [In equation (3), X represents a halogen atom, R 5 is an allerene group or C1~C 10 [Represents a cyclic or otherwise divalent hydrocarbon group]

[0060] A step of reacting an alcohol substituted with a halogen atom represented by, Benzyl halogens and the following general formula (4): [ka] [In equation (4), X represents a halogen atom.]

[0061] It is produced by a manufacturing method that includes a step of reacting one or more types selected from the halomethylstyrene represented by . The benzyl halogen may be benzyl chloride or benzyl bromide, and benzyl halogen and the halomethylstyrene may be used in combination.

[0062] In one embodiment, R of general formula (2) 1 ~R 4 And n are R as described for general formula (1). 1 ~R 4 And are the same base and integer as n.

[0063] 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.

[0064] 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.

[0065] In one embodiment, the halomethylstyrene represented by general formula (3) is preferably fluoromethylstyrene, chloromethylstyrene, or bromomethylstyrene, and is particularly preferably chloromethylstyrene.

[0066] [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).

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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 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.

[0072] Organosilicon compounds containing carbon-carbon unsaturated double bond groups can be used individually, or in combination of two or more.

[0073] In one embodiment, the molar concentration of the mixture of an amino group-containing organosilicon compound represented by general formula (1) or its salt, relative to the total amount of organosilicon compounds, is preferably 1 to 30%. This enhances the impregnation of the glass cloth into the matrix resin. The molar concentration of the mixture of an amino group-containing organosilicon compound represented by general formula (1) or its salt is preferably 5 to 30%.

[0074] 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 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.

[0075] 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.

[0076] 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.

[0077] [Method for manufacturing glass cloth surface treatment agent] A preferred method for producing the glass cloth surface treatment agent of the present invention is either to directly add a mixture of an amino group-containing organosilicon compound represented by general formula (1) or a salt thereof 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 obtain an organic solvent solution, and then add the organic solvent solution to water.

[0078] [Surface treatment method for glass cloth] Possible methods for applying the glass cloth surface treatment agent to the glass cloth include (a) accumulating the glass cloth surface treatment agent in a bath and immersing and passing the glass cloth through it (hereinafter referred to as the "immersion method"), and (b) directly applying the glass cloth surface treatment agent to the glass cloth using a roll coater, die coater, or gravure coater. When applying using the immersion method described in (a) above, it is preferable to select an immersion time of 0.5 seconds or more and 1 minute or less for the glass cloth in the glass cloth surface treatment agent.

[0079] 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.

[0080] The heating and drying temperature is preferably 90°C or higher, and more preferably 100°C or higher, to ensure that the reaction between the organosilicon compound and the glass proceeds sufficiently. Furthermore, the heating and drying temperature is preferably 300°C or lower, and more preferably 200°C or lower, to prevent deterioration of the organic functional groups of the organosilicon compound.

[0081] [Glass cloth] The glass cloth surface treatment agent of the present invention exhibits excellent dispersibility (solubility) in aqueous solutions, enabling uniform surface treatment. This makes it possible to provide a surface-treated glass cloth with superior appearance, less silane-derived staining and uneven coating.

[0082] [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 that is less prone to retaining voids, has excellent appearance, and improved insulation reliability.

[0083] 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 the B stage (semi-cured state).

[0084] Any thermosetting resin or thermoplastic resin can be used as the matrix resin. The thermosetting resin is not particularly limited, but for example, 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 curable resin in which a compound having at least one of an allyl group, a methacrylic group, and an acrylic group is cured using a thermal decomposition type catalyst or a photodecomposition type catalyst as a reaction initiator; c) Maleimidotriazine resin obtained by reacting a compound having a cyanate group with a compound having a maleimide group and curing it; d) A thermosetting polyimide resin cured by reacting a maleimide compound with an amine compound; e) Examples include benzoxazine resins obtained by crosslinking and curing compounds having a benzoxazine ring by heat polymerization.

[0085] 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.

[0086] 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, excellent appearance, and improved insulation reliability. [Examples]

[0087] 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.

[0088] [Preparation of mixtures of amino group-containing organosilicon compounds represented by general formula (1) or their hydrochloride salts] (Example of combination) In a four-necked flask equipped with a magnetic stirrer bar, thermometer, Liebig condenser, and dropping funnel, 3-(2-aminoethyl)aminopropyltrimethoxysilane (product name: Dowsil OFS-6094SILANE, 222.4g, 1.0 mol) and 3-chloro-1-propanol (Tokyo Chemical Industries, 18.9g, 0.2 mol) were added and stirred at 50°C for 20 hours. Next, methanol (Tokyo Chemical Industries, 539g) and sodium methoxide (28% methanol solution, equivalent to 2.9 mol of sodium methoxide from Tokyo Chemical Industries) were added and stirred at 40°C for 4 hours. After that, benzyl chloride (Tokyo Chemical Industries, 25.3g, 0.2 mol) was added and stirred at 67°C for 4 hours. 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 40°C for 8 hours. Then, sodium methoxide (28% methanol solution, Tokyo Chemical Industries, equivalent to 0.1 mol of sodium methoxide) was added and the mixture was stirred at 40°C for 4 hours. Subsequently, 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 40°C for 8 hours. The by-product salt was filtered off by vacuum filtration using an Advantec GC90 filter to obtain the target amino group-containing organosilicon compound.

[0089] [Manufacturing of L2-1078 (raw fabric cloth)] Using L2 glass yarn, a cloth was woven in an air-jet loom with a weave density of 54 warp threads / 25mm and 54 weft threads / 25mm. The cloth width was woven to 1300mm. For the warp threads, L2 glass yarn with an average filament diameter of 5.0 μm, 200 filaments, and 1.0Z twist was used. Similarly, for the weft threads, L2 glass yarn with an average filament diameter of 5.0 μm, 200 filaments, and 1.0Z twist was used.

[0090] (Example 1) As an organosilicon compound, a glass cloth surface treatment agent was prepared by diluting 30 mol% of 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) and 70 mol% of 3-methacryloxypropyltrimethoxysilane (manufactured by Dow-Toray Industries, Ltd., trade name: XIAMETER OFS-6030 Silane) with water containing acetic acid and a surfactant, and stirring for 2 hours, so that the amount of organosilicon compound was 0.9% by mass.

[0091] The L2-1078 raw cloth was heat-treated at 400°C for 72 hours to remove oil. Subsequently, the cloth was immersed in the glass cloth surface treatment agent, squeezed with an NBR rubber roll, and then heat-dried in a hot air dryer to chemically bond the organosilicon compound to the glass surface. After drying, the cloth was washed with water and then dried in a hot air dryer to obtain a surface-treated glass cloth.

[0092] (Comparative Example 1) A surface-treated glass cloth was prepared using the same procedure as in Example 1, except that 30 mol% of an amino group-containing organosilicon compound or a mixture thereof of its hydrochloride salt (manufactured by Dow-Toray Industries, Ltd., trade name: XIAMETER OFS-6032 Silane) and 70 mol% of 3-methacryloxypropyltrimethoxysilane were used as the organosilicon compounds.

[0093] [Visual inspection of glass cloth] The glass cloths of the examples and comparative examples were visually inspected on a roll-to-roll inspection table under a tension of 100 N / 1300 mm and illuminated with a halogen lamp to check for any surface defects originating from the silane coupling agent on the glass cloth. The results are shown in Table 1. [Table 1]

[0094] As shown in Table 1, the glass cloth of Comparative Example 1 exhibited appearance defects such as stains and uneven coating, while the glass cloth of Example 1 did not exhibit any appearance defects. This is thought to be because the aminosilane in the present invention has improved dispersibility (solubility) in the aqueous solution of the surface treatment agent, preventing silane-derived stains and uneven coating during the glass cloth treatment.

Claims

1. A surface-treated glass cloth comprising a glass cloth composed of multiple glass filaments as warp and weft threads, wherein the surface of the glass cloth is provided with a surface treatment layer, The aforementioned surface treatment layer is defined by the following general formula (1): 【Chemistry 1】 [In formula (1), R １ is an allerene group or C １ ~C １０ Represents a cyclic or acyclic divalent hydrocarbon group, R ２ and R ３ These are, independently, hydrogen and C １ ~C １０ This represents a group selected from the group consisting of monovalent hydrocarbon groups. R ４ represents an arylene group or a cyclic or acyclic divalent hydrocarbon group of C １ to C １０ and n represents an integer of 0, 1, or 2. Q １ Q ２ , and Q ３ Each of these is independently a C atom substituted with a hydrogen atom, a benzyl group, a vinylbenzyl group, and one or more hydroxyl groups. １ ~C １０ Selected from the group consisting of monovalent hydrocarbon groups, where Q １ Q ２ , and Q ３ C, where at least one of the C groups is substituted with one or more hydroxyl groups １ ~C １０ [A monovalent hydrocarbon group, representing a functional group.] A surface-treated glass cloth, which is a layer treated with a mixture of an amino group-containing organosilicon compound or a salt thereof, represented by [the formula shown].

2. One mole of an amino group-containing organosilicon compound represented by the general formula (1) or a salt thereof contains one or more hydroxyl groups substituted with C １ ~C １０ The surface-treated glass cloth according to claim 1, wherein the content of monovalent hydrocarbon groups is 0.2 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): 【Chemistry 2】 [In formula (1), R １ is an allerene group or C １ ~C １０ Represents a cyclic or acyclic divalent hydrocarbon group, R ２ and R ３ These are, independently, hydrogen and C １ ~C １０ This represents a group selected from the group consisting of monovalent hydrocarbon groups. R ４ is an allerene group or C １ ~C １０ Represents a cyclic or acyclic divalent hydrocarbon group, n represents an integer of 0, 1, or 2. Q １ Q ２ , and Q ３ Each of these is independently a C atom substituted with a hydrogen atom, a benzyl group, a vinylbenzyl group, and one or more hydroxyl groups. １ ~C １０ Selected from the group consisting of monovalent hydrocarbon groups, where Q １ Q ２ , and Q ３ C, where at least one of the C groups is substituted with one or more hydroxyl groups １ ~C １０ [A monovalent hydrocarbon group, representing a functional group.] A glass cloth surface treatment agent comprising a mixture of an amino group-containing organosilicon compound represented by or a salt thereof.

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

12. One mole of an amino group-containing organosilicon compound represented by the general formula (1) or a salt thereof contains one or more hydroxyl groups substituted with C １ ~C １０ The glass cloth surface treatment agent according to claim 10, wherein the content of monovalent hydrocarbon groups is 0.2 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 0.01 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 30%.

18. A surface-treated glass cloth treated with the glass cloth surface treatment agent described in 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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