Mixture of amino group-containing organosilicon compounds or salts thereof, method for producing same, and surface treatment agent containing mixture of amino group-containing organosilicon compounds or salts thereof

Abstract

To provide: a mixture of amino group-containing organosilicon compounds or salts thereof having excellent water-dilutability for producing a surface treatment agent that has a hard texture, that is, high flexural rigidity, can suppress the occurrence of wrinkles during roll-to-roll conveyance, does not tend to leave voids in a printed wiring board, and can improve insulation reliability; a method for producing the same; and a surface treatment agent containing the mixture of amino group-containing organosilicon compounds or salts thereof. Also to provide: a mixture of amino group-containing organosilicon compounds or salts thereof having excellent water-dilutability and forming a uniform solution without gelation in an aqueous solvent; a method for producing the same; and a surface treatment agent containing the mixture of salts thereof. A mixture of amino group-containing organosilicon compounds represented by general formula (1): [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 C1-C10 monovalent hydrocarbon groups substituted by a hydrogen atom, a benzyl group, a vinylbenzyl group, or one or more hydroxyl groups, where at least one of Q1, Q2, and Q3 is a C1-C10 monovalent hydrocarbon group substituted by one or more hydroxyl groups] or salts thereof.

Description

A mixture of amino group-containing organosilicon compounds or salts thereof, a method for producing the same, and a surface treatment agent containing a mixture of amino group-containing organosilicon compounds or salts thereof.

[0001] The present invention relates to a mixture of amino group-containing organosilicon compounds or salts thereof, a method for producing the same, and a surface treatment agent containing a mixture of amino group-containing organosilicon compounds or salts thereof.

[0002] Currently, information terminals such as smartphones are becoming more high-performance, and high-speed communication, exemplified by 5G communication, is progressing. Against this backdrop, in particular, for printed circuit boards used in high-speed communication, there is a demand not only for improved heat resistance, which has been required since before, but also for further improvement in the dielectric properties of the insulating material (for example, lower dielectric loss tangent). Similarly, there is a demand for improved dielectric properties for prepregs used as insulating materials in printed circuit boards, and for the glass yarns and glass cloths contained in said prepregs.

[0003] To reduce the dielectric strength of insulating materials, a method is known in which insulating materials are constructed using a prepreg in which a low-dielectric resin (hereinafter referred to as "matrix resin") that is thermoset by a radical reaction, such as terminal-modified polyphenylene ether (terminal-modified PPE), is impregnated into glass cloth (Patent Document 1). Furthermore, in order to crosslink with the matrix resin and improve adhesion to the resin, a method is known in which the glass cloth used in the prepreg is surface-treated with a silane coupling agent having an acryloxy group or a methacryloxy group, or with an amino group-containing organosilicon compound (Patent Documents 2 to 4).

[0004] However, glass cloth treated with a silane coupling agent having an acryloxy group or methacryloxy group as described in Patent Document 2 had the problem that, because it was soft in texture, i.e., had low bending rigidity, it was prone to wrinkling during roll-to-roll transport, resulting in poor appearance and a low yield.

[0005] Furthermore, one of the required characteristics for glass cloth used in printed circuit boards is to reduce the number of remaining voids. The mechanism by which voids remain is that voids remaining in the prepreg, which is formed by impregnating glass cloth with a matrix resin and semi-curing it, remain even after the press molding process. Glass cloth treated with amino group-containing organosilicon compounds, as described in Patent Documents 3 and 4, had the problem of generating a large number of such voids.

[0006] Furthermore, although the surface treatment of glass cloth is carried out in the form of an aqueous solution, some types of silane coupling agents or amino group-containing organosilicon compounds have low dilution in water, making them prone to gelation in aqueous solvents. This can lead to problems such as uneven surface treatment or poor surface treatment efficiency.

[0007] International Publication No. 2014 / 203511 International Publication No. 2019 / 167391 JP 5-147979 JP 7-258415

[0008] The present invention has been made to solve the problems of the above-mentioned prior art, and aims to provide a mixture of amino group-containing organosilicon compounds or their salts (preferably hydrochloride salts) and a method for producing the same, as well as a surface treatment agent containing a mixture of amino group-containing organosilicon compounds or their salts, for producing a surface treatment agent that has a hard texture, i.e., high bending rigidity, can suppress the occurrence of wrinkles during roll-to-roll transport, is less likely to leave voids in printed wiring boards, and can improve insulation reliability. Furthermore, the present invention aims to provide a mixture of amino group-containing organosilicon compounds or their salts, a method for producing the same, and a surface treatment agent containing a mixture of the salts, which have excellent water dilution properties and form a uniform solution without gelling in an aqueous solvent.

[0009] The present inventors have diligently studied the above problems and arrived at the present invention. That is, in order to solve the above problems, one aspect of the present invention includes the following aspects.

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

[0011] A mixture of an amino group-containing organosilicon compound represented by or a salt thereof.

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

[0013] [3] The residual amounts of benzyl halide and vinylbenzyl halide as reaction raw materials with respect to 1 mol of the amino group-containing organosilicon compound represented by the general formula (1) or a salt thereof are each 0.01 mol or less, the mixture according to [1] or [2].

[0014] [4] The following general formula (2): [In the formula (2), R １ is an arylene group or a cyclic or acyclic divalent hydrocarbon group of C １ ~C １０ ; R２ 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]

[0015] For an amino group-containing organosilicon compound represented by the following general formula (3): [In formula (3), X represents a halogen atom, R ５ is an allerene group or C １ ~C １０ [Represents a cyclic or otherwise divalent hydrocarbon group]

[0016] A step of reacting an alcohol substituted with a halogen atom represented by the following general formula (4): [In formula (4), X represents a halogen atom.]

[0017] A method for producing a mixture of an amino group-containing organosilicon compound or a salt thereof, comprising the step of reacting one or more selected from halomethylstyrene represented by .

[0018] [5] A method for producing a mixture of an amino group-containing organosilicon compound or a salt thereof according to [4], characterized in that the alcohol substituted with a halogen atom is one or more selected from the group consisting of 3-chloro-1-propanol, 3-chloro-2,2-dimethyl-1-propanol, 4-chloro-1-butanol, trichloro-2-methyl-2-propanol, 5-chloro-1-pentanol, and 6-chloro-1-hexanonol.

[0019] [6] A method for producing a mixture of an amino group-containing organosilicon compound or a salt thereof according to [4] or [5], wherein the halomethylstyrene represented by the general formula (3) is chloromethylstyrene.

[0020] A surface treatment agent comprising a mixture described in any one of items [7] [1] to [3].

[0021] The present invention provides a surface treatment agent for producing glass cloth that has a hard texture, i.e., high bending rigidity, can suppress the occurrence of wrinkles during roll-to-roll transport, is less likely to leave voids in printed circuit boards, and can improve insulation reliability. Furthermore, the present invention provides a mixture of an amino group-containing organosilicon compound or its salt (preferably a hydrochloride salt) that has excellent water dilutability and forms a uniform solution without gelling in an aqueous solvent, as well as a method for producing the same, and a surface treatment agent containing the mixture of the salt.

[0022] The results of the stability evaluation of aqueous solutions of organosilicon compounds are shown. The amino group-containing organosilicon compounds of the present invention in Examples 1 to 3 were observed to exhibit excellent water dilution properties. In Comparative Example 6, it was confirmed that the water dilution properties were inferior to those of the examples.

[0023] 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.

[0024] 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.

[0025] [Mixture of amino group-containing organosilicon compounds or salts thereof] In the present invention, the amino group-containing organosilicon compound is of the following general formula (1):

[0026]

[0027] [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 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 The amino group-containing organosilicon compound according to the present invention is represented by a monovalent hydrocarbon group, and in the case of a salt, it 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.

[0028] In one embodiment, R １The arylene group is a substituted or unsubstituted divalent aromatic group, and the aromatic group 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.

[0029] 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.

[0030] In one embodiment, R ２ and R ３ C １ ~C １０The 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.

[0031] 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.

[0032] 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 a substrate such as glass cloth.

[0033] In one embodiment, 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 This represents a functional group that is a monovalent hydrocarbon group. Of these, the vinylbenzyl group is a group that forms a bond with the matrix resin impregnated into the glass cloth.

[0034] C substituted with one or more hydroxyl groups １ ~C １０ The monovalent hydrocarbon groups are, but are not limited to, alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups substituted with one or more hydroxyl groups; or groups in which some 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. 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 By being a monovalent hydrocarbon group, it is possible to provide a mixture of an amino group-containing organosilicon compound or a salt thereof that has excellent water dilution properties and forms a homogeneous solution without gelling in an aqueous solvent.

[0035] In one embodiment, C is substituted with one or more hydroxyl groups. １ ~C １０ The monovalent hydrocarbon group preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms.

[0036] In one embodiment, C is substituted with one or more hydroxyl groups. １ ~C １０ The monovalent hydrocarbon group is a linear or branched alkyl group substituted with one hydroxyl group.

[0037] The content of the benzyl group in 1 mol of the amino group-containing organosilicon compound represented by the general formula (1) of the present invention or its salt is 0.2 mol or more and 0.8 mol or less, preferably 0.2 mol or more and 0.6 mol or less, and more preferably 0.2 mol or more and 0.5 mol or less. By setting the content of the benzyl group within the above range, a glass cloth excellent in compatibility with the matrix resin can be provided.

[0038] The content of the vinylbenzyl group in 1 mol of the amino group-containing organosilicon compound represented by the general formula (1) of the present invention or its salt is 1.1 mol or more and 2.5 mol or less, preferably 1.3 mol or more and 2.3 mol or less, and more preferably 1.5 mol or more and 2.1 mol or less. By setting the content of the vinylbenzyl group within the above range, a glass cloth excellent in adhesion to the matrix resin can be provided.

[0039] The mixture of the amino group-containing organosilicon compound represented by the general formula (1) of the present invention or its salt is characterized in that the remaining amounts of benzyl halide (particularly, benzyl bromide or benzyl chloride) and vinylbenzyl halide (particularly, vinylbenzyl chloride or vinylbenzyl bromide) as reaction raw materials are small. The remaining amounts of benzyl halide and vinylbenzyl halide as reaction raw materials are each 0.01 mol or less with respect to 1 mol of the amino group-containing organosilicon compound represented by the general formula (1) or its salt. Preferably, the remaining amounts of benzyl chloride and vinylbenzyl chloride are each 0.009 mol or less with respect to 1 mol of the amino group-containing organosilicon compound represented by the general formula (1) or its salt. By setting the remaining amounts of benzyl chloride and vinylbenzyl chloride within the above range, a glass cloth excellent in compatibility with the matrix resin can be provided.

[0040] [Production method of mixture of amino group-containing organosilicon compound or its salt] The mixture of the amino group-containing organosilicon compound represented by the general formula (1) of the present invention or its salt is represented by the following general formula (2):

[0041] [In formula (2), R １ is an arylene group or C １~C １０ represents a cyclic or acyclic divalent hydrocarbon group, and 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 ~C １０ ; R ４ represents an arylene group or a cyclic or acyclic divalent hydrocarbon group of C １ ~C １０ ; n represents an integer of 0, 1 or 2]]

[0042] Reacting the amino group-containing organosilicon compound represented by with an alcohol substituted with a halogen atom represented by the following general formula (3): [In formula (3), X represents a halogen atom, and R ５ represents an arylene group or a divalent hydrocarbon group which may be cyclic of C １ ~C １０ , and reacting with one or more selected from benzyl halide and the following general formula (4): [In formula (4), X represents a halogen atom]]

[0043] The product is produced by a production method including the steps. The benzyl halide may be benzyl chloride or benzyl bromide, and benzyl halide and halomethylstyrene may be used in combination.

[0044] In one embodiment, R １ ~R ４ in the general formula (2) and n are the same groups and integers as R １ ~R ４ and n described for the general formula (1).

[0045] In one embodiment, the amino group-containing organosilicon compound represented by the general formula (2) is preferably one or more selected from the group consisting of 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, and 3-(2-aminoethylamino)propyldimethoxymethylsilane.

[0046] 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.

[0047] In one embodiment, the alcohol substituted with a halogen atom represented by general formula (3) is a C substituted with one or more halogen atoms. １ ~C １０ It may be a linear or branched alcohol.

[0048] In one embodiment, the alcohol substituted with a halogen atom represented by general formula (3) is preferably one or more selected from the group consisting of 3-chloro-1-propanol, 3-chloro-2,2-dimethyl-1-propanol, 4-chloro-1-butanol, trichloro-2-methyl-2-propanol, 5-chloro-1-pentanol, and 6-chloro-1-hexanonol.

[0049] In one embodiment, the halomethylstyrene represented by general formula (4) is preferably fluoromethylstyrene, chloromethylstyrene, or bromomethylstyrene, and is particularly preferably chloromethylstyrene.

[0050] [Surface treatment agent] The present invention also relates to a 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).

[0051] The surface treatment agent of the present invention may contain solvents such as water, alcohols, ethers, and ketones. The solvent contained in the 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.

[0052] 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.

[0053] In one embodiment, the surface treatment agent of the present invention is preferably acidic in order to improve the dispersibility and stability of a mixture of an amino group-containing organosilicon compound represented by general formula (1) or a salt thereof. Examples of acids for making the 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.

[0054] The solvents of the surface treatment agent of the present invention can be used alone, or two or more can be used in combination.

[0055] In one embodiment, the surface treatment agent of the present invention may contain an organosilicon compound having a carbon-carbon unsaturated double bond group, other than an amino group-containing organosilicon compound represented by the general formula (1) of the present invention or a mixture 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.

[0056] Organosilicon compounds containing carbon-carbon unsaturated double bond groups can be used individually, or in combination of two or more.

[0057] 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%.

[0058] In one embodiment, the 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 glutamates, dialkyl sulfosuccinates, alkane sulfonates, alpha-olefin sulfonates, linear alkylbenzene sulfonates, alkylbenzene sulfonates, naphthalene sulfonate-formaldehyde condensates, alkyl naphthalene sulfonates, N-methyl-N-acyl taurates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, oil sulfates, 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.

[0059] The concentration of the surfactant in the 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.

[0060] 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 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 surface treatment agent.

[0061] In one embodiment, the surface treatment agent of the present invention can be used to treat the surface of substrates such as glass, resin, metal, and ceramics. The shape of the substrate is not particularly limited, but may be in the form of fibers, plates, films, or parts.

[0062] [Method for producing the surface treatment agent] As a method for producing the surface treatment agent of the present invention, it is preferable to either 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 obtain an organic solvent solution, and then add the organic solvent solution to water.

[0063] 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.

[0064] [Preparation of mixtures of amino group-containing organosilicon compounds represented by general formula (1) or their hydrochloride salts] (Example 1) 3-(2-aminoethyl)aminopropyltrimethoxysilane (product name: Dowsil OFS-6094SILANE, 222.4 g, 1.0 mol) and 3-chloro-1-propanol (Tokyo Chemical Industries, 18.9 g, 0.2 mol) were added to a four-necked flask equipped with a magnetic stirrer bar, thermometer, Liebig condenser, and dropping funnel, and the mixture was stirred at 50°C for 20 hours. Next, methanol (Tokyo Chemical Industries, 539 g) and sodium methoxide (28% methanol solution, equivalent to 2.9 mol of sodium methoxide from Tokyo Chemical Industries) were added, and the mixture was stirred at 40°C for 4 hours. After that, benzyl chloride (Tokyo Chemical Industries, 25.3 g, 0.2 mol) was added, and the mixture was 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 a liquid temperature of 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. After that, 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 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.

[0065] The concentration of nonvolatile components at 110°C for 3 hours was 32.9% by weight, and the refractive index at 25°C was 1.405.

[0066] (Example 2) The same experiment as in Example 1 was carried out, except that the amount of 3-chloro-1-propanol used was 0.1 moles. The non-volatile component concentration of the obtained compound at 110°C for 3 hours was 35.3% by weight, and the refractive index at 25°C was 1.407.

[0067] (Example 3) The same experiment as in Example 1 was carried out, except that 6-chloro-1-hexanol was used instead of 3-chloro-1-propanol. The non-volatile component concentration of the obtained compound at 110°C for 3 hours was 35.3% by weight, and the refractive index at 25°C was 1.409.

[0068] (Comparative Example 1) In Example 1, when 28.4 g (0.3 mol) of 3-chloro-1-propanol was added, the contents of the flask gelled in the subsequent stage, and the target amino group-containing organosilicon compound could not be obtained.

[0069] (Comparative Example 2) In Example 1, when the amount of -chloro-1-propanol added was 37.8 g (0.4 mol), the contents of the flask gelled in the subsequent stage, and the target amino group-containing organosilicon compound could not be obtained.

[0070] (Comparative Example 3) In Example 1, when methanol was not added, the contents of the flask gelled during the reaction with chloromethylstyrene, and the target amino group-containing organosilicon compound could not be obtained.

[0071] (Comparative Example 4) In Example 1, when the order in which 3-chloro-1-propanol and benzyl chloride were added was reversed, the contents of the flask gelled after the addition of 3-chloro-1-propanol, and the target amino group-containing organosilicon compound could not be obtained.

[0072] (Comparative Example 5) In Example 1, when 3-chloro-1-propanol was added after the dropwise addition of chloromethylstyrene, the contents of the flask gelled, and the target amino group-containing organosilicon compound could not be obtained.

[0073] (Comparative Example 6) The reaction was carried out in Example 1 without adding 3-chloro-1-propanol.

[0074] [Stability evaluation of aqueous solutions of organosilicon compounds]

[0075] The solubility of the compound obtained in Example 1 in water was investigated by the following method. An aqueous acetic acid solution was prepared in advance so that the concentration of acetic acid was 0.5% by weight.

[0076] 100 g of aqueous acetic acid solution was stirred at room temperature, and the compounds synthesized in Examples 1, 2, and 3 (equivalent to 0.3 g of solid content) were added dropwise over approximately 5 minutes, followed by stirring for 10 minutes. After that, stirring was stopped, and the resulting aqueous solution was allowed to stand at room temperature. The formation of precipitate and turbidity after 72 hours was observed visually. The observation results are shown in Table 1 and Figure 1.

[0077] As shown in Table 1 and Figure 1, the amino group-containing organosilicon compound of the present invention was observed to exhibit excellent water dilution properties. This is due to the excellent effect of having hydrophilic hydroxyl groups. On the other hand, in Comparative Examples 1 to 5, the contents of the flasks gelled, and the target amino group-containing organosilicon compound could not be obtained. Furthermore, in Comparative Example 6, it was confirmed that the amino group-containing organosilicon compound lacked hydrophilic hydroxyl groups, resulting in inferior water dilution properties compared to the examples.

Claims

1. 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 monovalent hydrocarbon groups 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 hydrogen atom, a benzyl group, a vinylbenzyl group, and a monovalent hydrocarbon group of C １ to C １０ substituted with one or more hydroxyl groups, provided that at least one of Q １ , Q ２ , and Q ３ is a monovalent hydrocarbon group of C １ to C １０ substituted with one or more hydroxyl groups, representing a functional group], a mixture of an amino group-containing organosilicon compound represented thereby or a salt thereof.

2. One mole of an amino group-containing organosilicon compound represented by the general formula (1) or a salt thereof, containing one or more hydroxyl groups substituted with C １ ~C １０ The mixture according to claim 1, wherein the content of monovalent hydrocarbon groups is 0.2 or less.

3. The mixture according to claim 1, wherein the remaining 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.

4. The following general formula (2): [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 An amino group-containing organosilicon compound represented by [where n represents a cyclic or acyclic divalent hydrocarbon group, and n is an integer of 0, 1, or 2] is given the following general formula (3): [In formula (3), X represents a halogen atom, R ５ is an allerene group or C １ ~C １０ A step of reacting an alcohol substituted with a halogen atom represented by [which may be a cyclic divalent hydrocarbon group], and benzyl halide and the following general formula (4): A method for producing an amino group-containing organosilicon compound or a mixture of the same salt, comprising the step of reacting one or more selected from halomethylstyrene represented by [formula (4) where X represents a halogen atom].

5. A method for producing a mixture of an amino group-containing organosilicon compound or a salt thereof according to claim 4, characterized in that the halogen-substituted alcohol is one or more selected from the group consisting of 3-chloro-1-propanol, 3-chloro-2,2-dimethyl-1-propanol, 4-chloro-1-butanol, trichloro-2-methyl-2-propanol, 5-chloro-1-pentanol, and 6-chloro-1-hexanonol.

6. A method for producing a mixture of an amino group-containing organosilicon compound or a salt thereof according to claim 4, wherein the halomethylstyrene represented by the general formula (3) is chloromethylstyrene.

7. A surface treatment agent comprising the mixture described in any one of claims 1 to 3.

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