Composition containing organosilicon compound containing methacrylamido group and article surface-treated with the composition

Abstract

Provided is a composition comprising a methylacrylamido-containing organosilicon compound represented by the following formula (1) and an organosilicon compound represented by the following formula (2). (In the formulae, R 1 each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R 2 represents a methyl group or an ethyl group, Me represents a methyl group, m1 and m2 represent an integer of 1 to 3, and n1 and n2 represent an integer of 1 to 12.)

Description

Technical Field

[0001] The present invention relates to compositions comprising organosilicon compounds containing methacrylamide and articles surface-treated with the compositions, and more specifically, to compositions comprising organosilicon compounds containing methacrylamide and an organooxysilyl group in the molecule and articles surface-treated with the compositions. Background Technology

[0002] Organosilicon compounds containing hydrolyzable silane groups and reactive organic groups form covalent bonds with hydroxyl groups on the surface of inorganic materials through the hydrolysis of the silane groups, resulting in silanol groups. These organic groups then react with the organic materials, often enabling the bonding of difficult-to-bond organic and inorganic materials. This allows organic-inorganic composites to acquire properties such as heat resistance, water resistance, weather resistance, improved mechanical strength, better adhesion, better dispersibility, hydrophobicity, and rust prevention.

[0003] Taking advantage of these properties, the aforementioned organosilicon compounds are used in a wide range of fields as silane coupling agents, resin additives, surface treatment agents, fiber treatment agents, adhesives, coating additives, and polymer modifiers.

[0004] Among the aforementioned organosilicon compounds, organosilicon compounds containing polymerizable groups, represented by 3-methacryloylpropyltrimethoxysilane, have been widely used as surface treatment agents for glass products such as glass cloth and inorganic fillers, as well as adhesives for curing compositions.

[0005] For example, Patent Document 1 reports that the properties of prepregs can be improved by using glass cloth treated with 3-methacryloylpropyltrimethoxysilane. Furthermore, Patent Document 2 reports that the properties of thermosetting resins can be improved by using silica particles treated with 3-methacryloylpropyltrimethoxysilane.

[0006] In surface treatments using glass cloth and inorganic fillers, a typical method involves dissolving approximately 1% of a specified organosilicon compound in water that has been acidified with acids such as formic acid or acetic acid. However, if an organosilicon compound containing alkoxysilyl groups is dissolved in water, the alkoxysilyl group undergoes hydrolysis in the aqueous solution, leading to intermolecular condensation, an increase in molecular weight, and precipitation of insoluble components. Similarly, organosilicon compounds containing polymerizable groups, such as 3-methacryloylpropyltrimethoxysilane, also exhibit low stability when prepared as aqueous solutions, resulting in a short pot life for surface treatment solutions.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: International Publication No. 2020 / 194772

[0010] Patent Document 2: International Publication No. 2019 / 103086 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] The present invention was made in view of the above-mentioned circumstances, and its object is to provide a composition containing an organosilicon compound having excellent stability when prepared into an aqueous solution. The composition comprises an organosilicon compound containing polymeric groups and hydrolyzable silyl groups.

[0013] Methods for solving problems

[0014] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that aqueous solutions containing organosilicon compounds with methacrylamide and organooxy groups and specific organosilicon compounds having methacrylate sites have excellent stability, thus completing the present invention.

[0015] That is, the present invention provides:

[0016] 1. A composition comprising an organosilicon compound containing methacrylamide as represented by formula (1) below and an organosilicon compound as represented by formula (2) below,

[0017] [Chemistry 1]

[0018]

[0019] (where R is in the formula) 1 Each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R 2 (Me represents methyl or ethyl, m1 and m2 represent integers from 1 to 3, and n1 and n2 represent integers from 1 to 12.)

[0020] 2. The composition according to 1, wherein, in formulas (1) and (2), R 1 The methyl group is 3, and n1 and n2 are both 3.

[0021] 3. The composition according to 1 or 2, wherein the content of the organosilicon compound represented by formula (2) is 0.01 to 20 parts by mass relative to 100 parts by mass of the organosilicon compound containing methacrylamide represented by formula (1);

[0022] 4. The composition according to any one of 1 to 3, further comprising water, wherein the organosilicon compound containing methacrylamide represented by formula (1) and the organosilicon compound represented by formula (2) are dissolved in the water;

[0023] 5. The composition according to 4, wherein the water is water adjusted to be acidic;

[0024] 6. An article that has been surface treated with the composition according to any one of 1 to 5.

[0025] The effects of the invention

[0026] The compositions of the present invention, comprising organosilicon compounds containing methacrylamide and an organooxy group, exhibit excellent stability when prepared into aqueous solutions. Furthermore, articles surface-treated with the compositions of the present invention exhibit excellent strength. Detailed Implementation

[0027] The present invention will be described in detail below.

[0028] The composition of the present invention contains an organosilicon compound containing methacrylamide as represented by formula (1) below (hereinafter referred to as compound (1)) and an organosilicon compound as represented by formula (2) below (hereinafter referred to as compound (2)), and exhibits excellent stability when prepared into an aqueous solution.

[0029] [Chemistry 2]

[0030]

[0031] In the formula, R 1 Each of the following independently represents an alkyl group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms. R 2 Me represents methyl or ethyl, m1 and m2 represent integers from 1 to 3, and n1 and n2 represent integers from 1 to 12.

[0032] As R 1 Alkyl groups having 1 to 10 carbon atoms can be linear, cyclic, or branched. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

[0033] Specific examples of aryl groups with 6 to 10 carbon atoms include phenyl, α-naphthyl, and β-naphthyl.

[0034] Among these, as R 1 Preferably, it is an alkyl group having 1 to 3 carbon atoms, more preferably methyl or ethyl, and even more preferably methyl.

[0035] m1 and m2 represent integers from 1 to 3, preferably 2 or 3, and n1 and n2 represent integers from 1 to 12. From the viewpoint of raw material supply, integers from 1 to 8 are preferred, integers from 1 to 4 are more preferred, and 3 is even more preferred.

[0036] Therefore, R is particularly preferred as compound (1). 1 Compounds with a methyl group and n1 of 3 are preferred as compound (2), especially those with R. 1 It is a compound with a methyl group and n2 = 3.

[0037] Specific examples of compound (1) include methacryloamidomethyltrimethoxysilane, methacryloamidomethylmethyldimethoxysilane, methacryloamidomethyltriethoxysilane, methacryloamidomethylmethyldiethoxysilane, 3-methacryloamidopropyltrimethoxysilane, 3-methacryloamidopropylmethyldimethoxysilane, 3-methacryloamidopropyltriethoxysilane, 3-methacryloamidopropylmethyldiethoxysilane, 4-methacryloamidobutyltrimethoxysilane, 4-methacryloamidobutylmethyldimethoxysilane, and 4-methylpropenyl... Acylaminobutyltriethoxysilane, 4-methacrylaminobutylmethyldiethoxysilane, 8-methacrylaminooctyltrimethoxysilane, 8-methacrylaminooctylmethyldimethoxysilane, 8-methacrylaminooctyltriethoxysilane, 8-methacrylaminooctylmethyldiethoxysilane, 12-methacrylaminododecyltrimethoxysilane, 12-methacrylaminododecylmethyldimethoxysilane, 12-methacrylaminododecyltriethoxysilane, 12-methacrylaminododecylmethyldiethoxysilane, etc., but not limited to these. One of these can be used alone, or two or more can be used in combination.

[0038] Among these, compounds represented by the following formulas are preferred, and from the viewpoint of manufacturing and preparation in aqueous solution, compounds (1-1) and (1-3) are particularly preferred. It should be noted that in the following formulas, Me represents methyl and Et represents ethyl.

[0039] [Chemistry 3]

[0040]

[0041] There are no particular limitations on the manufacturing method of compound (1), and conventionally known manufacturing methods can be used. For example, it can be obtained by reacting methyl methacrylate and aminoalkylalkoxysilanes such as 3-aminopropyltrimethoxysilane in the presence of a polymerization inhibitor and an amidation catalyst at a temperature of about 100 to 200°C, according to the method described in Japanese Patent No. 3561501.

[0042] On the other hand, compound (2) acts as a compatibilizer for compound (1) and water, providing a composition with excellent water solubility.

[0043] Specific examples of compound (2) include N-(2-methoxycarbonyl-2-methyl)ethyl-3-aminopropyltrimethoxysilane, N-(2-methoxycarbonyl-2-methyl)ethyl-3-aminopropylmethyldimethoxysilane, N-(2-methoxycarbonyl-2-methyl)ethyl-3-aminopropyldimethylmethoxysilane, N-(2-methoxycarbonyl-2-methyl)ethyl-3-aminopropyldimethylmethoxysilane, N-(2-methoxycarbonyl-2-methyl)ethyl-3-aminopropyltriethoxysilane, N-(2-methoxycarbonyl-2-methyl)ethyl-3-aminopropylmethyldiethoxysilane, and N-(2-methoxycarbonyl-2-methyl)ethyl-3-aminopropyldimethylethoxysilane. The silanes include, but are not limited to, N-(2-ethoxycarbonyl-2-methyl)ethyl-3-aminopropyltrimethoxysilane, N-(2-ethoxycarbonyl-2-methyl)ethyl-3-aminopropylmethyldimethoxysilane, N-(2-ethoxycarbonyl-2-methyl)ethyl-3-aminopropyldimethylmethoxysilane, N-(2-ethoxycarbonyl-2-methyl)ethyl-3-aminopropyldimethylethoxysilane, etc. One of these may be used alone, or two or more may be used in combination.

[0044] Among these, compounds represented by the following formulas are preferred, and from the viewpoint of manufacturing and preparation in aqueous solution, compounds (2-1) and (2-3) are particularly preferred. It should be noted that in the following formulas, Me represents methyl and Et represents ethyl.

[0045] [Chemistry 4]

[0046]

[0047] There are no particular limitations on the manufacturing method of compound (2), and conventionally known manufacturing methods can be used. For example, it can be obtained by reacting methyl methacrylate or other methacrylates with aminoalkylalkoxysilanes such as 3-aminopropyltrimethoxysilane in a reaction solvent such as methanol at a temperature of about 0 to 200°C according to the method described in Japanese Patent No. 5494233.

[0048] The content of compound (2) in the composition is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of compound (1), more preferably 0.1 to 15 parts by mass, and even more preferably 0.5 to 13 parts by mass.

[0049] The composition of the present invention may contain water, in which case compounds (1) and (2) are dissolved in water in the composition.

[0050] When water is included, the content of compounds (1) and (2) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and even more preferably 0.1 to 1% by mass.

[0051] A water-containing composition (hereinafter sometimes referred to as an "aqueous solution") can be prepared by mixing a pre-prepared mixture of compound (1) and compound (2) (an anhydrous composition) with water, thereby dissolving compound (1) and compound (2) in water.

[0052] In this case, the mixture of compound (1) and compound (2) can be added to water, or water can be added to the mixture. It is preferred to add the mixture to water, and more preferably to add the mixture dropwise to water.

[0053] The preferred temperature for adding the product is 10–50°C, and more preferably 15–40°C.

[0054] Alternatively, compositions containing water can be obtained by dissolving compounds (1) and (2) separately in water. In this case, compound (1) can be added to water first, followed by compound (2), or compound (2) can be added to water first, followed by compound (1). Alternatively, by preparing mixtures of compound (1) and water and mixtures of compound (2) and water separately, and then mixing them, an aqueous solution (composition) containing compounds (1) and (2) can be obtained. In any case, either compound (1) or compound (2) can be added to water, or water can be added to either compound (1) or compound (2). The addition temperature is the same as described above.

[0055] In addition to compounds (1), (2), and water, the compositions of the present invention may contain organic solvents, without impairing the effects of the present invention.

[0056] There are no particular limitations on the organic solvents used, but organic solvents with excellent compatibility with water are preferred. Examples include alcohols such as methanol, ethanol, and isopropanol; ethers such as diethyl ether, tetrahydrofuran, and 1,4-dioxane; esters such as ethyl acetate; and ketones such as acetone and methyl ethyl ketone. One type can be used alone, or two or more types can be used in combination.

[0057] From a stability point of view, the composition of the present invention preferably uses water adjusted to acidity, without using the aforementioned organic solvents. Examples of acids used for adjusting to acidity include organic acids such as formic acid, acetic acid, and citric acid, and inorganic acids such as hydrochloric acid. When using an acid, its addition amount is preferably 0.001 to 0.5% by mass of the total composition, more preferably 0.01 to 0.1% by mass. Furthermore, when using an acid, water pre-mixed with acid and water to adjust to acidity can be used, or acid can be added to the composition of the present invention to adjust to acidity.

[0058] In order to improve the adhesion and bonding properties with the substrate, organosilicon compounds containing alkoxy groups, silazane compounds, etc., other than compounds (1) and (2) can be added to the composition of the present invention.

[0059] Specific examples of organosilicon compounds containing alkoxy groups include 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, p-styryltrimethoxysilane, and 8-methacryloyloxyoctyltrimethoxysilane. These can be used individually or in combination of two or more.

[0060] Specific examples of silazane compounds include 1,1,3,3-tetramethyldisilazane, 1,1,1,3,3,3-hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,1,1,3,3,5,5,5-octamethyltrisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, and 1,1,3,3,5,5-trimethyltrivinylcyclotrisilazane. These can be used individually or in combination of two or more.

[0061] When adding organosilicon compounds containing alkoxy groups and compounds containing silazane structures, the amount of each added is preferably 0.01 to 0.2 molar equivalents relative to the total amount of compounds (1) and (2).

[0062] Furthermore, other additives may be added to the composition of the present invention as needed, without impairing the effects of the present invention. Specific examples of additives include water-soluble resins, curing catalysts, physical property modifiers that adjust the tensile properties of the resulting cured film, storage stability improvers, surfactants, metal passivators, ozone deterioration inhibitors, lubricants, pigments, etc.

[0063] By applying the composition of the present invention to the surface of a substrate and heating and drying it, it is possible to obtain an article that has been surface-treated with the composition of the present invention.

[0064] There are no particular limitations on the substrate, but inorganic materials are preferred. Examples of inorganic fillers include silicon dioxide, titanium dioxide, zirconium oxide, calcium carbonate, magnesium carbonate, aluminum oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, talc, clay, and mica; various fibers such as monofilaments, twisted yarns, loose textured yarns, short fibers, nonwoven fabrics, tapes, and nets; glass fibers and glass fiber products such as glass fiber bundles, glass yarn, glass roving, chopped strands, ground fibers, and glass cloth; ceramics such as ceramics, cement, enamel, and fine ceramics; metals such as iron, aluminum, copper, silver, gold, and magnesium; and various items that use these materials.

[0065] From the viewpoint of the reactivity of organooxysilyl groups, inorganic fillers such as silica, glass fibers, and glass fiber products are particularly preferred. When the substrate is an inorganic filler or glass fiber, a prepreg blank can be formed by mixing it with a matrix resin. The prepreg blank obtained using the composition of the present invention is suitable for use in printed wiring boards due to its excellent strength. Furthermore, conventionally known matrix resins can be used as the matrix resin for the prepreg blank, such as thermosetting silicone resins, polyimide resins, maleimide resins, epoxy resins, cyanate ester resins, and (meth)acrylic resins.

[0066] There are no particular limitations on the method for applying the composition of the present invention to the surface of a substrate, but the optimal method can be appropriately selected depending on the shape of the material, etc. Specifically, methods for direct application to the substrate include flow coating (immersion coating) and spin coating. In addition, the composition of the present invention can also be added to and mixed into a compound consisting of an inorganic filler and a resin that serves as a dispersion medium, thereby performing a compounding process.

[0067] Preferably, after applying the composition of the present invention to various substrates, it is heated and dried to remove the solvent, thereby allowing the alkoxy groups contained in the organosilicon compound in the composition to chemically react with the reactive groups on the surface of the substrate.

[0068] There are no particular restrictions on the heating conditions. The heating temperature can be appropriately adjusted according to the heat resistance of the substrate, preferably 60 to 180°C, more preferably 80 to 150°C. There are also no particular restrictions on the heating time, which can be appropriately adjusted according to the type of substrate used, the amount of the composition of the present invention, etc., preferably 1 minute to 2 hours, more preferably 5 minutes to 1 hour.

[0069] Example

[0070] The following examples, embodiments, and comparative examples illustrate the invention in more detail, but the invention is not limited to these embodiments. It should be noted that in the following formulas, Me represents methyl and Et represents ethyl.

[0071] [1] Synthesis of organosilicon compounds

[0072] [Synthesis example 1]

[0073] Referring to Japanese Patent No. 3561501, an organosilicon compound containing methacrylamide, represented by the following formula, was obtained (1-1).

[0074] [Chemistry 5]

[0075]

[0076] [Synthesis example 2]

[0077] Referring to Japanese Patent No. 3561501, organosilicon compounds containing methacrylamide, represented by the following formulas, were obtained (1-3).

[0078] [Chemistry 6]

[0079]

[0080] [Synthesis example 3]

[0081] Referring to Japanese Patent No. 5494233, an organosilicon compound (2-1) represented by the following formula was obtained.

[0082] [Chemistry 7]

[0083]

[0084] [2] Preparation of the composition

[0085] [Examples 1-1 to 1-4]

[0086] The compounds obtained in the above synthesis examples were mixed in the proportions shown in Table 1 to obtain a composition.

[0087] [Table 1]

[0088]

[0089] [3] Preparation of aqueous solutions

[0090] [Examples 2-1 to 2-4, Comparative Examples 2-1 to 2-3]

[0091] According to the proportions shown in Table 2, at 25°C, aqueous solutions were prepared by adding dropwise the compositions obtained in Examples 1-1 to 1-4, the compounds obtained in Synthetic Examples 1 and 2, or the comparative components to 0.05% acetic acid water.

[0092] The obtained aqueous solution was evaluated as follows. The results are shown in Table 2.

[0093] [Stability of aqueous solutions]

[0094] The appearance of the obtained aqueous solution after standing at 25°C for 1 day, 14 days, and 28 days is visually confirmed and evaluated according to the following standards.

[0095] 〇: It dissolved completely and became a homogeneous aqueous solution.

[0096] ×: Insoluble matter precipitated.

[0097] [Tensile strength of surface-treated glass cloth]

[0098] In the obtained aqueous solution, E glass cloth (thickness: 95 μm, mass per unit area: 107 g / m²) was added. 2 After impregnation, the surface-treated glass cloth was removed and dried at 110°C for 10 minutes to obtain surface-treated glass cloth. The tensile strength of the surface-treated glass cloth was determined according to JIS R 3420:2013 (General Test Methods for Glass Fibers). Furthermore, the tensile strength of the untreated glass cloth was 150 N / 25 mm.

[0099] [Table 2]

[0100]

[0101] KBM-503 (3-Methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

[0102] As shown in Table 2, the aqueous solutions of Examples 2-1 to 2-4 exhibit excellent stability. In addition, the glass cloth treated with the aqueous solutions of Examples 2-1 to 2-4 exhibits excellent tensile strength.

[0103] On the other hand, the aqueous solutions of Comparative Examples 2-1 to 2-3, which do not contain compound (2), have poor stability, and as a result, insoluble substances precipitate out over time.

Claims

1. A composition comprising an organosilicon compound containing methacrylamide as represented by formula (1), an organosilicon compound as represented by formula (2), and water adjusted to an acidic state. In the formula, R 1 Each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R 2 Me represents methyl or ethyl, m1 and m2 represent integers from 1 to 3, and n1 and n2 represent integers from 1 to 12. The content of the organosilicon compound represented by formula (2) is 0.01 to 20 parts by mass relative to 100 parts by mass of the organosilicon compound containing methacryloylamino represented by formula (1).

2. The composition according to claim 1, wherein, In equations (1) and (2), R 1 It is a methyl group, and n1 and n2 are 3.

3. The composition according to any one of claims 1 to 2, wherein, The organosilicon compound containing methacrylamide, represented by formula (1), and the organosilicon compound represented by formula (2) are dissolved in the water.

4. An article that has been surface-treated with the composition according to any one of claims 1 to 3.

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