Room-temperature curable resin composition with excellent antibacterial properties and its cured product

Abstract

To provide a room temperature curable resin composition which can efficiently impart sustainable antibacterial property to a surface of a cured product without impairing appearance and curability, and physical properties after curing.SOLUTION: A room temperature curable resin composition contains: (A) 100 pts.mass of an organic resin polymer having at least one reactive silyl group in one molecule and having viscosity at 23°C of 10 to 10,000,000 mPa s; (B) 0.01 to 10 pts.mass of a quaternary ammonium salt represented by the following general formula (1), (in the formula, R1 and R2 are alkyl groups having 1 to 10 carbon atoms, R3 is an alkyl group having 12 to 24 carbon atoms, R4 and R5 are alkyl groups having 1 to 6 carbon atoms, and X is a halogen atom); (C) 1 to 300 pts.mass of an inorganic filler; and (D) 1 to 30 pts.mass of a hydrolyzable organosilane compound having at least three hydrolyzable groups in one molecule and / or its partially hydrolyzed condensate.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a room-temperature curable resin composition with excellent antibacterial properties and its cured product. [Background technology]

[0002] Room-temperature curable resin compositions, which are liquid or paste-like in nature, are filled and sealed in moisture-proof packaging containers for storage, and when used, they are dispensed from the container, harden upon reaction with moisture in the atmosphere, and become a rubbery elastic material after hardening. These compositions are widely used as sealants and coatings in industrial applications such as construction, civil engineering, and electrical and electronics, as well as in general consumer applications such as DIY projects. As room-temperature curable resin compositions, various organic resin polymers having at least one reactive silyl group in the molecule as a crosslinking site are preferably used, such as those mainly composed of polyorganosiloxane (room-temperature curable silicone rubber compositions, room-temperature curable silicone gel compositions, etc.), those mainly composed of polyoxyalkylene (room-temperature curable modified silicone resin compositions, etc.), those mainly composed of acrylic polymer (room-temperature curable silylated acrylate resin compositions), and those mainly composed of polyisobutylene (room-temperature curable polyisobutylene resin compositions).

[0003] Room-temperature curable resin compositions used as sealing and coating materials for construction and civil engineering are prone to mold and fungi growth on the surface of the cured composition (cured surface) depending on the usage environment. Therefore, it has long been common practice to impart antifungal and antibacterial properties to these compositions, and the most common method is to incorporate antifungal and antibacterial agents into the room-temperature curable resin composition. For imparting antifungal properties, benzimidazole compounds such as carbendazim, triazole compounds such as tebuconazole and propiconazole, and isothiazolinone compounds such as octylisothiazolinone have been used for a long time. Although the amount added is limited to very small amounts to prioritize safety and suppression of yellowing, even a weak antifungal effect with limited amounts is suitable for use. This is because areas where mold easily grows outdoors are places exposed to rain, such as exterior walls, and indoors are areas with water, such as kitchens, washrooms, and bathrooms. Since these areas are easy to clean, even if the antifungal agent is not very effective, regular cleaning and ventilation can suppress the growth and proliferation of mold.

[0004] On the other hand, in recent years, due to the problem of food poisoning caused by pathogenic E. coli O157 and the increasing demand for antibacterial flooring, sanitary ware, and other antibacterial products, antibacterial properties are also becoming necessary for sealants and coatings used around these materials. However, conventional sealants, whose primary purpose is mold resistance, do not consider antibacterial properties, so sealants with antibacterial properties in addition to mold resistance are needed. Antibacterial agents used to impart antibacterial properties can be broadly divided into two types: organic and inorganic. Organic agents have a fast-acting bactericidal effect and strong antibacterial effect, but they are sensitive to heat, have a short duration of effect, and are also harmful to the human body, so they require careful use. Among organic agents, those derived from natural products are generally safer, but their duration of effect is insufficient, and the combinations that are compatible with the polymers they are blended with are limited. Inorganic agents are typically silver, copper, and zinc-based, and they exert their antibacterial effect through ions generated by the metals. Inorganic agents use metal ions supported on zeolites or clay minerals. While it is heat-resistant and has a long-lasting effect, it also has the property of forming complexes with various organic compounds from the usage environment, resulting in strong discoloration. Therefore, in applications where the aesthetic appearance of the cured surface of the composition (cured product surface) is important, the amount added must be kept to a minimum. Furthermore, in the case of thick antibacterial products, only the antibacterial agent present on the surface can contribute to the antibacterial effect, and most of the expensive antibacterial agent added is contained within, resulting in waste and economic disadvantage.

[0005] According to Patent Document 1, a silicone-based sealant has been proposed that is excellent in antifungal and antibacterial properties, is safe, weather-resistant, does not discolor, and maintains high antifungal and antibacterial properties even when used in wet areas. However, when disodium octaborate tetrahydrate, an essential component, is incorporated, the stability of the hydrolyzable silane is impaired, raising concerns about the storage stability of the composition itself.

[0006] According to Patent Document 2, an antibacterial and antifungal agent characterized by graft-bonding a polymer having 2-methyl-N-1,3-thiazol-2-acrylamide as a monomer to inorganic particles is difficult to elute, difficult to vaporize, has excellent dispersibility, and high durability can be obtained. However, since the active ingredient is bonded to the inorganic particles, it does not function efficiently on the surface of the composition, and there is still a cost disadvantage in applications with a certain thickness such as sealing materials.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0008] An object of the present invention is to simply provide a room-temperature curable resin composition such as a room-temperature curable silicone-based resin composition (room-temperature curable silicone rubber composition, room-temperature curable silicone gel composition) or a room-temperature curable modified silicone-based resin composition (room-temperature curable polyether resin composition having a reactive silyl group as a crosslinking point), which can efficiently impart sustainable antibacterial properties to the surface of the cured product without impairing the appearance, curability, and physical properties after curing.

Means for Solving the Problems

[0009] As a result of intensive research to achieve the above object, the present inventors have found that an organic resin polymer having at least one reactive silyl group in one molecule and a viscosity at 23°C of 10 to 10,000,000 mPa·s is combined with a quaternary ammonium salt silane represented by the following general formula (1).

Chemical Formula

[0010] That is, the present invention provides the following room temperature curable resin composition and a cured product thereof. [1] (A) An organic resin polymer having at least one reactive silyl group in one molecule and having a viscosity at 23°C of 10 to 10,000,000 mPa·s: 100 parts by mass, (B) A quaternary ammonium salt silane represented by the following general formula (1): 0.01 to 10 parts by mass, [Chemical formula] (In the formula, R 1 and R 2 are independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R 3 is an alkyl group having 12 to 24 carbon atoms, and R 4 and R 5 are independently an alkyl group having 1 to 6 carbon atoms, X is a halogen atom, m is an integer of 1 to 20, and n is an integer of 1 to 3. ), (C) An inorganic filler: 1 to 300 parts by mass, and (D) A hydrolyzable organosilane compound having at least three hydrolyzable groups in one molecule and / or a partial hydrolysis condensate thereof: 1 to 30 parts by mass, A room temperature curable resin composition comprising. [2] (A) The room-temperature curable resin composition according to [1], wherein component (A) is at least one selected from linear diorganopolysiloxanes represented by the following general formulas (2-1) and (2-2). [ka] (In the formula, R 6 R is a monovalent hydrocarbon group of the same or different type, unsubstituted or substituted, and p is a number of 10 or more. 7 (where is an identical or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is an oxygen atom or an unsubstituted or substituted divalent hydrocarbon group having 1 to 6 carbon atoms, and q is an integer from 1 to 3.) [3] A cured product of the room-temperature curable resin composition described in [1] or [2]. [Effects of the Invention]

[0011] The room-temperature curable resin composition of the present invention can efficiently impart persistent antibacterial properties to the surface of a cured product without impairing its appearance, curability, or physical properties after curing. [Modes for carrying out the invention]

[0012] The present invention will be described in detail below. (A) An organic resin polymer having at least one reactive silyl group in one molecule of component and a viscosity of 10 to 10,000,000 mPa·s at 23°C is the main component (base polymer) of the room-temperature curable resin composition of the present invention.

[0013] (A) Typical examples of reactive silyl groups that serve as crosslinking sites, with at least one present in each molecule of component (A), include hydrolyzable silyl groups such as silanol groups (hydroxyl groups bonded to a silicon atom) and alkoxysilyl groups.

[0014] The polymer main chain may be an organic polymer such as an organopolysiloxane, polyoxyalkylene, polyoxyalkylene extended by urethane bonds, polyisobutylene, or acrylic polymer, or it may be a copolymer polymer that partially contains an organosiloxane.

[0015] (A) The type of organic resin polymer used in component (A) does not significantly affect the imparting of antibacterial properties, which is the main objective of the present invention, as long as it has at least one reactive silyl group in one molecule and is within the viscosity range mentioned above.

[0016] The viscosity of component (A) at 23°C is 10 to 10,000,000 mPa·s, preferably 100 to 1,000,000 mPa·s, and more preferably 1,000 to 100,000 mPa·s. If the viscosity of component (A) is too low, the cured product will become too hard and have poor conformability, and if the viscosity is too high, mixing during manufacturing will be difficult, as will workability during use. The above viscosity can usually be measured using a rotational viscometer (e.g., BL type, BH type, BS type, cone plate type, rheometer, etc.).

[0017] (A) The number of reactive silyl groups in one molecule of component should be at least one, but from the viewpoint of curability and hardness of the cured product, it is preferably an average of 1.1 to 4, more preferably an average of 1.5 to 3, and even more preferably an average of 2 to 3.

[0018] The organic resin polymer of component (A) is preferably at least one selected from the linear diorganopolysiloxanes represented by the following general formulas (2-1) and (2-2), and it is easy to exhibit antibacterial properties while ensuring suitable appearance, properties, and curability for use as a sealant and coating material.

[0019] [ka]

[0020] (In the formula, R 6R is a monovalent hydrocarbon group of the same or different type, unsubstituted or substituted, and p is a number of 10 or more. 7 (where is an identical or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is an oxygen atom or an unsubstituted or substituted divalent hydrocarbon group having 1 to 6 carbon atoms, and q is an integer from 1 to 3.)

[0021] Here, in the general formulas (2-1) and (2-2) above, R 6 The unsubstituted or substituted monovalent hydrocarbon groups are preferably those having 1 to 12 carbon atoms, particularly 1 to 8 carbon atoms, and the unsubstituted or substituted monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, and dodecyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; vinyl and allyl groups. Examples of these groups include alkenyl groups such as propenyl, isopropenyl, butenyl, pentenyl, and hexenyl groups; aryl groups such as phenyl, tolyl, xylyl, and α-,β-naphthyl groups; aralkyl groups such as benzyl, 2-phenylethyl, and 3-phenylpropyl groups; and groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as F, Cl, and Br, or cyano groups, such as 3-chloropropyl, 3,3,3-trifluoropropyl, and 2-cyanoethyl groups. Among these, it is preferable to exclude aliphatic unsaturated hydrocarbon groups such as alkenyl groups, and more preferably alkyl groups such as methyl and ethyl groups, and aryl groups such as phenyl groups, with methyl groups being particularly preferred.

[0022] In the above general formula (2-2), R 7Examples of unsubstituted or substituted monovalent hydrocarbon groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; and alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, pentenyl, and hexenyl groups. Among these, lower alkyl groups having 1 to 3 carbon atoms, such as methyl, ethyl, and propyl groups, are preferred, with methyl and ethyl groups being more preferred.

[0023] In the general formulas (2-1) and (2-2) above, Y is an oxygen atom or an unsubstituted or substituted divalent hydrocarbon group having 1 to 6 carbon atoms, and the unsubstituted or substituted divalent hydrocarbon group having 1 to 6 carbon atoms is given by formula: -(CH2) j - or - (CH=CH) k Alkylene groups and alkenylene groups represented by -(where j is an integer from 1 to 6, preferably an integer from 1 to 3, and k is an integer from 1 to 3, preferably 1 or 2) are preferred. Among these, oxygen atoms, -CH2-, -CH2CH2-, -CH2CH2CH2-, and -CH=CH- are preferred.

[0024] In the general formulas (2-1) and (2-2) above, p is a number of 10 or more, but usually the average value is preferably 50 to 2,000, and more preferably 100 to 1,000. In the present invention, the degree of polymerization of an organic resin polymer such as a linear diorganopolysiloxane represented by the general formulas (2-1) and (2-2) can usually be determined by the number-average molecular weight (or number-average degree of polymerization) in polystyrene terms obtained by gel permeation chromatography (GPC) analysis using toluene, THF (tetrahydrofuran), etc., as the developing solvent.

[0025] The amount of the organic resin polymer of component (A) is preferably 30 to 95% by mass, and more preferably 50 to 90% by mass, relative to the total amount of the room-temperature curable resin composition of the present invention.

[0026] The quaternary ammonium salt silane represented by the following general formula (1) of component (B) is the most important component essential for imparting antibacterial properties to the room-temperature curable resin composition of the present invention.

[0027] [ka]

[0028] (In the formula, R 1 and R 2 Each of these is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R 3 R is an alkyl group having 12 to 24 carbon atoms. 4 and R 5 Each of these is an alkyl group having 1 to 6 carbon atoms, X is a halogen atom, m is an integer from 1 to 20, and n is an integer from 1 to 3.

[0029] R 1 The alkyl group has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. The alkyl group may be linear, branched, or cyclic, and specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, and the like.

[0030] R 1 The aryl group has 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms. Specific examples of aryl groups include phenyl groups and tolyl groups.

[0031] Among these, R 1 The alkyl group is preferably a C1-C3 alkyl group, and more preferably a methyl group or an ethyl group.

[0032] R 2 The alkyl groups with 1 to 10 carbon atoms and the aryl groups with 6 to 10 carbon atoms are, respectively, R 1 The same can be cited, and among them, the methyl group is more preferred.

[0033] R 3 The alkyl group has 12 to 24 carbon atoms, preferably 12 to 20 carbon atoms, and more preferably 12 to 18 carbon atoms. The alkyl group may be linear, branched, or cyclic, and specific examples include n-dodecyl group, 2-methylundecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, n-heneicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, cyclododecyl group, etc. Among these, R 3 A carbon atom with 14 to 18 carbon atoms is preferred, and an n-octadecyl group is more preferred from the viewpoint of raw material availability and environmental impact during use.

[0034] R 4 and R 5 The alkyl group having 1 to 6 carbon atoms can be linear, branched, or cyclic, and specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, etc. Among these, R 4 and R 5 In all cases, alkyl groups having 1 to 3 carbon atoms are preferred, and methyl groups are more preferred from the viewpoint of raw material availability and environmental impact during use.

[0035] m is an integer between 1 and 20, preferably between 3 and 12.

[0036] Examples of halogen atoms in X include chlorine atoms and bromine atoms.

[0037] (B)Specific examples of component include octadecyldimethyl(1-trimethoxysilylmethyl)ammonium chloride, octadecyldimethyl(1-triethoxysilylmethyl)ammonium chloride, octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, octadecyldimethyl(3-triethoxysilylpropyl)ammonium chloride, octadecyldimethyl(4-trimethoxysilylbutyl)ammonium chloride, octadecyldimethyl(4-triethoxysilylbutyl)ammonium chloride, octadecyldimethyl(6-trimethoxysilylhexyl)ammonium chloride, octadecyldimethyl(6-triethoxysilylhexyl)ammonium chloride, octadecyldimethyl(8-trimethoxysilyloctyl)ammonium chloride, octadecyldimethyl(8 -Dimethoxymethylsilyloctyl)ammonium chloride, octadecyldimethyl(8-diethoxymethylsilyloctyl)ammonium chloride, octadecyldimethyl(10-trimethoxysilyldecyl)ammonium chloride, octadecyldimethyl(10-triethoxysilyldecyl)ammonium chloride, octadecyldimethyl(11-trimethoxysilylundecyl)ammonium chloride, octadecyldimethyl(11-triethoxysilylundecyl)ammonium chloride, octadecyldimethyl(12-trimethoxysilyldodecyl)ammonium chloride, octadecyldimethyl(12-triethoxysilyldodecyl)ammonium chloride, dodecyldimethyl(8-triethoxysilyloctyl)ammonium chloride, dodecyldimethyl(8-dimethoxymethylsilyloctyl)ammonium chloride, tetradecyldimethyl(8-triethoxysilyloctyl) Examples include ammonium chloride, tetradecyldimethyl(8-dimethoxymethylsilyloctyl)ammonium chloride, octadecyldiethyl(8-triethoxysilyloctyl)ammonium chloride, and octadecyldiethyl(8-dimethoxymethylsilyloctyl)ammonium chloride. These can be used individually or in combination of two or more.

[0038] The quaternary ammonium salt silane represented by the above general formula (1) is obtained by reacting an organosilicon compound represented by the following general formula (a) with a tertiary amine represented by the following general formula (b) under an atmospheric environment or an inert gas atmosphere such as nitrogen.

[0039] [ka]

[0040] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 (X, m, and n are the same as above.)

[0041] Examples of compounds represented by the above general formula (a) include 1-chloromethyltrimethoxysilane, 1-chloromethyltriethoxysilane, 1-bromomethyltrimethoxysilane, 1-bromomethyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-bromopropyltrimethoxysilane, 3-bromopropyltriethoxysilane, 4-chlorobutyltrimethoxysilane, 4-chlorobutyltriethoxysilane, 4-bromobutyltrimethoxysilane, 4-bromobutyltriethoxysilane, 6-chlorohexyltrimethoxysilane, 6-chlorohexyltriethoxysilane, 6-bromohexyltrimethoxysilane, 6-bromohexyltriethoxysilane, 8-chlorooctyltrimethoxysilane, 8-chlorooctyltriethoxysilane, 8-chloro Examples include octyldimethoxymethylsilane, 8-chlorooctyldiethoxymethylsilane, 8-bromooctyltrimethoxysilane, 8-bromooctyltriethoxysilane, 8-bromooctyldimethoxymethylsilane, 8-bromooctyldiethoxymethylsilane, 10-chlorodecyltrimethoxysilane, 10-chlorodecyltriethoxysilane, 10-bromodecyltrimethoxysilane, 10-bromodecyltriethoxysilane, 11-chloroundecyltrimethoxysilane, 11-chloroundecyltriethoxysilane, 11-bromoundecyltrimethoxysilane, 11-bromoundecyltriethoxysilane, 11-bromoundecyltriethoxysilane, 12-chlorododecyltrimethoxysilane, 12-chlorododecyltriethoxysilane, 12-bromododecyltrimethoxysilane, and 12-bromododecyltriethoxysilane. These can be used individually or in combination of two or more types.

[0042] Examples of tertiary amines represented by the above general formula (b) include dodecyldimethylamine, dodecyldiethylamine, tridecyldimethylamine, tridecyldiethylamine, tetradecyldimethylamine, tetradecyldiethylamine, pentadecyldimethylamine, pentadecyldiethylamine, hexadecyldimethylamine, hexadecyldiethylamine, heptadecyldimethylamine, heptadecyldiethylamine, octadecyldimethylamine, octadecyldiethylamine, nonadecyldimethylamine, nonadecyldiethylamine, eicosyldimethylamine, eicosyldiethylamine, heneicosyldimethylamine, heneicosyldiethylamine, docosyldimethylamine, docosyldiethylamine, tricosyldimethylamine, tricosyldiethylamine, tetracosyldimethylamine, and tetracosyldiethylamine. These can be used individually or in combination of two or more.

[0043] Among these, octadecyldimethylamine and octadecyldiethylamine are preferred, with octadecyldimethylamine being more preferred.

[0044] The above reaction can be carried out without a solvent, but it can also be carried out in an alcohol solvent such as methanol or ethanol as needed, provided that it does not inhibit the reaction.

[0045] The reaction temperature is preferably 80 to 150°C, and more preferably 100 to 130°C. The reaction time is preferably 1 to 30 hours, and more preferably 5 to 25 hours.

[0046] The preferred ratio of the organosilicon compound represented by the above general formula (a) to the tertiary amine represented by the above general formula (b) during the reaction is 0.7 to 1.3 moles of organosilicon compound (a) per mole of tertiary amine (b).

[0047] (B) When incorporating component (B), it may be used in the form of a solution or dispersion containing alcohols such as methanol and ethanol, or other additives, to the extent that it does not impair the objective of the present invention. Examples of other additives include organic acids such as citric acid and surfactants. Adding these is preferable because it creates a highly stable solution state, allowing for uniform dispersion in the room-temperature curable resin composition of the present invention, preventing liquid phase separation and precipitation of aggregates in the composition before use (curing), resulting in a composition with an excellent appearance and a cured surface with an excellent appearance (design).

[0048] The amount of component (B) is 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, per 100 parts by mass of component (A). If the amount is less than 0.01 parts by mass, there is no effect, and if it is more than 10 parts by mass, it is not only economically disadvantageous but also deteriorates the properties, appearance, and curability.

[0049] The inorganic filler of component (C) consists of particles made of inorganic materials. Examples include silica, alumina, titania, zirconia, ferrite, magnesia, silica-titania, silicon carbide, silicon nitride, activated carbon, carbon black, carbon nanofiber, carbon nanotube, calcium carbonate, barium sulfate, zinc oxide, zinc carbonate, aluminum hydroxide, diatomaceous earth, bentonite, and perlite. Of these, silica and calcium carbonate are preferred. The inorganic filler of component (C) may be surface-treated with a surface-modifying agent, such as a silane compound. These can be used individually or in combination of two or more.

[0050] The size of the inorganic particles is not particularly limited, but considering blending and dispersion in the polymer, the average particle size is preferably 1 nm to 1000 μm, more preferably 3 nm to 500 μm. The shape of the inorganic particles may be irregular, spherical, cubic, plate-like, rod-like, etc., but spherical and cubic shapes are preferred considering dispersibility. The particles may also have a cavity in the core or be porous. The average particle size is measured as the mass-average value D50 by laser diffraction / scattering. When the inorganic particles are silica, from the viewpoint of blending and dispersibility in the polymer, the specific surface area measured by BET adsorption is 50 to 400 m². 2 / g, especially 90-200m 2 It is preferable that the value is / g.

[0051] The amount of component (C) is 1 to 300 parts by mass, preferably 2 to 200 parts by mass, per 100 parts by mass of component (A). Within the above particle size range, a small amount is sufficient for relatively fine particles, but a larger amount is required for larger particles. If the amount exceeds the appropriate amount, the viscosity of the room-temperature curable resin composition of the present invention will become too high, impairing workability. If the amount is insufficient, it will be difficult to uniformly disperse component (B) in the composition, leading to a decrease in antibacterial performance and deterioration of appearance.

[0052] (D) A hydrolyzable organosilane compound and / or a partially hydrolyzed condensate thereof having at least three hydrolyzable groups in one molecule of component (D) acts as a curing agent (crosslinking agent), preservation stabilizer, and dehydrating agent in the room-temperature curable resin composition of the present invention. Examples of such hydrolyzable groups include ketoxime groups, alkoxy groups, acetoxy groups, alkenoxy groups, etc., with ketoxime groups and alkoxy groups being preferred. In the present invention, a partially hydrolyzed condensate means an organosiloxane oligomer having at least two, preferably three or more residual hydrolyzable groups in one molecule, which is produced by the partial hydrolysis and condensation of hydrolyzable silane compounds.

[0053] As such hydrolyzable organosilane compounds having at least three hydrolyzable groups in one molecule, hydrolyzable organosilane compounds represented by the following general formula (3) are preferred.

[0054] [ka]

[0055] (In the formula, R 8 (wherein is an unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, Z is an independently hydrolyzable group, and r is 0 or 1, preferably 1.)

[0056] In the above general formula (3), R 8 Examples of unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; alkenyl groups such as vinyl, allyl, butenyl, pentenyl, and hexenyl groups; aryl groups such as phenyl, tolyl, xylyl, and α-,β-naphthyl groups; and aralkyl groups such as benzyl, 2-phenylethyl, and 3-phenylpropyl groups. Among these, alkyl groups such as methyl, ethyl, and propyl groups, and alkenyl groups such as vinyl groups are preferred, with methyl, ethyl, propyl, isobutyl, and vinyl groups being particularly preferred.

[0057] Furthermore, examples of hydrolyzable groups of Z include alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and tert-butoxy; alkenyloxy groups such as vinyloxy, alyloxy, propenoxy, isopropenoxy, and cyclopentenoxy; ketoxime groups such as dimethylketoxime, diethylketoxime, methylethylketoxime, and methylisobutylketoxime; acyloxy groups such as acetoxy; and alkylamino groups such as n-butylamino, diethylamino, and dimethylamino. These are typically monovalent groups having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. Among these, ketoxime groups, alkoxy groups, acetoxy groups, and alkenoxy groups are preferred, and ketoxime groups, alkoxy groups, and alkenoxy groups are more preferred.

[0058] Specific examples of component (D) include ketoxime group-containing silanes such as methyltris(methylethylketoxime)silane, vinyltris(methylethylketoxime)silane, methyltris(methylisobutylketoxime)silane, and vinyltris(methylisobutylketoxime)silane; alkoxysilanes such as methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, and methyltriethoxysilane; alkenoxysilanes such as methyltris(cyclopentenoxy)silane, vinyltris(cyclopentenoxy)silane, and vinyltriisopropenoxysilane; and partially hydrolyzed condensates of these silanes. These can be used individually or in combination of two or more.

[0059] The amount of component (D) is 1 to 30 parts by mass, preferably 2 to 15 parts by mass, per 100 parts by mass of component (A). If the amount is less than 1 part by mass, the storage stability of the room-temperature curable resin composition of the present invention will be impaired, and thickening and gelation will occur in the packaging container. If the amount is more than 30 parts by mass, it will not only adversely affect the curability and mechanical properties after curing, but will also be economically disadvantageous.

[0060] In addition to the above components (A) to (D), the room-temperature curable resin composition of the present invention may optionally contain various additives such as (E) a curing catalyst, (F) a plasticizer, and (G) an adhesion promoter, as long as they do not impair the effects of the invention.

[0061] The curing catalyst of component (E) is an optional component that can be added as needed to improve the curability of the room-temperature curable resin composition of the present invention. Examples of this curing catalyst of component (E) include organic carboxylates, alcoholides, and chelates of metals such as tin, titanium, zirconium, aluminum, iron, antimony, bismuth, and manganese. More specifically, examples include tin compounds such as dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin dilaurate, dibutyltin maleate ester, dimethyltin dineodecanoate, dibutyltin dimethyloxide, dioctyltin dineodecanoate, and stanus octoate; and organic compounds such as aluminum tris(acetylacetonate), aluminum tris(ethylacetoacetate)diisopropoxyaluminum ethylacetoacetate, and triethoxyaluminum. Examples include aluminum; organozirconium compounds such as zirconium tetrakis(acetylacetonate), tetraisopropoxyzirconium, tetrabutoxyzirconium, tributoxyzirconium acetylacetonate, and tributoxyzirconium stearate; alkoxytitanium compounds such as tetran-n-butoxytitanium, tetrakis(2-ethylhexoxy)titanium, tetraisopropoxytitanium, and tetratertiary-butoxytitanium; titanium chelate compounds such as diisopropoxybis(acetylacetonate)titanium, diisopropoxybis(ethylacetoacetate)titanium, and dibutoxybis(methylacetoacetate)titanium; amine compounds such as dibutylamine, laurylamine, tetramethylguanidine, and tetramethylguanidylpropyltrimethoxysilane, and their salts. Among the above example compounds, tin compounds, bismuth compounds, and titanium compounds are preferred due to their good curability and minimal change in appearance after curing, and among these, alkyltin, bismuth carboxylates, alkoxytitaniums, and titanium chelate compounds are particularly preferred.

[0062] The curing catalyst of component (E) can be used alone or in combination of two or more types. The amount of component (E) is preferably 10% by mass or less (0 to 10% by mass), and more preferably 3% by mass or less (0 to 3% by mass), based on the room-temperature curable resin composition. When component (E) is included, the lower limit of the amount can be 0.01% by mass or more, and more preferably 0.1% by mass or more, based on the room-temperature curable resin composition.

[0063] The plasticizer of component (F) is an optional component that can be added as needed to adjust the viscosity of the room-temperature curable resin composition of the present invention and improve its workability. Examples of this plasticizer of component (F) include so-called non-functional organopolysiloxanes (silicone oils) such as diorganopolysiloxanes in which both ends of the molecular chain are sealed with triorganosiloxy groups, paraffin oils such as isoparaffin, aromatic ester compounds such as dialkylphthalates, and polyether compounds such as polypropylene oxide, polyethylene oxide, and ethylene oxide-propylene oxide copolymers.

[0064] The plasticizer of component (F) can be used alone or in combination of two or more types. The amount of component (F) is preferably 50% by mass or less (0 to 50% by mass), and more preferably 30% by mass or less (0 to 30% by mass), based on the room-temperature curable resin composition. When component (F) is included, the lower limit of the amount can be 0.1% by mass or more, and more preferably 1% by mass or more, based on the room-temperature curable resin composition.

[0065] The adhesion-imparting agent of component (G) is an optional component that can be added as needed to improve the adhesion of the cured product of the room-temperature curable resin composition of the present invention to various substrates. Suitable adhesion-imparting agents of component (G) include, for example, silane coupling agents (i.e., so-called carbon-functional hydrolyzable silanes or carbon functional silanes having a monovalent hydrocarbon group (carbon functional group) substituted with a functional group containing heteroatoms such as nitrogen, oxygen, or sulfur atoms in the molecule, and a hydrolyzable group such as an alkoxy group bonded to a silicon atom). The silane coupling agent is preferably an amine-based silane coupling agent having an alkoxysilyl group as a hydrolyzable group. Examples include N-(2-aminoethyl)3-aminopropyltrimethoxysilane, N-(2-aminoethyl)3-aminopropyltriethoxysilane, N-(2-aminoethyl)3-aminopropyl(methyl)dimethoxysilane, N-(2-aminoethyl)3-aminopropyl(methyl)diethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-aminomethylbenzylamino)propyltrimethoxysilane, and 3-(N-aminomethylbenzylamino)propyltriethoxysilane.

[0066] The adhesion-imparting agent of component (G) can be used alone or in combination of two or more types. The amount of component (G) is preferably 10% by mass or less (0 to 10% by mass), and more preferably 3% by mass or less (0 to 3% by mass), based on the room-temperature curable resin composition. When component (G) is included, the lower limit of the amount can be 0.1% by mass or more, and more preferably 0.5% by mass or more, based on the room-temperature curable resin composition.

[0067] The room-temperature curable resin composition of the present invention can be prepared, for example, as follows: Components (A), (B), and (C) are placed in a container at room temperature (23°C ± 15°C) under normal pressure (1 atm) or reduced pressure and mixed until uniform. Then, component (D) is added, and under reduced pressure degassing and mixing operations are performed in an environment where moisture is minimized by passing an inert gas such as dry nitrogen through until uniform, to prepare a uniform liquid or paste-like room-temperature curable resin composition. This can then be filled into packaging containers such as poly cartridges or tubes for storage. The room-temperature curable resin composition of the present invention, after being dispensed from a container, crosslinks at room temperature through a hydrolysis condensation reaction with moisture in the air, and hardening proceeds from the surface of the composition that comes into contact with air, thereby forming a cured product. When hardening at room temperature, tooling can be performed within the touch-dry time (tack-free time) after dispensing from the container, allowing the composition to be shaped before hardening is complete. The cured product becomes an elastic, rubbery cured product (elastomer).

[0068] The room-temperature curable resin composition of the present invention, when not in use, is stored in a sealed, moisture-proof packaging container, for example, in liquid or paste form. When in use, it is dispensed from the container, reacts with moisture in the atmosphere to harden, and becomes a cured product.

[0069] The room-temperature curable resin composition of the present invention contains a quaternary ammonium salt silane with antibacterial properties supported and dispersed on an inorganic filler. Therefore, it is less prone to separation and precipitation during sealed storage, maintaining a uniform dispersion state. Upon removal from the container and reaction with atmospheric moisture, the quaternary ammonium salt silane migrates and localizes to the surface of the cured material as the curing reaction progresses, exhibiting antibacterial properties. Furthermore, since the quaternary ammonium salt silane is immobilized by chemical bonding with silyl groups in the polymer via silyl groups, it is less likely to dissolve, be extracted, and disappear after curing, thus ensuring sustained antibacterial performance. In particular, by using a silicone composition, antibacterial properties can be imparted without degrading appearance, curability, or cured material properties, allowing for a wide range of applications as a sealing material and coating material in construction, civil engineering, and electrical and electronic applications. [Examples]

[0070] The present invention will be specifically described below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to the following. <Synthesis of quaternary ammonium salt silanes> [Synthesis Example 1] In a nitrogen-purged 300 mL pressurized reaction vessel, 39.7 g of 3-chloropropyltrimethoxysilane, 59.6 g of octadecyldimethylamine, and 99.3 g of methanol were added and reacted at 120°C for 20 hours. After the reaction, filtration was performed to obtain 190 g of methanol solution of octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride (solid content concentration 50% by mass) (quaternary ammonium salt silane solution 1).

[0071] [Synthesis Example 2] 62.2 g of 8-chlorooctyltriethoxysilane, 59.6 g of octadecyldimethylamine, and 122 g of ethanol were placed in a nitrogen-purged 300 mL pressurized reaction vessel and reacted at 120°C for 20 hours. After the reaction, 235 g of an ethanol solution of octadecyldimethyl(8-triethoxysilyloctyl)ammonium chloride (solid content concentration 50% by mass) was obtained by filtration (quaternary ammonium salt silane solution 2).

[0072] <Preparation of room-temperature curable resin composition> [Example 1] Dimethylpolysiloxane in which both ends of the molecular chain are sealed with silanol groups (viscosity at 23°C is 50,000 mPa·s, in formula (2-1) above, R 6 100 parts by mass of methyl group (p=approx. 850), 38 parts by mass of dimethylpolysiloxane (viscosity 100 mPa·s at 23°C) with both ends of the molecular chain sealed with trimethylsiloxy groups, 7 parts by mass of methyltris(methylethylketoxime)silane, and fuzzy silica (BET specific surface area 115 m²) surface-treated with dimethyldichlorosilane. 2Mix 14 parts by mass of (g) until homogeneous, add 0.75 parts by mass of dioctyltin dilaurate, 0.75 parts by mass of 3-(2-aminoethylamino)propyltrimethoxysilane, and 0.75 parts by mass of "Quaternary ammonium salt silane solution 1" prepared in [Synthesis Example 1], and mix uniformly under reduced pressure while removing air bubbles to prepare a room-temperature curable resin composition.

[0073] [Example 2] A room-temperature curable resin composition was prepared in the same manner as in Example 1, except that 0.75 parts by mass of "Quaternary ammonium salt silane solution 1" was changed to 1.5 parts by mass.

[0074] [Example 3] A room-temperature curable resin composition was prepared in the same manner as in Example 1, except that 0.75 parts by mass of "Quaternary ammonium salt silane solution 1" was replaced with 0.75 parts by mass of "Quaternary ammonium salt silane solution 2" prepared in [Synthesis Example 2].

[0075] [Comparative Example 1] Atomized silica surface treated with dimethyldichlorosilane (BET specific surface area 115 m²) 2 A room-temperature curable resin composition was prepared in the same manner as in Example 1, except that 14 parts by mass of ( / g) were not included.

[0076] [Comparative Example 2] A room-temperature curable resin composition was prepared in the same manner as in Example 1, except that 0.75 parts by mass of "Quaternary ammonium salt silane solution 1" prepared in [Synthesis Example 1] was not included.

[0077] The room-temperature curable resin compositions obtained in Examples 1-3 and Comparative Examples 1-2 were evaluated for the following performance. The results are shown in Table 1.

[0078] [exterior] The appearance of each composition obtained in the above examples and comparative examples was visually observed 24 hours after preparation, while keeping it protected from moisture. If a uniform state was maintained, it was judged as a pass and recorded as "○". If there was a non-uniform state such as liquid phase separation (oil bleed) or precipitation of aggregates, it was judged as a fail and recorded as "×". Furthermore, Comparative Example 1, which did not contain (C) fumarole silica, an inorganic filler, was judged to be unacceptable due to the non-uniform appearance of the composition, and the following evaluation was not performed.

[0079] [Touch dry time] Using the compositions obtained in the above examples and comparative examples, a touch-dry time test in accordance with JIS A 1439 was conducted and the results were recorded.

[0080] [Hardness] Each composition obtained in the above examples and comparative examples was molded into a 2 mm thick sheet, left to stand in a constant temperature and humidity chamber at 23°C and 50% RH for 7 days, and then three sheets were stacked to a total thickness of 6 mm. The hardness was measured using a Type A durometer in accordance with JIS K 6253 and the results were recorded.

[0081] <Evaluation of antibacterial properties> Using the 2mm thick sheet described above, antibacterial tests were conducted against Staphylococcus aureus and Escherichia coli in accordance with JIS Z 2801 (Antibacterial processed products - Antibacterial test methods and antibacterial effects), and the antibacterial activity value was calculated. Based on our own criteria, a value of 2.5 or higher was considered a pass and recorded as "○". A value less than 2.5 was considered a fail and recorded as "×" (generally, an antibacterial activity value of 2.0 or higher is considered antibacterial).

[0082] [Table 1]

Claims

1. (A) Organic resin polymer having at least one reactive silyl group in one molecule and a viscosity of 10 to 10,000,000 mPa·s at 23°C: 100 parts by mass, (B) A quaternary ammonium salt silane represented by the following general formula (1): 0.01 to 5 parts by mass, 【Chemistry 1】 (In the formula, R １ and R ２ Each of these is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R ３ R is an alkyl group having 12 to 24 carbon atoms. ４ and R ５ Each of these is an alkyl group having 1 to 6 carbon atoms, X is a halogen atom, m is an integer from 8 to 20, and n is an integer from 1 to 3. (C) Inorganic filler: 1 to 300 parts by mass, and (D) Hydrolyzable organosilane compounds and / or partially hydrolyzed condensates thereof having at least three hydrolyzable groups in one molecule: 1 to 30 parts by mass, A room-temperature curable resin composition for construction, civil engineering, and electrical / electronic applications, comprising the above.

2. The room-temperature curable resin composition according to claim 1, wherein component (A) is at least one selected from linear diorganopolysiloxanes represented by the following general formulas (2-1) and (2-2). 【Chemistry 2】 (In the formula, R ６ R is a monovalent hydrocarbon group, either identical or different, unsubstituted or substituted, and p is a number of 10 or more. ７ (where is an identical or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is an oxygen atom or an unsubstituted or substituted divalent hydrocarbon group having 1 to 6 carbon atoms, and q is an integer from 1 to 3.)

3. A cured product of the room-temperature curable resin composition according to claim 1 or 2.

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