Water-based coating agent composition

Abstract

Provided is an aqueous coating agent composition which contains the following (A)-(F) components and from which a cured film having excellent adhesiveness to a substrate, abrasion resistance, and / or abnormal noise generation suppression performance can be obtained. (A) is a polyorganosiloxane containing hydroxyl groups at both terminals and / or a branched (partially crosslinked) polyorganosiloxane containing a hydroxyl group at a terminal. (B) is elastomer particles having a volume-average particle diameter of 0.1-80 μm. (C) is a trifunctional silane compound represented by the general formula R1Si(OR2)3 (in the formula, R1 is a phenyl group, an alkenyl group, or an alkyl group having one or two carbon atoms, and R2s are the same or different unsubstituted monovalent hydrocarbon groups) and / or a partially hydrolyzed condensate thereof. (D) is an amino group-containing alkoxysilane represented by the general formula (R3O)3-n(R4)nSiR5-NH-R6 (in the formula, R3 and R4 are the same or different unsubstituted monovalent hydrocarbon groups, n is 0 or 1, R5 is an unsubstituted divalent hydrocarbon group, and R6 is a hydrogen atom, a monovalent hydrocarbon group that is unsubstituted or substituted with a halogen or a cyano group, or an aminoalkyl group) and / or a partially hydrolyzed condensate thereof. (E) is water. (F) is a synthetic resin [excluding (A) and (B)].

Description

[Technical Field]

[0001] The present invention relates to a water-based coating agent composition that can be used as a surface treatment agent or coating agent for, for example, automotive weatherstrip materials, printer blades, vibration-damping rubber, or rubber parts of building material gaskets. Background technology

[0002] Conventionally, ethylene-propylene-diene terpolymer (EPDM) rubber and various other rubber products used as automotive weatherstrips have been coated with a polyorganosiloxane composition to impart properties such as non-stickiness, water repellency, abrasion resistance, slipperiness, and noise suppression to their surfaces.

[0003] Examples of such coating agents include compositions in which a polydiorganosiloxane having hydroxyl groups at its termini is combined with a polyorganosiloxane and / or organoalkoxysilane having hydrogen atoms bonded to silicon atoms, and a curing catalyst.

[0004] However, since these compositions contain organic solvents, development is underway on water-based emulsion-type coating agents that do not use organic solvents. Furthermore, with the recent electrification of automobiles, there is a demand for greater quietness inside the vehicle, and development is progressing on coating agents with noise suppression capabilities to meet this demand.

[0005] As emulsion-type silicone coating agents that improve the durability and adhesion (adhesion) of the film of water-based coating agents, various compositions combining siloxane compounds (Japanese Patent Publication No. 8-245882), coating agents that combine a chlorinated polyolefin having maleic anhydride groups with a de-alcoholization condensation type silicone emulsion (Japanese Patent Publication No. 2001-207106), and coating agents that combine a specific adhesion-enhancing component (aminosilane compounds, epoxysilane compounds, carboxylic acids, etc.) with a dehydrogenation condensation type silicone emulsion (Japanese Patent Publication No. 2002-188057) have been proposed.

[0006] Furthermore, these conventional coating agents contain organotin compounds such as dibutyltin dilaurate, that is, compounds having an Sn-C bond in which at least one carbon atom is directly bonded to a tin atom, as a curing catalyst in order to obtain a sufficiently cured film in a short time.

[0007] Japanese Patent Publication No. 2019-19188 describes an invention of a rubber film-forming silicone emulsion composition comprising (A) an organopolysiloxane having at least two hydroxyl groups in one molecule, (B) an aminoalkyltrialkoxysilane and (C) a vinyltrialkoxysilane which serve as crosslinking agents for component (A), (D) a surfactant, and (E) water, and which does not contain organotin compounds. Furthermore, regarding its uses, it states, "Examples of uses for the rubber film-forming silicone emulsion composition of the present invention include damage protection agents, water repellents, and release agents for paper, plastic sheets, and rubber articles; damage protection agents, water repellents, waterproofing agents, texture improvers, and sealants for fabrics; and water repellents, waterproofing agents, and release agents for concrete, mortar, and wood." (paragraph number 0057). Summary of the Invention

[0008] In one embodiment, the present invention aims to provide a water-based coating agent composition that yields a cured film with excellent adhesion to a substrate, abrasion resistance, and / or noise suppression performance.

[0009] In one embodiment, the present invention is: (A) Polyorganosiloxane containing hydroxyl groups at both ends and / or branched (partially crosslinked) polyorganosiloxane containing hydroxyl groups at the ends [hereinafter referred to as component (A)], (B) Elastomer particles having a volume average particle diameter of 0.1 to 80 μm [hereinafter referred to as component (B)], (C) General formula: R 3 , 3 Si(OR 2 )3 (In the formula, R 1 is a phenyl group, an alkenyl group or an alkyl group having 1 or 2 carbon atoms, and R 2 is the same or different unsubstituted monovalent hydrocarbon group.) A trifunctional silane compound represented by and / or its partial hydrolysis condensate [hereinafter referred to as component (C)], (D) General formula: (R 3 O) 3-n (R 4 ) n SiR 5 -NH-R 6 (In the formula, R 3 and R 4 are the same or different unsubstituted monovalent hydrocarbon groups, and n is 0 or 1. R 5 is an unsubstituted divalent hydrocarbon group, and R 6 is a hydrogen atom, an unsubstituted or halogen- or cyano-substituted monovalent hydrocarbon group, or an aminoalkyl group.) An amino group-containing alkoxysilane represented by and / or its partial hydrolysis condensate [hereinafter referred to as component (D)], (E) Water [hereinafter referred to as component (E)], and (F) Synthetic resin (excluding components (A) and (B)) [hereinafter referred to as component (F)] provided is an aqueous coating agent composition containing.

[0010] In one embodiment, the aqueous coating agent composition of the present invention can form a cured film excellent in adhesion to a substrate, abrasion resistance and / or suppression performance of abnormal sound generation. Mode for carrying out the invention

[0011] <Component (A)> In one embodiment, Component (A) is a dihydroxyl-terminated polyorganosiloxane and / or a branched (partially crosslinked) polyorganosiloxane having hydroxyl groups at the terminals. Component (A) may participate in the curing reaction by the reactivity of the hydroxyl groups (hydroxyl groups) bonded to the silicon atoms at the molecular terminals.

[0012] In one embodiment, examples of the organic groups bonded to the silicon atoms of the polydiorganosiloxane of Component (A) include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, and hexyl group; alkenyl groups such as vinyl group and propenyl group; aryl groups such as phenyl group; aralkyl groups such as phenethyl group; and those in which some of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms or nitrile groups, etc. In one embodiment, a methyl group is preferred in view of ease of synthesis and balance with the physical properties of the film after curing. In one embodiment, Component (A) can be formulated as an emulsion containing Component (A) and Component (E) when producing the composition of the present invention. Note that the emulsion referred to in the present invention may be used in the sense that it also includes a solid-liquid dispersion.

[0013] In one embodiment, the viscosity of component (A) polydiorganosiloxane is preferably 50 to 10,000,000 mPa·s at 25°C, more preferably 1,000 to 5,000,000 mPa·s, and even more preferably 100,000 to 2,000,000 mPa·s, in the case of a linear polyorganosiloxane containing hydroxyl groups at both ends. Below 50 mPa·s, the cured film may become brittle, and above 10,000,000 mPa·s, it may be difficult to obtain a stable emulsion containing component (A). In one embodiment, for terminal hydroxyl group-containing branched (partially crosslinked) polyorganosiloxanes, the viscosity when diluted with 50% toluene at 25°C is preferably 100 to 10,000,000 mPa·s, more preferably 10,000 to 5,000,000 mPa·s, and even more preferably 100,000 to 1,000,000 mPa·s. Below 100 mPa·s, the cured film may become brittle, and above 10,000,000 mPa·s, it may be difficult to obtain a stable emulsion containing component (A). This viscosity may be measured using a rotational viscometer (AMETEK Brookfield DVPLUS) at 25°C.

[0014] In one embodiment, component (A) may be used alone or as a mixture of two or more types. Also, in one embodiment, if the viscosity is 100,000 mPa·s or higher, it is preferable to produce a stable emulsion containing component (A) by known emulsion polymerization.

[0015] <(B) component> In one embodiment, component (B) is elastomer particles having a volume-average particle diameter of 0.1 to 80 μm. In one embodiment, the material of the elastomer particles of component (B) is not particularly limited as long as it is an entropy elastic material that deforms under external force and recovers its deformation when the external force is removed, in other words, an elastomer, and examples include various known elastomers. Specifically, examples include synthetic rubbers such as urethane rubber, silicone rubber, acrylic rubber, fluororubber, chloroprene rubber, butadiene rubber, EPDM (ethylene-propylene-diene copolymer rubber), and epichlorohydrin rubber, as well as polyolefins, styrene-based elastomers such as styrene-butadiene rubber, vinyl chloride-based elastomers such as polyblends of nitrile rubber and vinyl chloride, and synthetic resins such as silicone resin elastomers. In one embodiment, among these, component (B) is preferably elastomer particles selected from silicone elastomer particles made of silicone rubber and polyurethane particles made of urethane rubber, and more preferably elastomer particles selected from silicone elastomer particles made of silicone rubber. In one embodiment, component (B) may be used alone or as a mixture of two or more types.

[0016] In one embodiment, component (B) can be incorporated as an emulsion containing component (B) and component (E) when producing the composition of the present invention.

[0017] In one embodiment, the silicone elastomer particles are a polyorganosiloxane having at least two hydroxyl groups, i.e., silanol groups, bonded to silicon atoms in one molecule, and the general formula: R 7 m Si(OR 8 ) 4-m It can be produced by condensing a trifunctional or tetrafunctional silane compound represented by , or a partially hydrolyzed condensate thereof, and then emulsifying the resulting liquid crosslinkable polyorganosiloxane in water in the presence of a surfactant, and then crosslinking and curing it by condensation. Here, R7 R is a substituted or unsubstituted monovalent hydrocarbon group, which may be the same or different from each other. Specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, and dodecyl groups; alkenyl groups such as vinyl and allyl groups; aryl groups such as phenyl, tolyl, and xylyl groups; and aralkyl groups such as 2-phenylethyl and 2-phenylpropyl groups. In one embodiment, R 7 Examples of preferred groups include methyl, ethyl, vinyl, or phenyl groups. 8 R is an unsubstituted monovalent hydrocarbon group that may be identical or different from each other. 8 Examples of preferred groups include methyl, ethyl, or propyl groups. m is 0 or 1.) Alternatively, as silicone elastomer particles, particles can be used in which polyorganosiloxane and polyorganohydrogenloxane containing vinyl groups in their molecules are emulsified in water with a surfactant, a platinum compound is added as a catalyst to induce a hydrosilylation reaction, and the resulting crosslinked and cured material forms the core, which is then coated with silicone resin.

[0018] In one embodiment, component (B) may have a volume-average particle diameter of 0.1 to 80 μm, preferably 1 to 50 μm, and more preferably 5 to 50 μm. If the volume-average particle size of component (B) is less than 0.1 μm, the slipperiness may be poor, and the wear resistance and noise suppression performance may decrease. Also, if the volume-average particle size of component (B) exceeds 80 μm, the particles may easily detach from the hardened coating, and the wear resistance may deteriorate. In one embodiment, the volume-average particle diameter of component (B) may be measured by a particle size distribution analyzer (LS-230; manufactured by Beckman Coulter) (see Example 1 of Japanese Patent Application Publication No. 2006-104456).

[0019] In one embodiment, when using a non-emulsion form of component (B) in the production of the composition of the present invention, it is preferable to use a pre-mixed mixture of component (B) and a surfactant. In one embodiment, an amphoteric surfactant is preferred. An example of an amphoteric surfactant is alkylamine oxide. An example of an alkylamine oxide is dimethylalkylamine oxide. Examples of the alkyl group in the alkylamine oxide include a lauryl group, a myristyl group, or a group derived from natural oils such as coconut oil. In one embodiment, the alkylamine oxide can be added after being pre-mixed with component (B) in the form of an emulsion or aqueous solution (solid content ratio of 10-50% by mass). In another embodiment, even if component (B) is in emulsion form, a surfactant such as alkylamine oxide can be added to stabilize the dispersion of elastomer particles.

[0020] <(C) component> In one embodiment, component (C) is of the general formula: R 1 Si(OR 2 )3(wherein, R 1 R is a phenyl group, an alkenyl group, or an alkyl group having 1 or 2 carbon atoms. 2 R is the same or different unsubstituted monovalent hydrocarbon group. The formula is a trifunctional silane compound and / or a partial hydrolysis condensate thereof represented by ). In one embodiment, component (C) is a component that acts as a crosslinking component of component (A). In the above formula, R 1 The number of carbon atoms in the alkenyl group may be, for example, 2 to 4. In the above formula, R 1 Examples of preferred groups include methyl, ethyl, vinyl, or phenyl groups. In the above formula, R 2 The number of carbon atoms in the monovalent hydrocarbon group may be, for example, 1 to 6. In the above formula, R 2 Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, or hexyl groups, but methyl or ethyl groups are preferred.

[0021] In one embodiment, component (C) is preferably selected from vinyltriethoxysilane, vinyltrimethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, and ethyltriethoxysilane. In one embodiment, component (C) may be used alone or as a mixture of two or more.

[0022] <(D) component> In one embodiment, component (D) is of the general formula: (R 3 O) 3-n (R 4 ) n SiR 5 -NH-R 6 (In the formula, R 3 and R 4 R is an identical or different unsubstituted monovalent hydrocarbon group, and n is 0 or 1. 5 R is an unsubstituted divalent hydrocarbon group, 6 R is a hydrogen atom, an unsubstituted or unsubstituted monovalent hydrocarbon group substituted with a halogen or cyano group, or an aminoalkyl group. ) is an amino group-containing alkoxysilane and / or a partially hydrolyzed condensate thereof. Component (D) may be a component that acts as a catalyst when component (A) undergoes a crosslinking reaction. In the above formula, R 3 and R 4 An example of this is R in the formula showing component (C) mentioned above. 2 Similar groups are given as examples. R 2 All of the above statements relating to R 3 and R 4 This may also apply to the following. In the above formula, R 5 The number of carbon atoms in the divalent hydrocarbon group may be, for example, 1 to 6. 5 Examples include alkylene groups such as methylene, ethylene, propylene, tetramethylene, hexamethylene, and methylethylene, but in one embodiment, propylene is preferred. 6is a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group with a halogen or cyano group, or an aminoalkyl group. The number of carbon atoms in the unsubstituted or substituted monovalent hydrocarbon group may be, for example, 1 to 8. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, and butyl groups; aryl groups such as phenyl and tolyl groups; and aralkyl groups such as phenylmethyl (benzyl) and phenylethyl (phenethyl) groups. The number of carbon atoms in the aminoalkyl group may be, for example, 1 to 6. Examples of aminoalkyl groups include aminoethyl and N-aminoethylaminoethyl groups. 6 Examples of preferred components include hydrogen atoms and aminoethyl groups. Component (D) can be used individually or as a mixture of two or more.

[0023] In one embodiment, an example of component (D) is selected from 3-(2-aminoethylamino)propyldimethoxymethylsilane, 3-(2-aminoethylamino)propyltrimethoxysilane, oligomers (hydrolyzed condensates) of 3-(2-aminoethylamino)propyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyltriethoxysilane, and 3-aminopropyltrimethoxysilane.

[0024] <(F) component> In one embodiment, component (F) is a synthetic resin (excluding components (A) and (B)). In one embodiment, component (F) is preferably a component that improves the abrasion resistance and adhesion of the cured film formed on a substrate by the aqueous coating agent composition of the present invention. For example, component (F) may be an adhesion-improving component. The synthetic resins related to the present invention are not particularly limited and include polymerization resins, condensation polymerization resins, or addition polymerization resins. In one embodiment, examples of the synthetic resin of component (F) include polymerization resins such as polyolefin, acrylic, vinyl, styrene, and butadiene; condensation polymerization resins such as alkyd, polyester, polyamide, polyimide, phenol, urea, melamine, and guanamine; and addition polymerization resins such as polyether, polythioether, polysulfone, polycarbonate, polyurea, polyurethane, polyurethane-polyurea, epoxy, fluorine, and silicone. In one embodiment, component (F) is preferably selected from polyolefin resins and polyurethane resins, and more preferably from polyolefin resins having carboxyl groups or their neutralized salts, and polyurethane resins having carboxyl groups or their neutralized salts. When component (F) has carboxyl groups, it is preferable that the carboxyl groups contained in the resin are neutralized with a basic compound described later for the production of an aqueous dispersion and to improve stability. In the case of polyolefin resins, polypropylene and polyethylene are examples, but polyethylene is preferred, and those that are partially chlorinated or copolymerized with monomers having acrylic groups or methacrylic groups can also be used. In one embodiment, component (F) can be used alone or as a mixture of two or more. In one embodiment, component (F) can be a commercially available acid-modified resin.

[0025] In one embodiment, a method for incorporating carboxyl groups into a synthetic resin may be used to copolymerize a compound having at least one carboxyl group or acid anhydride group within the molecule (within the monomer unit), such as random copolymerization, block copolymerization, or graft copolymerization. Specifically, in the case of polyolefin resins, examples of compounds having at least one carboxyl group or acid anhydride group within the molecule (within the monomer unit) include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, and crotonic acid, as well as half-esters and half-amides of unsaturated dicarboxylic acids. Among these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferred, and acrylic acid and maleic anhydride are particularly preferred. In the case of polyurethane resins, diglycolic acid, represented by 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylollactic acid, may be used as a chain length extender.

[0026] In one embodiment, ammonia or an organic amine compound is preferred as the basic compound that neutralizes the carboxyl group. Examples of organic amine compounds include triethylamine, N,N-dimethylethanolamine, aminoethanolamine, N-methyl-N,N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine, and N-ethylmorpholine.

[0027] In one embodiment, when producing the composition of the present invention, component (F) is preferably used in the form of an aqueous dispersion such as an emulsion or suspension. Examples of methods for producing an aqueous dispersion containing component (F) include forced emulsification using a surfactant and ionomerization, in which the carboxyl group in the molecule is neutralized with a basic compound to disperse it in water. If an organic solvent is used during the reaction, it is preferable to remove it after the reaction. When component (F) is used in an aqueous dispersion, it is preferable that the solid content concentration is in the range of 10 to 40% by mass.

[0028] <Optional ingredients, composition, etc.> In one embodiment, the aqueous coating agent composition of the present invention may further contain a pigment as an optional component. As the pigment, for example, a known pigment can be selected depending on the application of the aqueous coating agent composition. In one embodiment, carbon black is preferred as the pigment. The carbon black can be formulated in the form of an aqueous dispersion.

[0029] In one embodiment, if component (F) is a resin having a carboxyl group or a neutralized salt thereof, the aqueous coating composition of the present invention may further contain, as an optional component, a crosslinking agent that can react with the carboxyl group of component (F) for the purpose of improving abrasion resistance and / or imparting chemical resistance. As the crosslinking agent, a known crosslinking agent can be selected according to the application of the aqueous coating composition. Examples of crosslinking agents that are preferably selected from polyisocyanates, carbodiimides, melamines, epoxys, and oxazolines.

[0030] In one embodiment, the aqueous coating agent composition of the present invention may appropriately contain inorganic and organic ultraviolet absorbers, matting agents, surfactants, thickeners, defoaming agents, and / or preservatives, etc., to improve weather resistance, within the range in which the effects of the present invention are obtained.

[0031] In one embodiment, the aqueous coating agent composition of the present invention can form a cured film with excellent adhesion to the substrate, abrasion resistance, and / or noise suppression performance, even without containing tin-based or other metal elements derived from the curing catalyst.

[0032] In one embodiment, the content of component (B) in the aqueous coating agent composition of the present invention is preferably 5 to 120 parts by mass, more preferably 10 to 100 parts by mass, and even more preferably 15 to 80 parts by mass, based on 100 parts by mass of component (A). In one embodiment, the content of component (C) in the aqueous coating agent composition of the present invention is preferably 3 to 40 parts by mass, more preferably 5 to 30 parts by mass, and even more preferably 10 to 20 parts by mass, based on 100 parts by mass of component (A). In one embodiment, the content of component (D) in the aqueous coating agent composition of the present invention is preferably 0.3 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, and even more preferably 1 to 2 parts by mass, based on 100 parts by mass of component (A). In one embodiment, the content of component (E) in the aqueous coating agent composition of the present invention is preferably 50 to 2000 parts by mass, more preferably 100 to 1500 parts by mass, and even more preferably 300 to 1000 parts by mass, per 100 parts by mass of component (A). In one embodiment, the content of component (F) in the aqueous coating agent composition of the present invention is preferably 30 to 200 parts by mass, more preferably 40 to 180 parts by mass, and even more preferably 50 to 150 parts by mass, per 100 parts by mass of component (A).

[0033] In one embodiment, the content of components (A) to (F) in the aqueous coating agent composition of the present invention is preferably 10 to 120 parts by mass of component (B), more preferably 15 to 100 parts by mass of component (A), preferably 3 to 40 parts by mass of component (C), more preferably 5 to 30 parts by mass of component (C), preferably 0.3 to 5 parts by mass of component (D), more preferably 0.5 to 3 parts by mass of component (D), preferably 50 to 2000 parts by mass of component (E), more preferably 100 to 1500 parts by mass of component (E), and preferably 30 to 200 parts by mass of component (F), more preferably 40 to 180 parts by mass of component (F). These content ranges may be arbitrarily combined.

[0034] The content of optional components in the aqueous coating agent composition of the present invention can be appropriately determined considering the use and properties of the optional components, but for example, it may be selected from the range of 0 to 500 parts by mass or 0 to 300 parts by mass per 100 parts by mass of component (A). In one embodiment, the surfactant may be used in an amount of 5 to 50 parts by mass or 10 to 30 parts by mass per 100 parts by mass of component (A). In another embodiment, the pigment may be used in an amount of 0.3 to 5 parts by mass or 0.5 to 3 parts by mass per 100 parts by mass of component (A).

[0035] In one embodiment, the aqueous coating agent composition of the present invention may contain components (A) to (F) in total, for example, 50 to 100% by mass, preferably 70 to 100% by mass, based on the total mass of the composition.

[0036] In one embodiment of the aqueous coating agent composition of the present invention, when components (A) to (D) and component (F) are used as compounding components in the form of a dispersion such as an emulsion, the above parts by mass or mass % may be calculated based on the solid content. The amount of component (E) may be the amount calculated as the total amount including that used by the other components as a dispersion medium.

[0037] In one embodiment, the aqueous coating agent composition of the present invention can be produced by mixing components (A) to (F) and an optional component. The mixing order of each component can be appropriately determined considering the properties and form of each component.

[0038] In one embodiment, the aqueous coating agent composition of the present invention can be used by applying the aqueous coating agent composition of the present invention to the surface of a substrate made of paper, rubber, plastic, metal, etc., to be treated by methods such as dip coating, spray coating, brush coating, knife coating, or roll coating.

[0039] Next, the coating can be cured by leaving it at room temperature (10-30°C) for several days, or by heating it appropriately depending on the heat resistance of the substrate. Preferred heating conditions are, for example, 120-180°C for 30 seconds to 5 minutes if the substrate is paper, 80-180°C for 1 to 10 minutes if the substrate is rubber, and 70-150°C for 30 seconds to 5 minutes if the substrate is plastic.

[0040] In one embodiment, the aqueous coating agent composition of the present invention does not contain organotin compound-based curing catalysts, which are increasingly subject to restrictions and regulations due to concerns about their toxicity. Therefore, it can be used safely and with confidence across various applications, fields of use, and countries of use.

[0041] In one embodiment, when the surface of various substrates is treated with the aqueous coating agent composition of the present invention, a cured film is obtained that exhibits excellent uniformity in application, adhesion to the substrate, abrasion resistance, and / or noise suppression performance. That is, one embodiment of the present invention includes a cured film obtained by curing the aqueous coating agent composition of the present invention.

[0042] In one embodiment, the aqueous coating agent composition of the present invention can form a coating with excellent adhesion, abrasion resistance, and noise suppression performance even on substrates such as rubber or plastic, where conventional non-adhesive film-forming silicone compositions could not obtain a coating with sufficient adhesion, and especially on substrates made of foamed or non-foamed EPDM rubber.

[0043] Furthermore, in one embodiment, the aqueous coating composition of the present invention exhibits excellent stability after the formulation of each component and has a long pot life. Also in one embodiment, the aqueous coating composition of the present invention can be used to treat substrates with low heat resistance or large substrates that are difficult to heat treat. Also in one embodiment, the cured film of the aqueous coating composition of the present invention has good non-stick properties to other substances, is water-repellent, and / or has excellent abrasion resistance and noise suppression performance. Examples

[0044] The following describes some embodiments of the present invention with reference to examples, but the present invention is not limited to the following examples. In the examples, all physical property values ​​such as viscosity are given at 25°C and 50% relative humidity, and % represents mass%.

[0045] (A) component (A)-1: Polyorganosiloxane emulsion containing hydroxyl groups at both ends, manufactured in-house by Momentive, emulsion polymerization emulsion with a solids content of 50% (polymer viscosity approximately 1,400,000 mPa·s) (A)-2: Terminal hydroxyl group-containing branched (partially crosslinked) polyorganosiloxane emulsion, manufactured in-house by Momentive, emulsion polymerization emulsion with a solids content of 50% (polymer viscosity of approximately 400,000 mPa·s when diluted with 50% toluene)

[0046] (B) Component (B)-1: Silicone elastomer particle emulsion, manufactured in-house by Momentive, emulsion polymerized silicone elastomer particle emulsion with 40% solids content (starting from diethoxy-terminated polyorganosiloxane with viscosity of approximately 100 mPa·s, volume average particle diameter of approximately 15 μm) (B)-2: Silicone elastomer particle emulsion, manufactured in-house by Momentive, emulsion polymerized silicone elastomer particle emulsion with 40% solids content (starting from diethoxy-terminated polyorganosiloxane with viscosity of approximately 100 mPa·s, with a volume average particle size of approximately 5 μm). (B)-3: Silicone elastomer particle emulsion, manufactured in-house by Momentive, emulsion polymerized silicone elastomer particle emulsion with 40% solids content (starting from diethoxy-terminated polyorganosiloxane with viscosity of approximately 100 mPa·s, volume average particle size approximately 50 μm) (B)-4: Silicone elastomer particles, Serasnow SP-14 manufactured by KCC, with a volume-average particle size of approximately 11 μm. (B)-5: Polyurethane particles, Artpearl C-800T manufactured by Negami Kogyo Co., Ltd., polyurethane particles with a volume average particle diameter of approximately 6 μm.

[0047] (B') component (comparative component of (B) component) (B')-1: Silicone elastomer particle emulsion, manufactured in-house by Momentive, emulsion polymerized silicone elastomer particle emulsion with 40% solids content (starting from diethoxy-terminated polyorganosiloxane with viscosity of approximately 90 mPa·s, volume average particle size of approximately 90 μm) (B')-2: Silicone resin particles, Tospearl 145 manufactured by Momentive, with a volume-average particle size of approximately 5 μm. (B)-4, (B)-5, and (B')-2 were pre-mixed with the surfactants described later before use.

[0048] (C) Component (crosslinking component) (C)-1: Vinyltriethoxysilane, manufactured by Momentive, Silquest A-151 (C)-2: Vinyltrimethoxysilane, manufactured by Momentive, Silquest A-171 (C)-3: Phenyltriethoxysilane, reagent manufactured by Tokyo Chemical Industry Co., Ltd. (C)-4: Methyltriethoxysilane, manufactured by Momentive, Silquest A-1622 (C)-5: Ethyltriethoxysilane, reagent manufactured by Tokyo Chemical Industry Co., Ltd.

[0049] (C') component (comparative component of (C) component) (C')-1: Propyltriethoxysilane, reagent manufactured by Tokyo Chemical Industry Co., Ltd. (C')-2: Hexyltriethoxysilane, reagent manufactured by Tokyo Chemical Industry Co., Ltd. (C')-3:n-octyltriethoxysilane, manufactured by Momentive, Silquest A-137

[0050] (D) Component (D)-1:3-(2-aminoethylamino)propyldimethoxymethylsilane, Silquest A-2120, manufactured by Momentive. (D)-2:3-(2-aminoethylamino)propyltrimethoxysilane, Silquest A-1120, manufactured by Momentive. (D)-3: Oligomer (hydrolyzed condensate) of 3-(2-aminoethylamino)propyldimethoxymethylsilane, manufactured in-house by Momentive. (D)-4:3-aminopropyldiethoxymethylsilane, reagent manufactured by Tokyo Chemical Industry Co., Ltd. (D)-5:3-aminopropyltri Methoxy Silane, manufactured by Momentive, Silquest A-1110 (D)-6:3-aminopropyltri Ethoxy Silane, manufactured by Momentive, Silquest A-1100

[0051] (D') component (comparative component of (D) component) (D')-1: Ammonia aqueous solution (28%), reagent manufactured by Tokyo Chemical Industry Co., Ltd. (D')-2: Aminoethanol, reagent manufactured by Tokyo Chemical Industry Co., Ltd. (D')-3: Triethylamine, reagent manufactured by Tokyo Chemical Industry Co., Ltd.

[0052] (E) Component Component (E) may be deionized water.

[0053] (F) component (F)-1: Acid-modified chlorinated polyolefin resin emulsion, Hardlen EW-5303 manufactured by Toyobo Co., Ltd., solid content concentration 30%, synthetic resin having dimethylaminoethanol salt of carboxyl group. (F)-2: Acid-modified polyurethane resin aqueous dispersion, Hydran WLS-201 manufactured by DIC Corporation, solid content concentration 35%, synthetic resin having ammonium salts of carboxyl groups. (F)-3: Acid-modified polyethylene resin aqueous dispersion, Arrowbase SB-1010 manufactured by Unitika Ltd., solids content 25%, synthetic resin having dimethylaminoethanol salt of carboxyl group. (F)-4: Acid-modified polypropylene resin aqueous dispersion, Arrowbase DA-1010 manufactured by Unitika Ltd., solids content concentration 25%, synthetic resin having dimethylaminoethanol salt of carboxyl group.

[0054] Surfactants: Anchitol 20N manufactured by Kao Corporation, lauryldimethylamine oxide aqueous solution, solid content concentration 35% Pigment: Carbon black aqueous dispersion, Micropigmo WMBK-5 manufactured by Oriental Chemical Co., Ltd., solids content concentration 20%

[0055] Examples 1-26 and Comparative Examples 1-15 Water-based coating compositions were prepared by mixing the components shown in Tables 1 to 6. Each coating composition was applied to the surface of a foamed EPDM rubber sheet using a spray gun. Then, the sheets were heated and dried in a 150°C oven for 5 minutes to obtain test molded articles with a cured film approximately 10 μm thick on the surface of the foamed EPDM rubber sheet. The following tests were performed using these test molded articles. The results are shown in Tables 1 to 6.

[0056] (Particle shedding) The surface of the cured film was rubbed with a finger to evaluate whether or not particles were detached. Good: No particle loss. Defect: Particle detachment present. Note that since Comparative Examples 10 and 14 did not contain component (B), particle shedding properties were not evaluated.

[0057] (Adhesiveness) The surface of the cured coating was rubbed with a work glove to evaluate whether or not the cured coating peeled off. Good: No peeling. Defect: Peeling present

[0058] (Bleed-out properties) The surface of the cured coating was rubbed with a finger, and the presence or absence of abrasion marks was evaluated. Good: No scratches remain. Defective: Bleed material has been removed, but scratches remain.

[0059] (Noise generation evaluation - 1) The hardened coating surface was rubbed against a painted plate, and the presence or absence of abnormal noise was evaluated. A: There is no stick-slip phenomenon causing snagging, and no abnormal noises are generated. B: There is some stick-slip behavior, but no abnormal noises are produced. C: Abnormal noise detected. D: During evaluation, particle detachment and peeling of the hardened coating occurred, making evaluation impossible.

[0060] (Noise generation evaluation - 2) The hardened coating surface was rubbed against an unpainted steel plate, and the presence or absence of abnormal noise was evaluated. A: There is no stick-slip phenomenon causing sticking, and no abnormal noises are generated. B: There is some stick-slip behavior, but no abnormal noises are produced. C: Abnormal noise detected. D: During evaluation, particle detachment and peeling of the hardened coating occurred, making evaluation impossible.

[0061] (Abrasion resistance evaluation) The wear of the hardened coating surface was evaluated using a Japan Society for the Promotion of Science (JSPS) type friction (clock meter) testing machine. Passing criteria: Using a No. 3 metal cloth as the friction element, the material passed if the base surface remained unexposed even after 10,000 cycles of abrasion under a 1 kg load. Defective: In the abrasion test under the above conditions, any material in which the surface of the substrate was exposed before 10,000 cycles had elapsed was considered defective.

[0062] [Table 1]

[0063] [Table 2]

[0064] [Table 3]

[0065] [Table 4]

[0066] [Table 5]

[0067] [Table 6]

[0068] In one embodiment, the aqueous coating agent composition of the present invention can be used in applications where various types of rubber (e.g., EPDM rubber) and various types of plastics are used, for example, as a surface treatment agent for rubber parts such as automotive weatherstrips, printer blades, vibration damping rubber, or gaskets for building materials.

[0069] In one further embodiment, the aqueous coating agent composition of the present invention can be used to impart non-stick properties and / or water repellency to various substrates, including various types of rubber (e.g., EPDM rubber) and various types of plastics.

Claims

1. (A) Polyorganosiloxanes containing hydroxyl groups at both ends and / or branched (partially crosslinked) polyorganosiloxanes containing hydroxyl groups at both ends [hereinafter referred to as component (A)] (B) Elastomer particles having a volume-average particle diameter of 0.1 to 80 μm [hereinafter referred to as component (B)] (C) General form: R １ Si(OR) ２ ) ３ (In the formula, R １ R is a phenyl group, an alkenyl group, or an alkyl group having 1 or 2 carbon atoms. ２ (These are identical or different unsubstituted monovalent hydrocarbon groups.) A trifunctional silane compound represented by and / or a partially hydrolyzed condensate thereof [hereinafter referred to as component (C)], (D) General form: (R) ３ O) ３－ｎ (R) ４ ) ｎ SiR ５ -NH-R ６ (In the formula, R ３ and R ４ R is an identical or different unsubstituted monovalent hydrocarbon group, and n is 0 or 1. ５ R is an unsubstituted divalent hydrocarbon group, ６ (This is a hydrogen atom, an unsubstituted or unsubstituted monovalent hydrocarbon group substituted with a halogen or cyano group, or an aminoalkyl group.) The amino group-containing alkoxysilane and / or its partially hydrolyzed condensate shown in (D), (E) Water [hereinafter referred to as component (E)], (F) A synthetic resin selected from polyolefin resins having carboxyl groups or their neutralized salts, and polyurethane resins having carboxyl groups or their neutralized salts [excluding components (A) and (B)], wherein the synthetic resin is a component that improves the abrasion resistance and adhesion of the cured film formed on the substrate by the water-based coating agent composition [hereinafter referred to as component (F)]. A water-based coating agent composition containing a mixture of the following components, used as a surface treatment agent for rubber parts such as automotive weatherstrips, printer blades, vibration damping rubber, or building material gaskets.

2. The aqueous coating composition according to claim 1, wherein the polydiorganosiloxane of component (A) is a linear polyorganosiloxane containing hydroxyl groups at both ends having a viscosity of 50 to 10,000,000 mPa·s at 25°C, or a branched (partially crosslinked) polyorganosiloxane containing hydroxyl groups at both ends having a viscosity of 100 to 10,000,000 mPa·s when diluted with 50% toluene at 25°C.

3. The aqueous coating agent composition according to claim 1, wherein component (B) is silicone elastomer particles and / or polyurethane particles.

4. The aqueous coating agent composition according to claim 3, wherein component (B) is silicone elastomer particles and / or polyurethane particles having a volume average particle diameter of 1 to 50 μm.

5. In the formula for component (C), R １ R is a phenyl group, an alkenyl group having 2 to 4 carbon atoms, or an alkyl group having 1 to 2 carbon atoms. ２ The aqueous coating agent composition according to claim 1, wherein is the same or different unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms.

6. The aqueous coating agent composition according to claim 5, wherein component (C) is a trifunctional silane compound selected from vinyltriethoxysilane, vinyltrimethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, and ethyltriethoxysilane, and / or a partially hydrolyzed condensate thereof.

7. (D) In ​​the formula of component, R ３ and R ４ Each of these is an identical or different unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, R ５ R is a divalent hydrocarbon group having 1 to 6 carbon atoms. ６ The aqueous coating agent composition according to claim 1, wherein is a hydrogen atom, an unsubstituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms with a halogen or cyano group, or an aminoalkyl group having 1 to 6 carbon atoms.

8. The aqueous coating agent composition according to claim 7, wherein component (D) is an amino group-containing alkoxysilane and / or a partially hydrolyzed condensate thereof selected from 3-(2-aminoethylamino)propyldimethoxymethylsilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyltriethoxysilane, and 3-aminopropyltrimethoxysilane.

9. The aqueous coating agent composition according to claim 1, comprising 100 parts by mass of component (A), 10 to 120 parts by mass of component (B), 3 to 40 parts by mass of component (C), 0.3 to 5 parts by mass of component (D), 50 to 2000 parts by mass of component (E), and 30 to 200 parts by mass of component (F).

10. The aqueous coating agent composition according to claim 1, further comprising a pigment.

11. The aqueous coating agent composition according to claim 1, which does not contain an organotin compound-based curing catalyst.

12. A cured film obtained by curing the aqueous coating agent composition according to any one of claims 1 to 11.

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