Inorganic tin emulsion composition and method for producing the same

Abstract

To provide an inorganic-tin emulsion having good storage stability and a method for producing the inorganic-tin emulsion.SOLUTION: The present invention relates to an inorganic-tin emulsion composition comprising (A) 100 pts.mass of an inorganic tin compound, (B) 5-100 pts.mass of a hydrocarbon oil, (C) 5-50 pts.mass of a surfactant, and (D) 50-2,000 pts.mass of water.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an inorganic tin emulsion composition and a method for producing the same.

Background Art

[0002] Silicone emulsions that form rubber films during drying have conventionally had various compositions and are used as fiber treatment agents, rubber coating agents, building material coating agents, paper and plastic film coating agents, etc. or additives thereof for the purpose of imparting slipperiness, water repellency, and peelability.

[0003] As a method for forming a rubber film, there is a method of forming a film of silicone elastomer by an addition reaction between an alkenylsilyl group and a hydrosilyl group during drying. Examples of the composition include an emulsion composition comprising a vinyl group-terminated diorganopolysiloxane, an organohydropolysiloxane, and a platinum catalyst, and an emulsion composition comprising a diorganopolysiloxane containing a vinyl group at the molecular chain terminal or on the side chain, a polysiloxane having a hydrogen atom bonded to a silicon atom, colloidal silica, and a platinum catalyst. However, in these compositions, when a siloxane containing a hydrosilyl group and a platinum catalyst coexist, the reaction proceeds over time or hydrogen gas is generated, so it is necessary to mix the silicone emulsion and the platinum catalyst before use, which is inconvenient. In addition, there is a drawback that if the substrate to be coated contains a compound that inhibits the addition reaction, such as a compound containing amine, tin, phosphorus, sulfur, etc., it will not cure sufficiently.

[0004] As a method for forming a silicone rubber film other than the addition reaction, there is a method of promoting the condensation reaction of silicone during drying. A silicone emulsion composition (Patent Document 1) comprising an anionically stabilized hydroxylated diorganopolysiloxane, colloidal silica, and an organotin compound or an organic amine compound and having a pH of 9 to 11.5 is known. In compositions that harden by condensation reactions, obtaining a sufficiently hardened rubber film in a short time requires the use of organotin compounds with high catalytic activity. However, in recent years, the use of organotin compounds has been avoided due to their toxicity.

[0005] As a method for forming a silicone rubber film without using organotin compounds, Patent Document 2 proposes a composition in which a mixture of a hydroxy-containing organopolysiloxane and an aminooxy-containing siloxane and / or silane is emulsified. Although this composition does not require a condensation catalyst for the formation of a cured film, it has the problem of producing amino compounds as by-products during the condensation reaction.

[0006] Patent Document 3 proposes a silicone emulsion composition comprising an organopolysiloxane, trialkoxysilane, or tetraalkoxysilane having an alkyl group containing a hydroxyl group and / or an amino group bonded to a silicon atom at the end of the molecular chain, and a metal compound. This composition can produce a sufficiently cured rubber film in a short time by a condensation reaction without using a tin compound. However, the organopolysiloxane, which is a raw material for this composition, gradually polymerizes over time, increasing its molecular weight, making it unsuitable for long-term storage. Furthermore, the organopolysiloxane emulsion in this composition cannot be produced by emulsion polymerization, making it impossible to obtain an organopolysiloxane emulsion with a high degree of polymerization.

[0007] Furthermore, silicone emulsion compositions comprising hydroxyl group-containing organopolysiloxanes, colloidal silica, amide group and carboxyl group-containing silanes, and epoxy group-containing silanes (Patent Document 4) have also been proposed. Patent Document 5 proposes the use of bismuth compounds.

[0008] When organotin compounds are not used, there is a problem in that the curing properties are inferior and the strength of the rubber coating is reduced. As an alternative to using organotin compounds, the use of inorganic tin compounds can be considered. While inorganic tin compounds can be effective alternatives to organotin curing catalysts in solvent systems, their use in aqueous systems is difficult due to their tendency to hydrolyze and become inactive. Prior art does not describe the use of inorganic tin compounds in aqueous systems. In order to use inorganic tin compounds as curing catalysts in aqueous compositions, it is important to obtain an emulsion composition mainly composed of an inorganic tin compound with excellent stability. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] Japanese Unexamined Patent Publication No. 56-16553 [Patent Document 2] Japanese Patent Application Publication No. 6-73291 [Patent Document 3] Japanese Patent Publication No. 2005-306994 [Patent Document 4] Japanese Patent Publication No. 2008-231276 [Patent Document 5] Japanese Patent Publication No. 2014-224164 [Overview of the project] [Problems that the invention aims to solve]

[0010] This invention has been made in view of the above circumstances, and aims to provide an inorganic tin emulsion with good storage stability and a method for producing the same. [Means for solving the problem]

[0011] This invention was made to achieve the above objective, (A) Inorganic tin compound: 100 parts by mass (B) Hydrocarbon oil: 5 to 100 parts by mass (C) Surfactant: 5-50 parts by mass (D) Water: 50~2,000 parts by mass Provided is an inorganic tin emulsion composition characterized by containing

[0012] With this configuration, an inorganic tin emulsion composition excellent in storage stability and usable as an aqueous curing catalyst can be obtained.

[0013] In this case, the component (B) can be an aliphatic hydrocarbon oil having 10 to 50 carbon atoms.

[0014] Thereby, an inorganic tin emulsion composition having more excellent storage stability can be obtained.

[0015] Also, the component (A) can be at least one of tin bis(2-ethylhexanoate) and tin bis(neodecanoate).

[0016] These are excellent in availability and handleability and can be preferably used in the present invention.

[0017] The average particle diameter of the emulsion particles of the inorganic tin emulsion composition can be 500 nm or less.

[0018] Thereby, the stability is excellent and a more preferable emulsion composition is obtained.

[0019] The emulsion composition can be free of organic tin compounds.

[0020] Thereby, the influence on the environment and toxicity can be further reduced.

[0021] A film-forming silicone emulsion composition containing the emulsion composition can be obtained.

[0022] Thereby, a film having improved film properties such as film hardness and tensile strength can be obtained.

[0023] Furthermore, the emulsion composition may be used as a coating agent.

[0024] This makes it possible to obtain a superior coating agent.

[0025] In this invention, (A) Inorganic tin compound: 100 parts by mass (B) Hydrocarbon oil: 5 to 100 parts by mass (C) Surfactant: 5-50 parts by mass (D) Water: 50~2,000 parts by mass The present invention provides a method for producing an inorganic tin emulsion composition, comprising the step of forming emulsion particles by emulsifying a mixture containing the above using an emulsifier.

[0026] This manufacturing method makes it possible to produce an inorganic tin emulsion composition with excellent storage stability.

[0027] The manufacturing method of the present invention may further include a step of reducing the particle size of emulsion particles using an emulsifier that reduces the particle size of emulsion particles using high pressure.

[0028] By reducing the particle size of the emulsion particles, it is possible to produce an inorganic tin emulsion composition with superior storage stability.

[0029] In the manufacturing method described above, in the step of reducing the particle size of emulsion particles using an emulsifier that reduces the particle size of emulsion particles using high pressure, the average particle size of the emulsion particles can be reduced to 500 nm or less.

[0030] This makes it possible to produce inorganic tin emulsion compositions with even better storage stability. [Effects of the Invention]

[0031] As described above, the inorganic tin emulsion composition of the present invention is useful as an aqueous curing catalyst because it has high storage stability. Furthermore, since it does not contain organotin compounds, it has low toxicity and environmental impact. [Modes for carrying out the invention]

[0032] As mentioned above, there was a need for the development of an inorganic tin emulsion composition with excellent storage stability.

[0033] As a result of diligent research into the above-mentioned problems, the inventors of the present invention have found that an inorganic tin emulsion composition containing the following components (A) to (D) exhibits excellent storage stability and can be used as an aqueous curing catalyst, thereby completing the present invention.

[0034] In other words, the present invention is (A) Inorganic tin compound: 100 parts by mass (B) Hydrocarbon oil: 5 to 100 parts by mass (C) Surfactant: 5-50 parts by mass (D) Water: 50~2,000 parts by mass This is an inorganic tin emulsion composition characterized by containing [a specific substance]. Furthermore, the manufacturing method of the present invention is (A) Inorganic tin compound: 100 parts by mass (B) Hydrocarbon oil: 5 to 100 parts by mass (C) Surfactant: 5-50 parts by mass (D) Water: 50~2,000 parts by mass This is a method for producing an inorganic tin emulsion composition, comprising the step of forming emulsion particles by emulsifying a mixture containing the above using an emulsifier.

[0035] The present invention will be described in detail below, but the present invention is not limited to these descriptions.

[0036] (A) component Component (A) of the present invention is an inorganic tin compound. In this invention, an inorganic tin compound refers to a tin compound that does not have a tin-carbon bond. Component (A) is not particularly limited as long as it is an inorganic tin compound, but tin carboxylates are preferred. Among these, bis(2-ethylhexanoate)tin and bisneodecanoate tin are particularly preferred from the viewpoint of availability and handling. Component (A) can be used alone or in appropriate combinations of two or more.

[0037] (B) Component Component (B) of this invention is a hydrocarbon oil. In this invention, by incorporating an appropriate amount of component (B), an inorganic tin compound, which is inherently unstable in water-based systems, can be transformed into an emulsion with good storage stability. There are no restrictions on the linear or branched shape of hydrocarbon oils. Examples include α-olefin oligomers, isoparaffins, isododecanes, isohexadecanes, squalanes, synthetic squalanes, vegetable squalanes, ceresin, paraffins, paraffin waxes, polyethylene waxes, polyethylene-polypropylene waxes, (ethylene / propylene / styrene) copolymers, (butylene / propylene / styrene) copolymers, liquid paraffins, pristanes, polyisobutylenes, hydrogenated polyisobutenes, microcrystalline waxes, and petrolatum. Component (B) is preferably an aliphatic hydrocarbon oil having 10 to 50 carbon atoms, and more preferably an aliphatic hydrocarbon oil having 10 to 40 carbon atoms. Examples of aliphatic hydrocarbon oils having 10 to 50 carbon atoms include isoparaffin, isododecane, isohexadecane, and liquid paraffin. Liquid paraffin is particularly preferred. Component (B) may be used alone or in combination of two or more types.

[0038] The amount of component (B) is 5 to 100 parts by mass per 100 parts by mass of component (A). 8 to 70 parts by mass is preferred, 10 to 50 parts by mass is more preferred, and 20 to 40 parts by mass is particularly preferred. (B) If the amount of component is below the lower limit, the storage stability of the emulsion will be poor, and if it exceeds the upper limit, the amount of hydrocarbon oil in the composition will be too high and the catalytic activity will decrease.

[0039] (C) Component Component (C) of the present invention is a surfactant, and is an emulsifier for emulsifying and dispersing components (A) and (B) in water to form an emulsion composition. The surfactant of component (C) is not particularly limited and may be a nonionic surfactant, anionic surfactant, cationic surfactant, or amphoteric surfactant. These can be used individually or in appropriate combinations of two or more.

[0040] Examples of nonionic surfactants used here include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, polyoxyethylene-modified organopolysiloxanes, and polyoxyethylene polyoxypropylene-modified organopolysiloxanes.

[0041] Examples of anionic surfactants include alkyl sulfate esters such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate, alkylbenzene sulfonate, polyoxyethylene alkylphenyl ether sulfonate, alkyl diphenyl ether disulfonate, alkane sulfonate, N-acyl taurate, dialkyl sulfosuccinate, monoalkyl sulfosuccinate, polyoxyethylene alkyl ether sulfosuccinate, fatty acid salts, polyoxyethylene alkyl ether carboxylate, N-acyl amino acid salt, monoalkyl phosphate salt, dialkyl phosphate salt, and polyoxyethylene alkyl ether phosphate salt.

[0042] Examples of cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, polyoxyethylenealkyldimethylammonium salts, dipolyoxyethylenealkylmethylammonium salts, tripolyoxyethylenealkylammonium salts, alkylbenzyldimethylammonium salts, alkylpyridinium salts, monoalkylamine salts, and monoalkylamidoamine salts.

[0043] Examples of amphoteric surfactants include alkyldimethylamine oxide, alkyldimethylcarboxybetaine, alkylamidopropyldimethylcarboxybetaine, alkylhydroxysulfobetaine, and alkylcarboxymethylhydroxyethylimidazolinium betaine.

[0044] As a surfactant, a nonionic surfactant is preferred because it can emulsify the oil phase components in small amounts and form fine particles.

[0045] From the viewpoint of emulsion stability, the HLB value of the nonionic surfactant (or the HLB value of the entire mixture if multiple surfactants are used) is preferably in the range of 9.0 to 18.0, more preferably 10.0 to 17.0, and even more preferably 11.0 to 16.0. The HLB value is calculated using the Griffin method. The HLB value is calculated using the following formula. N = N1 × W1 + N2 × W2 N: HLB value when using two types of surfactants with different HLB values N1, N2: HLB of each surfactant W1, W2: Weight fraction of each surfactant (W1 + W2 = 1)

[0046] The amount of component (C) used is 5 to 50 parts by mass per 100 parts by mass of component (A), preferably 7 to 30 parts by mass, and particularly preferably 10 to 25 parts by mass. If the amount of component (C) used is less than 5 parts by mass per 100 parts by mass of component (A), the stability of the emulsion decreases, and if it exceeds 50 parts by mass, the catalytic activity decreases.

[0047] (D) Component The emulsion composition of the present invention contains water as component (D). Any type of water can be used as component (D), such as deionized water or purified water. The amount of water added is 50 to 2,000 parts by mass per 100 parts by mass of component (A), with 100 to 1,000 parts by mass being more preferable. If the amount of water added is less than 50 parts by mass per 100 parts by mass of component (A), emulsification becomes difficult, and if it exceeds 2,000 parts by mass, the concentration of inorganic tin in component (A) becomes low, making it difficult to use as a catalyst because a large amount of the emulsion composition would need to be added to utilize it as a catalyst.

[0048] The manufacturing method of the present invention will be described below. An inorganic tin emulsion composition is prepared by emulsifying a mixture containing components (A), (B), (C), and (D) using an emulsifier. Emulsification can be performed using emulsifiers such as homodispersers, homomixers, colloid mills, line mixers, universal mixers, ultramixers, planetary mixers, combimixes, and high-pressure homogenizers. Alternatively, after preparing the emulsion composition by emulsifying the mixture containing components (A), (B), (C), and (D) using a homodisperser, homomixer, etc., the emulsion particles may be further reduced in size using an emulsifier that uses high pressure, such as a high-pressure homogenizer. One or more types of emulsifiers may be used. More preferably, the manufacturing method uses an emulsifier that reduces the size of emulsion particles using high pressure, such as a high-pressure homogenizer. A manufacturing method that uses an emulsifier, such as a high-pressure homogenizer, to reduce the particle size of emulsion particles, thereby achieving an average particle size of 500 nm or less, is particularly preferred.

[0049] The average particle size of the emulsion particles in the emulsion composition of the present invention is preferably 800 nm or less. More preferably 500 nm or less, and particularly preferably 400 nm or less. There is no particular lower limit, but it is about 50 nm or more. An average particle size exceeding 800 nm is undesirable because it reduces the stability of the emulsion. Note that the average particle size of the emulsion particles is the particle size at 50% volume integration by the laser diffraction-scattering method.

[0050] From an environmental and toxicity standpoint, the emulsion composition of the present invention preferably does not contain organotin compounds.

[0051] The emulsion composition of the present invention may contain inorganic powders, pigments, dyes, thickeners, preservatives, antibacterial agents, deodorants, rust inhibitors, antioxidants, defoamers, antistatic agents, ultraviolet absorbers, antifreeze agents, water-soluble resins, organic resin emulsions, and the like.

[0052] The emulsion composition of the present invention can be used as a catalyst to replace conventionally used organotin compounds. For example, it can be used as a catalyst for urethane reactions, esterification reactions, transesterification reactions, and silicone condensation reactions. Because the emulsion composition of the present invention has good storage stability, it is particularly suitable as a catalyst for aqueous compositions, and can be used, for example, as a curing catalyst for silicone emulsions.

[0053] The emulsion composition of the present invention is useful as a curing catalyst for silicone emulsions. By using the emulsion composition of the present invention as a curing catalyst for film-forming silicone emulsions, it is possible to improve the film properties such as hardness and tensile strength of the film. In this invention, a film-forming silicone emulsion is a silicone emulsion that can form a film after drying. For example, an emulsion containing an organopolysiloxane having a cross-linked structure can form a film after drying and is therefore a film-forming silicone emulsion. Whether or not a film is formed can be evaluated by weighing each silicone emulsion composition into a 15cm x 10cm PP (polypropylene) tray so that the non-volatile content is 8.0g, drying it at 25°C for 48 hours, and then drying it further at 105°C for 1 hour, and then checking whether a film is formed.

[0054] Examples of silicones having a cross-linked structure include organopolysiloxanes, which have a viscosity of 300,000 mPa·s or more at 25°C, as shown by the following formula. [ka] (In the formula, R 1 R is a hydrogen atom or a monovalent organic group having 1 to 20 substituted or unsubstituted carbon atoms, independently of each other. 2 These are independent of each other, as described above R 1 The group selected from the options is a hydroxyl group or an alkoxy group having 1 to 20 carbon atoms, where a, b, c, and d are values ​​that satisfy the viscosity of the organopolysiloxane at 25°C to be 300,000 mPa·s or more, with a≧2, c≧0, d≧0, and c+d≧1, and b can typically take a value of 200 or more, preferably 500 or more. However, if the value of c+d is large, the number of crosslinking units increases, so the viscosity may be 300,000 mPa·s or more even if b is 200 or less.

[0055] In this invention, viscosity was measured at 25°C using a BM-type or BH-type rotational viscometer. For viscosity that can be measured in liquid form, the viscosity was measured directly; for viscosity that is too high to measure in liquid form, the viscosity dissolved in 15% or 10% toluene was measured. For viscosity that is too high to measure in liquid form, the viscosity is always 300,000 mPa·s or higher.

[0056] Compositions utilizing the composition of the present invention as a catalyst can be widely applied, for example, as 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; water repellents, waterproofing agents, and release agents for concrete, mortar, and wood; binders for inorganic or organic substances; fiber treatment agents; paints; mold release agents; coatings; and so on. [Examples]

[0057] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. The "%" representing concentration and content indicates "mass%".

[0058] (A) Inorganic tin compounds (A-1) Neostan U-28 (product name): Manufactured by Nitto Kasei Co., Ltd., bis(2-ethylhexanoate)tin (A-2) Neostan U-50 (product name): Manufactured by Nitto Kasei Co., Ltd., tin bisneodecanate

[0059] (B) Liquid paraffin (B-1) KAYDOL (product name): Manufactured by Sonneborn, liquid paraffin, average carbon number 35

[0060] (C) Surfactants (C-1) Emulgen 1108 (product name): Manufactured by Kao Chemical Co., Ltd., polyoxyethylene alkyl lauryl ether, HLB value = 13.5 (C-2) Emulgen 104P (product name): Manufactured by Kao Chemical Co., Ltd., polyoxyethylene lauryl ether, HLB value = 9.6 (C-3) Emulgen 123P (product name): Manufactured by Kao Chemical Co., Ltd., polyoxyethylene lauryl ether, HLB value = 16.9 (E) Organotin compounds (E-1) Neostan U-810 (product name): Manufactured by Nitto Kasei Co., Ltd., dioctyl tin dilaurate

[0061] [Average particle size of emulsion] The particle size at 50% volume integration was measured using a laser diffraction / scattering particle size distribution analyzer LA-960 (manufactured by Horiba, Ltd.).

[0062] [Example 1] (A-1) Neostan U-28: 100 parts by mass (B-1)KAYDOL: 18.0 parts by mass (C-1) Emulgen 1108: 9.6 parts by mass (D) Water: 191.9 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an emulsion composition. Subsequently, the mixture was passed through a high-pressure homogenizer at a pressure of 60 MPa to reduce the particle size of the emulsified emulsion, thereby obtaining an inorganic tin emulsion composition (I-1). The average particle size of the obtained (I-1) was 330 nm.

[0063] [Example 2] (A-1) Neostan U-28: 100 parts by mass (B-1)KAYDOL: 28.5 parts by mass (C-1) Emulgen 1108: 20.2 parts by mass (D) Water: 105.4 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an emulsion composition. Subsequently, the mixture was passed through a high-pressure homogenizer at a pressure of 60 MPa to reduce the particle size of the emulsified emulsion, thereby obtaining an inorganic tin emulsion composition (I-2). The average particle size of the obtained (I-2) was 310 nm.

[0064] [Example 3] (A-1) Neostan U-28: 100 parts by mass (B-1)KAYDOL: 19.1 parts by mass (C-2) Emulgen 104P: 11.9 parts by mass (C-3) Emulgen 123P: 2.4 parts by mass (D) Water: 105.9 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an emulsion composition. Subsequently, the mixture was passed through a high-pressure homogenizer at a pressure of 60 MPa to reduce the particle size of the emulsified emulsion, thereby obtaining an inorganic tin emulsion composition (I-3). The average particle size of the obtained (I-3) was 350 nm.

[0065] [Example 4] (A-1) Neostan U-28: 100 parts by mass (B-1)KAYDOL: 19.1 parts by mass (C-1) Emulgen 1108: 13.5 parts by mass (D) Water: 105.4 parts by mass The mixture was mixed and emulsified using a homomixer to obtain emulsion composition (I-4). The average particle size of the obtained (I-4) was 440 nm.

[0066] [Example 5] (A-1) Neostan U-28: 100 parts by mass (B-1)KAYDOL: 22.0 parts by mass (C-2) Emulgen 104P: 12.9 parts by mass (C-3) Emulgen 123P: 1.8 parts by mass (D) Water: 104.6 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an emulsion composition. Subsequently, the mixture was passed through a high-pressure homogenizer at a pressure of 60 MPa to reduce the particle size of the emulsified emulsion, thereby obtaining an inorganic tin emulsion composition (I-5). The average particle size of the obtained (I-5) was 280 nm.

[0067] [Example 6] (A-2) Neostan U-50: 100 parts by mass (B-1)KAYDOL: 19.1 parts by mass (C-2) Emulgen 104P: 11.4 parts by mass (C-3) Emulgen 123P: 1.7 parts by mass (D) Water: 105.9 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an emulsion composition. Subsequently, the mixture was passed through a high-pressure homogenizer at a pressure of 60 MPa to reduce the particle size of the emulsified emulsion, thereby obtaining an inorganic tin emulsion composition (I-6). The average particle size of the obtained (I-6) was 490 nm.

[0068] [Example 7] (A-2) Neostan U-50: 100 parts by mass (B-1)KAYDOL: 25.5 parts by mass (C-1) Emulgen 1108: 13.5 parts by mass (D) Water: 107.0 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an emulsion composition. Subsequently, the mixture was passed through a high-pressure homogenizer at a pressure of 60 MPa to reduce the particle size of the emulsified emulsion, thereby obtaining an inorganic tin emulsion composition (I-7). The average particle size of the obtained (I-7) was 390 nm.

[0069] [Example 8] (A-2) Neostan U-50: 100 parts by mass (B-1)KAYDOL: 19.5 parts by mass (C-2) Emulgen 104P: 11.4 parts by mass (C-3) Emulgen 123P: 1.7 parts by mass (D) Water: 105.9 parts by mass The mixture was mixed and emulsified using a homomixer to obtain emulsion composition (I-8). The average particle size of the obtained (I-8) was 520 nm.

[0070] [Example 9] (A-1) Neostan U-28: 100 parts by mass (B-1)KAYDOL: 9.0 parts by mass (C-1) Emulgen 1108: 12.5 parts by mass (D) Water: 110.5 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an emulsion composition. Subsequently, the mixture was passed through a high-pressure homogenizer at a pressure of 60 MPa to reduce the particle size of the emulsified emulsion, thereby obtaining an inorganic tin emulsion composition (I-9). The average particle size of the obtained (I-9) was 450 nm.

[0071] [Example 10] (A-1) Neostan U-28: 100 parts by mass (B-1)KAYDOL: 20.0 parts by mass (C-1) Emulgen 1108: 8.5 parts by mass (D) Water: 110.0 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an emulsion composition. Subsequently, the mixture was passed through a high-pressure homogenizer at a pressure of 60 MPa to reduce the particle size of the emulsified emulsion, thereby obtaining an inorganic tin emulsion composition (I-10). The average particle size of the obtained (I-10) was 500 nm.

[0072] [Comparative Example 1] (A-1) Neostan U-28: 100 parts by mass (C-1) Emulgen 1108: 15.0 parts by mass (D) Water: 105.0 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an emulsion composition. Subsequently, the mixture was passed through a high-pressure homogenizer at a pressure of 60 MPa to reduce the particle size of the emulsified emulsion, thereby obtaining an inorganic tin emulsion composition (II-1). The average particle size of the obtained (II-1) was 1120 nm.

[0073] [Comparative Example 2] (A-1) Neostan U-28: 100 parts by mass (B-1)KAYDOL: 3.5 parts by mass (C-1) Emulgen 1108: 15.0 parts by mass (D) Water: 105.0 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an emulsion composition. Subsequently, the mixture was passed through a high-pressure homogenizer at a pressure of 60 MPa to reduce the particle size of the emulsified emulsion, thereby obtaining an inorganic tin emulsion composition (II-2). The average particle size of the obtained (II-2) was 850 nm.

[0074] [Comparative Example 3] (A-1) Neostan U-28: 100 parts by mass (B-1)KAYDOL: 15.0 parts by mass (C-1) Emulgen 1108: 4.5 parts by mass (D) Water: 105.0 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an emulsion composition. Subsequently, the mixture was passed through a high-pressure homogenizer at a pressure of 60 MPa to reduce the particle size of the emulsified emulsion, thereby obtaining an inorganic tin emulsion composition (II-3). The average particle size of the obtained (II-3) was 1200 nm.

[0075] [Comparative Example 4] Organotin Compounds (E-1) Neostan U-810: 100 parts by mass (B-1)KAYDOL: 18.0 parts by mass (C-1) Emulgen 1108: 9.6 parts by mass (D) Water: 191.9 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an emulsion composition. Subsequently, the mixture was passed through a high-pressure homogenizer at a pressure of 60 MPa to reduce the particle size of the emulsified emulsion, thereby obtaining organotin emulsion composition (II-4). The average particle size of the obtained (II-4) was 320 nm.

[0076] [Average particle size of emulsion] The particle size at 50% volume integration was measured using a laser diffraction / scattering particle size distribution analyzer LA-960 (manufactured by Horiba, Ltd.).

[0077] [Storage stability (25℃)] Each emulsion composition obtained in the examples and comparative examples was stored at 25°C for 3 months. After storage, the emulsion compositions were visually inspected. Those in which layer separation was observed within 1 month were marked with ×, those in which layer separation was not observed within 1 month but was observed within 2 months were marked with △, those in which layer separation was not observed within 2 months but was observed within 3 months were marked with ○, and those in which layer separation was not observed even after 3 months were marked with ◎.

[0078] [Storage stability (40℃)] Each emulsion composition obtained in the examples and comparative examples was stored at 40°C for two weeks. After storage, the emulsion compositions were visually inspected. Compositions where layer separation was observed within one week were marked with ×, those where separation was not observed within one week but was observed within two weeks were marked with △, and those where separation was not observed even after two weeks were marked with ○.

[0079] [Table 1]

[0080] [Table 2]

[0081] [Table 3]

[0082] As shown in Tables 1 to 3, in each example of the present invention, the average particle size, storage stability at 25°C, and storage stability at 40°C all showed good results. On the other hand, in Comparative Examples 1 to 3, the average particle size was large, and the storage stability at 25°C and 40°C was poor. Furthermore, each example of the present invention, similar to Comparative Example 4 which used an organotin compound, shows that the average particle size, storage stability at 25°C, and storage stability at 40°C are not poor.

[0083] [Film properties] Following the example in Patent Document 5, Manufacturing Example 1, an organopolysiloxane emulsion was prepared as follows. 498 g of octamethylcyclotetrasiloxane, 2 g of triethoxyphenylsilane, 50 g of 10% sodium lauryl sulfate aqueous solution, and 50 g of 10% dodecylbenzenesulfonic acid aqueous solution were charged and uniformly emulsified in a homomixer. Then, 400 g of water was gradually added to dilute the mixture, and it was passed through a high-pressure homogenizer at a pressure of 30 MPa to obtain a uniform white emulsion. This emulsion was transferred to a glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerization was carried out at 50°C for 24 hours. After aging at 110°C for 24 hours, it was neutralized with 12 g of 10% sodium carbonate aqueous solution. The average composition formula obtained from the above procedure was [ka] An emulsion (III) containing the organopolysiloxane shown was prepared. 30 g of the obtained emulsion (III) was added to 200 g of IPA with stirring to break down the emulsion and extract the organopolysiloxane. After drying this organopolysiloxane at 105°C for 3 hours, the viscosity was measured at 25°C using a rotational viscometer, but it was not possible to measure it directly. Therefore, the viscosity was measured using a 15% toluene solution and was found to be 1350 mPa·s. The film properties were measured using emulsion (III) as follows.

[0084] (III): 100 parts by mass (IV) Colloidal silica (Snowtex C, manufactured by Nissan Chemical Industries): 30 parts by mass Emulsion of tin compound obtained in each example and comparative example: 3 parts by mass The mixture was prepared, and 20g was poured into a disposable polypropylene resin tray (150mm x 105mm x 19mm). After being left for 48 hours in an atmosphere of 25°C and 60% relative humidity, it was heated at 105°C for 1 hour to produce a cured film with a thickness of approximately 1mm. The hardness, tensile strength, and elongation of this film were measured in accordance with JIS K 6249. The results are shown in the table below. Comparative Example 5 is a comparative example that does not contain any of the emulsion compositions (I) or (II) obtained in the aforementioned Examples and Comparative Examples.

[0085] [Table 4]

[0086] [Table 5]

[0087] [Table 6]

[0088] As is clear from the above results, the inorganic tin emulsion composition of the present invention has better storage stability than Comparative Examples 1 to 3, has curability equivalent to that of the organotin catalyst of Comparative Example 4, and exhibits superior curability compared to the inorganic tin emulsion composition of Comparative Example 5 and a composition containing no organotin emulsion.

[0089] This specification includes the following embodiments: [1]: (A) Inorganic tin compound: 100 parts by mass, (B) Hydrocarbon oil: 5 to 100 parts by mass An inorganic tin emulsion composition characterized by containing (C) surfactant: 5 to 50 parts by mass, and (D) water: 50 to 2,000 parts by mass. [2]: The emulsion composition of [1] above, wherein component (B) is an aliphatic hydrocarbon oil having 10 to 50 carbon atoms. [3]: The emulsion composition of [1] or [2] above, wherein component (A) is at least one of bis(2-ethylhexanoate)tin and bisneodecanoate tin. [4]: Any emulsion composition according to [1] to [3] above, wherein the average particle size of the emulsion particles of the inorganic tin emulsion composition is 500 nm or less. [5]: An emulsion composition according to any of [1] to [4] above, which does not contain an organotin compound. [6]: A film-forming silicone emulsion composition comprising any of the compositions described in [1] to [5] above. [7]: A coating agent comprising any of the compositions described in [1] to [6] above. [8]: A method for producing an inorganic tin emulsion composition, characterized by comprising the step of forming emulsion particles by emulsifying a mixture containing (A) an inorganic tin compound: 100 parts by mass, (B) a hydrocarbon oil: 5 to 100 parts by mass, (C) a surfactant: 5 to 50 parts by mass, and (D) water: 50 to 2,000 parts by mass using an emulsifier. [9]: A method for producing the inorganic tin emulsion composition according to [8], further comprising the step of reducing the particle size of the emulsion particles using an emulsifier that reduces the particle size of the emulsion particles using high pressure.

[10] : The manufacturing method according to [9] above, wherein in the step of reducing the particle size of emulsion particles using an emulsifier that reduces the particle size of emulsion particles using the high pressure, the average particle size of the emulsion particles is reduced to 500 nm or less. [Industrial applicability]

[0090] The inorganic tin emulsion composition of the present invention has good storage stability and excellent curability. It is suitable as a curing catalyst for aqueous compositions.

[0091] It should be noted that the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention.

Claims

1. (A) Inorganic tin compound, which is a tin carboxylate: 100 parts by mass (B) Hydrocarbon oil: 5 to 100 parts by mass (C) Surfactant: 5 to 50 parts by mass (D) Water: 50 to 2,000 parts by mass An inorganic tin emulsion composition characterized by containing [a certain substance].

2. The emulsion composition according to claim 1, wherein component (B) is an aliphatic hydrocarbon oil having 10 to 50 carbon atoms.

3. The emulsion composition according to claim 1, wherein component (A) is at least one of bis(2-ethylhexanoate)tin and bisneodecanoate tin.

4. The emulsion composition according to claim 1, wherein the average particle size of the emulsion particles of the inorganic tin emulsion composition is 500 nm or less.

5. The emulsion composition according to claim 1, which does not contain organotin compounds.

6. A film-forming silicone emulsion composition comprising the composition of claim 1.

7. A coating agent comprising the composition according to any one of claims 1 to 6.

8. (A) Inorganic tin compound, which is a tin carboxylate: 100 parts by mass (B) Hydrocarbon oil: 5 to 100 parts by mass (C) Surfactant: 5 to 50 parts by mass (D) Water: 50 to 2,000 parts by mass A method for producing an inorganic tin emulsion composition, comprising the step of forming emulsion particles by emulsifying a mixture containing using an emulsifier.

9. Furthermore, the method for producing an inorganic tin emulsion composition according to claim 8, further comprising the step of reducing the particle size of the emulsion particles using an emulsifier that reduces the particle size of the emulsion particles using high pressure.

10. The manufacturing method according to claim 9, wherein in the step of reducing the particle size of emulsion particles using an emulsifier that reduces the particle size of emulsion particles using the aforementioned high pressure, the average particle size of the emulsion particles is reduced to 500 nm or less.

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