Amino-modified silicone emulsion composition, as well as paint additives and paints.

Abstract

This amino-modified silicone emulsion composition comprises: 100 parts by mass of (A) an amino-modified silicone having a viscosity of 3,000-150,000 mPa∙s at 25ºC and an amino group equivalent of 5,000-30,000 g / mol; 0.5-15 parts by mass of (B) a polyether-modified silicone having a viscosity of 10-25,000 mPa∙s at 25ºC; 1.0-15 parts by mass of (C) an organic solvent having an SP value of 10.0-16.0; 3-50 parts by mass of (D) a surfactant; and 10-2,000 parts by mass of (E) water. This composition can be applied to an aqueous resin, and has suppressed cissing, favorable appearance after coating, and excellent stability when blended into paint.

Description

Technical Field

[0001] The present invention ,a is related to an amino-modified silicone emulsion composition , as well as a paint additive and a paint.

Background Art

[0002] For furniture, household appliances, automobiles, transportation equipment such as trains, and even various daily items, coating with paint is carried out for various purposes such as improving appearance, imparting gloss, and preventing dirt. Paint additives such as leveling agents and defoaming agents are formulated in the paint so as not to impair the appearance after coating. As a paint excellent in leveling property and dirt-preventing property, a composition using an additive containing fluorine in the molecule (Patent Document 1) is generally known, but the material is expensive and a fluorine-free additive is required from the viewpoint of environmental problems.

[0003] As a fluorine-free paint additive, polyether-modified silicone is widely used as a paint additive for the purpose of leveling property and defoaming property on the surface (Patent Documents 2 and 3). In the paint field, in recent years, with awareness of the environmental aspect, the shift from solvent-based resins to water-soluble resins and water-dispersible resins has been progressing. However, in water-based resins, there is a problem that repellency and pinholes are likely to occur on the appearance surface as compared with solvent-based resins. When the compatibility with the resin component in the paint is low, repellency occurs during coating, resulting in poor appearance. On the other hand, in order to prevent repellency, if a silicone component having high compatibility with the resin component in the paint is used, the reactivity with the resin may increase, and there is a risk that the stability as a paint may decrease.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] In view of the problems of the above prior art, the present invention provides an amino-modified silicone emulsion that can be applied to aqueous resins, suppresses repellency, has a good appearance after coating, and is excellent in stability when blended into paints composition , a paint additive, and a paint.

Means for Solving the Problems

[0006] As a result of intensive studies to achieve the above object, the present inventor has found that an amino-modified silicone emulsion composition containing the following components (A) to (E) can solve the above problems, and has thus completed the present invention.

[0007] Therefore, the present invention provides the following inventions. 1. (A) The following average compositional formula (I)

Chemical Formula

[0008] The amino-modified silicone emulsion composition of the present invention suppresses paint repellency after coating, provides a good appearance after coating, and exhibits excellent stability when compounded into paints, making it suitable as a water-based paint additive and for compounding with paints. [Modes for carrying out the invention]

[0009] The present invention will be described in detail below. Hereinafter, "amino-modified silicone emulsion composition" may be simply referred to as "composition". [(A) component] Component (A) of the present invention is the following average composition formula (I) [ka] [In the formula, R1 These are, independently of each other, unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R 2 These are independent of each other, and the general formula (1) -R 4 -(NH-R 5 ) p -NH2(1) (R 4 and R 5 These are independently divalent organic groups with 1 to 6 carbon atoms, and p is either 0 or 1. It is a group represented by R 3 R 1 , R 2 The group is selected from -OH, -OCH3, and -OC2H5, and a, b, c, d, and e are numbers satisfying the ranges 2≦a≦10, 100≦b≦2,000, 0≦c≦50, 0≦d≦5, and 0≦e≦5. However, if c=0, R 3 is R 2 That is the case. It is an amino-modified silicone expressed as such, with a viscosity of 3,000 to 150,000 mPa·s at 25°C and an amino group equivalent of 5,000 to 30,000 g / mol, and can be used alone or in combination of two or more types.

[0010] R 1 These are unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, independently of each other. 1 Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, tetradecyl, and octadecyl groups; alkenyl groups such as vinyl, allyl, 5-hexenyl, and oleyl groups; and aryl groups such as phenyl, tolyl, and naphthyl groups. Among these, methyl, long-chain (6-20 carbon atoms) alkyl groups, and phenyl groups are preferred, with methyl and phenyl groups being more preferred.

[0011] R 2 These are independent of each other, and the general formula (1) -R 4 -(NH-R 5 ) p -NH2(1) (R 4 and R 5 These are independently divalent organic groups with 1 to 6 carbon atoms, and p is either 0 or 1. This is a group represented by . Examples of divalent organic groups having 1 to 6 carbon atoms include divalent hydrocarbon groups such as alkylene groups, alkenylene groups, and arylene groups. Examples of groups represented by general formula (1) include 2-aminoethyl group, 3-aminopropyl group, 6-aminohexyl group, N-(2-aminoethyl)-3-aminopropyl group, N-(3-aminopropyl)-3-aminopropyl group, and N-(2-aminoethyl)-6-aminohexyl group. Among these, the 3-aminopropyl group or the N-(2-aminoethyl)-3-aminopropyl group is preferred from the standpoint of ease of obtaining raw materials.

[0012] R 3 R 1 , R 2 A group selected from -OH, -OCH3, and -OC2H5, where c=0 is R 3 is R 2 That is the case.

[0013] The value of a is 2 ≤ a ≤ 10, preferably 2 ≤ a ≤ 5, and more preferably a = 2. If a exceeds 10, the viscosity of the amino-modified silicone becomes too low, and its emulsifying properties decrease.

[0014] The value of b is 100 ≤ b ≤ 2,000, preferably 300 ≤ b ≤ 1,800, and more preferably 500 ≤ b ≤ 1,600. If b is less than 100, the gloss after coating decreases when used as a paint additive, and if b exceeds 2,000, the viscosity of the amino-modified silicone becomes too high, reducing its emulsifying properties.

[0015] c is 0 ≤ c ≤ 50, preferably 1 ≤ c ≤ 30, more preferably 1 ≤ c ≤ 20, and even more preferably 2 ≤ c ≤ 10. If c is less than 1, the amount of amino groups in the amino-modified silicone is too small, and the compatibility with the resin component of the paint decreases. However, R 3 =R 2In this case, c may be less than 1, or c may be 0. On the other hand, if c exceeds 50, the amount of amino groups in the amino-modified silicone is too high, reducing its stability when mixed with paint.

[0016] d is 0 ≤ d ≤ 5, and d = 0 is preferable. If d exceeds 5, the viscosity of the amino-modified silicone becomes too low, resulting in poor emulsification.

[0017] e is 0 ≤ e ≤ 5, and e = 0 is preferable. If e exceeds 5, the viscosity of the amino-modified silicone becomes too low, resulting in poor emulsification.

[0018] The viscosity of component (A) at 25°C is 3,000 to 150,000 mPa·s, preferably 5,000 to 120,000 mPa·s, more preferably 6,000 to 110,000 mPa·s, and even more preferably 10,000 to 100,000 mPa·s. If the viscosity is below the lower limit, the gloss after coating will decrease when used as a paint additive. By setting the viscosity to 6,000 mPa·s or higher, paint repellency after coating is further suppressed. If the viscosity exceeds the upper limit, the emulsifying properties will deteriorate. In this invention, the viscosity is the value measured using a BM type viscometer (for example, manufactured by Tokyo Keiki Co., Ltd.) at 25°C. The rotor, rotation speed, and rotation time are appropriately selected according to the viscosity based on conventional methods.

[0019] The amino group equivalent of component (A) is 5,000 to 30,000 g / mol, preferably 7,000 to 27,000 g / mol, and more preferably 8,000 to 25,000 g / mol. If the amino group equivalent is below the lower limit, there are too many amino groups, reducing stability when mixed with paint. On the other hand, if the amino group equivalent exceeds the upper limit, there are too few amino groups, resulting in insufficient hydrophilicity as an amino-modified silicone, which leads to poor emulsification. In this invention, the amino group equivalent is the number of grams of amino-modified silicone that can be neutralized with 1 mole of hydrochloric acid, and theoretically, it is molecular weight / number of nitrogen atoms. The amino group equivalent can be measured by neutralization titration, for example, by an automatic titrator manufactured by Hiranuma Sangyo Co., Ltd. More specifically, it can be measured by the following method. The amino group equivalent is measured by dissolving the target amino-modified silicone in a solvent mixture of toluene and IPA in a mass ratio of 1:1, and then titrating with hydrochloric acid using an automatic titrator to the endpoint of pH=7. The amino group equivalent is calculated as the molecular weight of silicone per mole of amino groups, and is calculated using the following formula. Amino group equivalent (g / mol) = {[Sample volume (g)] × 1,000} / {[Hydrochloric acid normality (N)] × [Hydrochloric acid titration volume (mL)] × [Hydrochloric acid titer (F)]}

[0020] (A) Amino-modified silicones can be readily obtained by known synthesis methods. For example, as described in the examples of International Publication WO2021 / 1320571, they can be obtained by equilibrating a cyclic siloxane such as octamethylcyclotetrasiloxane with 3-aminopropyldiethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane, or a hydrolysate thereof, and a compound selected from hexamethyldisiloxane, dimethyl silicone represented by the following formula (2), etc., as other raw materials, in the presence of a catalyst such as alkali metal hydroxide or tetramethylammonium hydroxide. [ka] (In the equation, x is between 1 and 100.) Note that x is between 1 and 100, preferably between 3 and 50, and more preferably between 3 and 20.

[0021] [(B) Component] Component (B) of the present invention is the following average composition formula (II) [ka] [In the formula, R 1 These are, independently of each other, unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R 6 These are independent of each other, and the general formula (3) -C h H 2h O(C2H4O) i (C3H6O) j R 8 (3) It is a monovalent organic group represented by R 7 is, R 1 , R 6 A group selected from -OH, -OCH3 and -OC2H5, R 8 is a group selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an acetyl group, where h is an integer from 1 to 5, i is a number from 5 to 50, and j is a number from 0 to 40. f and g are 0 ≤ f ≤ 200 and 0 ≤ g ≤ 30. However, if g = 0, R 7 is R 6 That is the case. It is a polyether-modified silicone expressed as such, with a viscosity of 10 to 25,000 mPa·s at 25°C, and can be used alone or in combination of two or more types.

[0022] R 1These are unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, independently of each other. Examples include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, tetradecyl, and octadecyl groups; alkenyl groups such as vinyl, allyl, 5-hexenyl, and oleyl groups; and aryl groups such as phenyl, tolyl, and naphthyl groups. Among these, methyl, long-chain (6 to 20 carbon atoms) alkyl groups, and phenyl groups are preferred, with methyl and phenyl groups being more preferred.

[0023] R 6 These are independent of each other, and the general formula (3) -C h H 2h O(C2H4O) i (C3H6O) j R 8 (3) It is a monovalent organic group represented by R. 8 R is a group selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an acetyl group. 8 Specific examples include hydrogen atoms, alkyl groups such as methyl groups, ethyl groups, propyl groups, butyl groups, and pentyl groups, or acetyl groups. Furthermore, h is an integer from 1 to 5, preferably 2 to 4, and i is a number from 5 to 50, preferably 5 to 35, and more preferably 5 to 30. The j / i of component (B) is preferably 0 to 2.0, more preferably 0.05 to 1.5, even more preferably 0.25 to 1.3, and particularly preferably 0.50 to 1.2.

[0024] The HLB value of component (B) is preferably 3 to 15, more preferably 4 to 13, and even more preferably 4.5 to 10. The HLB value in this invention is calculated using the Griffin method.

[0025] R 7 is, R 1 , R 6 A group selected from -OH, -OCH3 and -OC2H5, and when g=0, R 7 is R 6 That is the case.

[0026] f is 0 ≤ f ≤ 200, preferably 0 ≤ f ≤ 100, and more preferably 0 ≤ f ≤ 70. g is 0 ≤ g ≤ 30, preferably 0 ≤ g ≤ 20, and more preferably 0 ≤ g ≤ 10. However, if g = 0, R 7 is R 6 That is the case.

[0027] The viscosity of component (B) at 25°C is 10 to 25,000 mPa·s, preferably 100 to 20,000 mPa·s, and more preferably 200 to 10,000 mPa·s.

[0028] The content of component (B) is 0.1 to 15.0 parts by mass per 100 parts by mass of component (A), preferably 0.2 to 10 parts by mass, more preferably 0.4 to 5.0 parts by mass, and even more preferably 0.6 to 4.0 parts by mass. If the amount of component (B) is too small, repellency is likely to occur after coating, and if the amount of component (B) is too large, the stability of the paint formulation will decrease.

[0029] [(C) component] Component (C) of the present invention is an organic solvent having an SP value of 10.0 to 16.0, and can be used alone or in combination of two or more. The SP value is a solubility parameter, also expressed as the solubility coefficient, and is a characteristic value proposed by Hildebrand that serves as a measure of the miscibility between liquids. Examples of such organic solvents include alcohol compounds, ketone compounds, ester compounds, ether compounds, glycol compounds, etc. Specifically, examples include cellosolve, propyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, methyl carbitol, carbitol, propyl carbitol, butyl carbitol, cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, 2,2,4-trimethyl-1,3-pentadiol monoisobutyrate, ethylene glycol, propylene glycol, 1,3-butylene glycol, etc. Among these, propylene glycol monomethyl ether, ethylene glycol, and 1,3-butylene glycol are preferred.

[0030] (C) The SP value of component C is more preferably 11.0 to 15.5, and even more preferably 12.0 to 15.0. If the SP value is less than 10.0 or greater than 16.0, it may be difficult to prepare the emulsion, or the emulsion stability when emulsified may decrease, resulting in poor appearance and stability when compounded into paint.

[0031] The content of component (C) is 1 to 15 parts by mass per 100 parts by mass of component (A), preferably 1.0 to 15 parts by mass, more preferably 1.5 to 12 parts by mass, and even more preferably 2.0 to 10 parts by mass. If the amount of component (C) is too low, the compatibility with the resin component in the paint decreases, making it easier for poor appearance after coating to occur, and if the amount of component (C) is too high, the emulsion stability decreases.

[0032] [(D) component] Component (D) of the present invention is a surfactant, which can be used alone or in combination of two or more. The surfactant is not particularly limited and includes nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.

[0033] Examples of nonionic surfactants 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.

[0034] 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.

[0035] Examples of cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, polyoxyethylenealkyldimethylammonium salts, dipolyoxyethylenealkylmethylammonium salts, tripolyoxyethylenealkylammonium salts, alkylbenzyldimethylammonium salts, alkylpyridinium salts, monoalkylamine salts, and monoalkylamidoamine salts.

[0036] Examples of amphoteric surfactants include alkyldimethylamine oxide, alkyldimethylcarboxybetaine, alkylamidopropyldimethylcarboxybetaine, alkylhydroxysulfobetaine, and alkylcarboxymethylhydroxyethylimidazolinium betaine.

[0037] (D) Component is more preferably a nonionic surfactant, and more preferably polyoxyethylene alkyl ethers and polyoxyethylene polyoxypropylene alkyl ethers. In particular, poly(oxyethylene) secondary alkyl ethers, which are obtained by adding an EO chain to the hydroxyl group of a linear secondary alcohol, are preferred.

[0038] (D) The nonionic surfactant has an HLB value of 9.0 to 17.0, B 11.0 to 16.0 is more preferable, and 12.0 to 15.0 is even more preferable.

[0039] The content of component (D) is 3 to 50 parts by mass per 100 parts by mass of component (A), preferably 5 to 30 parts by mass, more preferably 6 to 15 parts by mass, and even more preferably 7 to 10 parts by mass. If the amount of component (D) is too small, repellency is likely to occur after coating, and if the amount of component (D) is too large, the stability of the paint formulation will decrease.

[0040] [(E) component] The composition of the present invention contains (E) water. The water content is 10 to 2,000 parts by mass per 100 parts by mass of component (A), and preferably 30 to 1,000 parts by mass.

[0041] [(F)Organic acid] Component (F) is an organic acid, which can be used alone or in appropriate combinations of two or more. Specifically, examples include monocarboxylic acids, dicarboxylic acids, hydroxycarboxylic acids, aromatic carboxylic acids, and acidic amino acids. More specifically, examples include monocarboxylic acids such as acetic acid, propionic acid, and caprylic acid; dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, and fumaric acid; hydroxycarboxylic acids such as glycolic acid, lactic acid, hydroxyacrylic acid, glyceric acid, malic acid, tartaric acid, and citric acid; aromatic carboxylic acids selected from benzoic acid, salicylic acid, and phthalic acid; and acidic amino acids such as glutamic acid and aspartic acid.

[0042] (F) When component (F) is included, its content is 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass, and more preferably 0.2 to 1 part by mass, per 100 parts by mass of component (A).

[0043] In the composition of the present invention, from the viewpoint of emulsion stability and separation suppression, the average particle size of the emulsion particles is preferably 450 nm or less, more preferably 400 nm or less, and even more preferably 350 nm or less. If the average particle size is greater than 450 nm, the emulsion stability is low and separation may occur quickly. There is no lower limit to the average particle size, but it can be, for example, 80 nm. In this invention, the average particle size of the emulsion particles is the particle size at 50% of the volume integrated value in the particle size distribution determined by the laser diffraction-scattering method. There is no particular limit to the equipment used for the laser diffraction-scattering method, but for example, the LA960 manufactured by HORIBA can be used.

[0044] In the composition of the present invention, when (A) the content of amino-modified silicone is (Aw), (B) the content of polyether-modified silicone is (Bw), and (D) the content of surfactant is (Dw), the ratio [(Bw) + (Dw)] / (Aw) is preferably 0.05 to 0.25, more preferably 0.07 to 0.20, and even more preferably 0.08 to 0.15. Setting [(Bw) + (Dw)] / (Aw) to 0.05 or higher further enhances emulsion stability. Setting it to 0.25 or lower further enhances stability when compounded into paints. Note that w is mass.

[0045] (A) When the amino group equivalent of the amino-modified silicone is (Aae), (B) the content of the polyether-modified silicone is (Bw), and (D) the content of the surfactant is (Dw), then (Aae) / [(Bw)+(Dw)] is preferably 1,000 or more, more preferably 1,200 or more, and even more preferably 1,600 or more. Setting (Aae) / [(Bw)+(Dw)] to 1,000 or more further enhances the stability when compounded into paint. There is no particular upper limit, but for example, it can be 4,000 or less, preferably 3,000 or less. Hereinafter, w is the mass.

[0046] The composition of the present invention preferably has a pH of 3.5 to 7.5 at 25°C, more preferably 3.7 to 7.0, and even more preferably 4.0 to 6.5. In this invention, pH refers to the emulsion. composition This value was measured at 25°C using a pH meter (LAQUA, manufactured by HORIBA).

[0047] [Manufacturing method] The composition of the present invention can be prepared, for example, by mixing component (E) with components (A), (B), (C), and (D), and emulsifying and dispersing them according to conventional methods. Among these, an oil-in-water (O / W) emulsion is preferred. Also, emulsion composition It can be further diluted with water and used for the purposes described later. There are no particular restrictions on the amount of water used for dilution; it can be adjusted as appropriate depending on the application.

[0048] Emulsion containing amino-modified silicone composition As a method for obtaining the amino-modified silicone, there is a so-called emulsion polymerization method in which the raw materials of the amino-modified silicone are emulsified and dispersed in water using a surfactant, and then polymerized in the emulsion by adding a catalyst. However, in the present invention, it is preferable to obtain component (A) by equilibrating a cyclic siloxane such as octamethylcyclotetrasiloxane with 3-aminopropyldiethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane, or a hydrolysate thereof, and a compound selected from other raw materials such as hexamethyldisiloxane or dimethyl silicone represented by the above formula (2) as one raw material, and then prepare an emulsion composition by mixing with components (B), (C), (D) and optionally (F), and emulsifying and dispersing in water according to a conventional method.

[0049] An example of the emulsification formulation details is as follows: For example, in a mixing device: Combimix (Primix Corporation), (A) amino-modified silicone, (B) polyether-modified silicone, (C) organic solvent, (D) surfactant, and a portion of (E) water are mixed and emulsified using a homomixer (a stirrer that uses the rotation of a rotor in a stator) at 500-5,000 rpm or a disper (a stirrer that uses the rotation of toothed blades) at 500-5,000 rpm and an anchor at 5-50 rpm. After the entire mixture is emulsified, it is stirred for 15-180 minutes using a disper at 500-5,000 rpm and an anchor at 5-50 rpm until the desired particle size is achieved, then the remaining (E) water is added and diluted with a homomixer at 2,000-3,000 rpm to obtain the amino-modified silicone emulsion of the present invention. composition Prepare it.

[0050] The emulsification temperature is not particularly limited, but is preferably 0-80°C, and more preferably 10-60°C. Emulsification is easier at temperatures between 10-60°C, and the resulting emulsion tends to be more stable. (Amino-modified silicone emulsion) composition When heated at 70-80°C for 1-30 hours, the particle size may decrease or the viscosity may decrease, therefore, amino-modified silicone emulsion compositionIn the manufacturing process, a heating step of 70-80°C may be included depending on the desired particle size and viscosity. When emulsifying, the pressure may be atmospheric pressure, reduced pressure, or increased pressure. When emulsifying under reduced or increased pressure, foam is less likely to be incorporated, which can lead to more effective emulsification. When using reduced pressure, it is preferable that the pressure be higher than the vapor pressure of the raw materials to prevent the raw materials from volatilizing. There is no specific requirement for the emulsification time; it should be the time it takes to reach the desired particle size, but it is generally selected appropriately between 30 and 360 minutes.

[0051] There are no particular restrictions on the emulsifier used for emulsification, as long as it can stir the raw materials and the emulsified composition. Colloid mills (IKA, PUC, Nippon Seiki Seisakusho, Iwaki), high-shear mixers (Silverson, Primix), homomixers (Primix), homodispers (Primix), ad-homomixers (Primix), combimix (Primix), which are three-screw dispersion kneaders that combine a homomixer, homodisperser, and anchor mixer, and twin-screw mixers with co-direction or anomalous-direction screws such as HAAKE Mini Lab II (Thermo Scientific), MC15, and MC5 (Leo Lab) can be used.

[0052] In addition to the components (A) to (F) described above, the composition of the present invention may contain various optional components in appropriate amounts as needed, provided that the objectives of the present invention are not impaired. Examples of such optional components include silicone components other than components (A) and (B), additives, and the like.

[0053] Examples of silicone components other than components (A) and (B) include, for example, silicone oils such as dimethyl silicone oil, methyl hydrogen silicone oil, methylphenyl silicone oil, and alkyl-modified silicone oil. When silicone components other than components (A) and (B) are included, the amount is preferably 0.5 to 10 parts by mass per 100 parts by mass of component (A).

[0054] Examples of additives include protective colloids, thickeners, antifreezes, preservatives, rust inhibitors, antioxidants, fragrances, UV absorbers, antibacterial agents, curing catalysts, organic powders, inorganic powders, dyes, and fillers. These can be used individually or in combination of two or more in appropriate amounts. The desired effect can be achieved even without the presence of fluorine. When these are added, the amount is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 1 part by mass, per 100 parts by mass of component (A).

[0055] [Paint additives and paints] Furthermore, the emulsion of the amino-modified silicone of the present invention composition It is also useful as a paint additive. For example, amino-modified silicone emulsions. composition The above amino-modified silicone emulsion can be incorporated into the paint, preferably at a concentration of 0.1 to 30% by mass, more preferably at 0.5 to 20% by mass. If the content is above the lower limit, leveling properties can be imparted, but if the content is below the upper limit, the leveling effect will be small, and there is a risk of poor appearance after coating. composition It can be made into a paint containing [the specified ingredient]. [Examples]

[0056] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. Note that, if a product name is specified, the amounts indicated refer to the amounts in that product.

[0057] The measurement method is shown below. Average particle size: Amino-modified silicone emulsion composition The values ​​were obtained by diluting the substance with water approximately 10 times and measuring it using a laser diffraction particle size analyzer (HORIBA LA960) (50% of the volume integrated value in the particle size distribution).

[0058] pH: Amino-modified silicone emulsion Composition This value was measured at 25°C using a pH meter (LAQUA, manufactured by HORIBA).

[0059] Viscosity: The value was measured using a BM-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at a temperature of 25°C.

[0060] Amino group equivalent: This value was measured using an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd.) according to the following method. The amino group equivalent is measured by dissolving the target amino-modified silicone in a solvent mixture of toluene and IPA in a mass ratio of 1:1, and then titrating with hydrochloric acid using an automatic titrator to the endpoint of pH=7. The amino group equivalent is calculated as the molecular weight of silicone per mole of amino groups, and is calculated using the following formula. Amino group equivalent (g / mol) = {([Sample volume (g)] × 1,000)} / {[Hydrochloric acid normality (N)] × [Hydrochloric acid titration volume (mL)] × [Hydrochloric acid titer (F)]}

[0061] The following ingredients were used. (A) Amino-modified silicone (A) Amino-modified silicone represented by the following average composition formula (A-1) [ka] Viscosity: 74,000 mPa·s, Amino group equivalent: 20,000 g / mol

[0062] (A-2) [ka] Viscosity: 32,000 mPa·s, Amino group equivalent: 19,000 g / mol

[0063] (A-3) [ka] Viscosity: 5,000 mPa·s, Amino group equivalent: 12,000 g / mol

[0064] (B) Polyether-modified silicone Polyether-modified silicone represented by the following average composition formula

[0065] (B-1) [ka] Viscosity: 15,000mPa·s HLB: 5.8

[0066] (B-2) [ka] Viscosity: 1,600mPa·s HLB: 6.2

[0067] (B-3) [ka] Viscosity: 1,300mPa·s HLB: 9.5

[0068] (C) Component (C-1): Ethylene glycol, SP value: 14.2 (C-2): 1,3-Butylene glycol, SP value: 14.2 (C-3): Butyl acetate, SP value: 8.5, comparative product

[0069] (D) Surfactants (D-1): Poly(oxyethylene) secondary alkyl ether [Softanol 90 (trade name): manufactured by Nippon Shokubai], HLB value 13.3 (D-2): Polyoxyethylene tridecyl ether [Newcol 1310 (trade name): manufactured by Nippon Emulsifier Co., Ltd.], HLB value 13.7

[0070] (F)Organic acid (F-1): Acetic acid

[0071] [Example 1] (A-1) 100 parts by mass of amino-modified silicone, (B-1) 2.78 parts by mass of polyether-modified silicone, (C-1) 5.56 parts by mass of ethylene glycol, (D-1) 10.56 parts by mass of softanol 90, (E) 158.58 parts by mass of ion-exchanged water, and (F-1) 0.31 parts by mass of acetic acid were mixed and emulsified using a homomixer to obtain amino-modified silicone emulsion composition (I-1). The average particle size of the emulsion particles was 310 nm, and the pH was 4.4.

[0072] [Example 2] (A-2) 100 parts by mass of amino-modified silicone, (B-1) 2.78 parts by mass of polyether-modified silicone, (C-1) 5.56 parts by mass of ethylene glycol, (D-1) 10.56 parts by mass of poly(oxyethylene) secondary alkyl ether, (E) 158.58 parts by mass of ion-exchanged water, and (F-1) 0.31 parts by mass of acetic acid were mixed using a homomixer and emulsified to obtain amino-modified silicone emulsion composition (I-2). The average particle size of the emulsion particles was 320 nm, and the pH was 4.7.

[0073] [Example 3] (A-1) 100 parts by mass of amino-modified silicone, (B-3) 1.11 parts by mass of polyether-modified silicone, (C-1) 6.11 parts by mass of ethylene glycol, (D-1) 9.17 parts by mass of poly(oxyethylene) secondary alkyl ether, (E) 161.08 parts by mass of ion-exchanged water, and (F-1) 0.31 parts by mass of acetic acid were mixed using a homomixer and emulsified to obtain amino-modified silicone emulsion composition (I-3). The average particle size of the emulsion particles was 300 nm, and the pH was 4.5.

[0074] [Example 4] (A-1) 100 parts by mass of amino-modified silicone, (B-2) 0.97 parts by mass of polyether-modified silicone, (C-1) 5.56 parts by mass of ethylene glycol, (D-1) 8.33 parts by mass of poly(oxyethylene) secondary alkyl ether, (E) 162.53 parts by mass of ion-exchanged water, and (F-1) 0.39 parts by mass of acetic acid were mixed and emulsified using a homomixer to obtain amino-modified silicone emulsion composition (I-4). The average particle size of the emulsion particles was 300 nm, and the pH was 4.3.

[0075] [Example 5] (A-1) 100 parts by mass of amino-modified silicone, (B-2) 1.39 parts by mass of polyether-modified silicone, (C-2) 5.56 parts by mass of 1,3-butylene glycol, (D-1) 9.17 parts by mass of poly(oxyethylene) secondary alkyl ether, (E) 161.36 parts by mass of ion-exchanged water, and (F-1) 0.31 parts by mass of acetic acid were mixed and emulsified using a homomixer to obtain amino-modified silicone emulsion composition (I-5). The average particle size of the emulsion particles was 290 nm, and the pH was 4.4.

[0076] [Example 6] (A-3) 100 parts by mass of amino-modified silicone, (B-2) 2.80 parts by mass of polyether-modified silicone, (C-1) 5.56 parts by mass of ethylene glycol, (D-1) 10.00 parts by mass of poly(oxyethylene) secondary alkyl ether, (E) 161.36 parts by mass of ion-exchanged water, and (F-1) 0.50 parts by mass of acetic acid were mixed using a homomixer and emulsified to obtain amino-modified silicone emulsion composition (I-6). The average particle size of the emulsion particles was 320 nm, and the pH was 4.3.

[0077] [Example 7] (A-3) 100 parts by mass of amino-modified silicone, (B-2) 0.95 parts by mass of polyether-modified silicone, (C-1) 5.56 parts by mass of ethylene glycol, (D-1) 3.50 parts by mass of poly(oxyethylene) secondary alkyl ether, (E) 161.36 parts by mass of ion-exchanged water, and (F-1) 0.50 parts by mass of acetic acid were mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (I-7). The average particle size of the emulsion particles was 320 nm, and the pH was 4.4.

[0078] [Comparative Example 1] (A-2) 100 parts by mass of amino-modified silicone, (D-2) 18.67 parts by mass of polyoxyethylene tridecyl ether, (E) 214.33 parts by mass of ion-exchanged water, and (F-1) 0.33 parts by mass of acetic acid were mixed using a homomixer and emulsified to obtain amino-modified silicone emulsion composition (II-1). The average particle size of the emulsion particles was 270 nm, and the pH was 4.9.

[0079] [Comparative Example 2] (A-1) 100 parts by mass of amino-modified silicone, (C-1) 5.56 parts by mass of ethylene glycol, (D-1) 10.56 parts by mass of poly(oxyethylene) secondary alkyl ether, (E) 161.36 parts by mass of deionized water, and (F-1) 0.31 parts by mass of acetic acid were mixed using a homomixer and emulsified to obtain amino-modified silicone emulsion composition (II-2). The average particle size of the emulsion particles was 330 nm, and the pH was 4.5.

[0080] [Comparative Example 3] (A-3) 100 parts by mass of amino-modified silicone, (C-1) 5.56 parts by mass of ethylene glycol, (D-1) 10.56 parts by mass of poly(oxyethylene) secondary alkyl ether, (E) 161.17 parts by mass of ion-exchanged water, and (F-1) 0.50 parts by mass of acetic acid were mixed using a homomixer and emulsified to obtain amino-modified silicone emulsion composition (II-3). The average particle size of the emulsion particles was 330 nm, and the pH was 4.7.

[0081] [Comparative Example 4] (A-1) 100 parts by mass of amino-modified silicone, (B-1) 15.28 parts by mass of polyether-modified silicone, (C-1) 5.56 parts by mass of ethylene glycol, (D-1) 10.56 parts by mass of poly(oxyethylene) secondary alkyl ether, (E) 146.08 parts by mass of ion-exchanged water, and (F-1) 0.31 parts by mass of acetic acid were mixed using a homomixer and emulsified to obtain amino-modified silicone emulsion composition (II-4). The average particle size of the emulsion particles was 310 nm, and the pH was 4.3.

[0082] [Comparative Example 5] (A-2) 100 parts by mass of amino-modified silicone, (B-1) 15.28 parts by mass of polyether-modified silicone, (C-1) 5.56 parts by mass of ethylene glycol, (D-1) 10.56 parts by mass of poly(oxyethylene) secondary alkyl ether, (E) 146.08 parts by mass of ion-exchanged water, and (F-1) 0.31 parts by mass of acetic acid were mixed using a homomixer and emulsified to obtain amino-modified silicone emulsion composition (II-5). The average particle size of the emulsion particles was 300 nm, and the pH was 4.4.

[0083] [Comparative Example 6] (A-1) 100 parts by mass of amino-modified silicone, (B-2) 15.23 parts by mass of polyether-modified silicone, (C-1) 5.56 parts by mass of ethylene glycol, (D-1) 4.76 parts by mass of poly(oxyethylene) secondary alkyl ether, (E) 163.33 parts by mass of ion-exchanged water, and (F-1) 0.31 parts by mass of acetic acid were mixed using a homomixer and emulsified to obtain amino-modified silicone emulsion composition (II-6). The average particle size of the emulsion particles was 320 nm, and the pH was 4.3.

[0084] [Comparative Example 7] (A-1) 100 parts by mass of amino-modified silicone, (B-2) 1.39 parts by mass of polyether-modified silicone, (C-3) 5.56 parts by mass of butyl acetate, (D-1) 9.17 parts by mass of poly(oxyethylene) secondary alkyl ether, (E) 161.36 parts by mass of deionized water, and (F-1) 0.31 parts by mass of acetic acid were mixed and emulsified using a homomixer to obtain amino-modified silicone emulsion composition (II-7). The average particle size of the emulsion particles was 300 nm, and the pH was 4.4.

[0085] The obtained silicone emulsion compositions were evaluated for "emulsion stability," "turbidity after coating," "repellency after coating," and "stability during paint formulation" using the methods described below. The results are shown in the table.

[0086] [Emulsion stability] 100g of each emulsion obtained in the examples and comparative examples was placed in a glass bottle and left to stand at 40°C for one month. After that, the non-volatile content of the upper and lower layers (105°C, 3 hours) was measured. The closer the value obtained by dividing the non-volatile content of the upper layer by the non-volatile content of the lower layer is to 1, the smaller the separation and the higher the stability. 1 The further a value is from the target, the more isolated and less stable it appears.

[0087] [Appearance after coating] 10 g of the main component of water-based high-durability two-component urethane varnish, clear (product name, manufactured by Asahi Paint Co., Ltd.) was mixed with 0.2 g of each amino-modified silicone emulsion composition obtained in the examples and comparative examples. Furthermore, 2 g of the hardener of water-based high-durability two-component urethane varnish, clear (product name, manufactured by Asahi Paint Co., Ltd.) was added and mixed to prepare the paint solution for evaluation. The evaluation coating solution prepared as described above was applied to uncoated cardboard (15cm x 7cm) using a No. 20 bar coater, and then dried at 25°C for 3 hours. After drying, the condition of the coating film was visually inspected, and those that were transparent were marked with "○", while those that showed cloudiness were marked with "×".

[0088] [Repelling after coating] 10 g of the main component of water-based high-durability two-component urethane varnish, clear (product name, manufactured by Asahi Paint Co., Ltd.) was mixed with 0.2 g of each amino-modified silicone emulsion composition obtained in the examples and comparative examples. Furthermore, 2 g of the hardener of water-based high-durability two-component urethane varnish, clear (product name, manufactured by Asahi Paint Co., Ltd.) was added and mixed to prepare the paint solution for evaluation. The evaluation coating solution prepared as described above was applied to uncoated cardboard (15cm x 7cm) using a No. 20 bar coater, and then dried at 25°C for 3 hours. After drying, the condition of the coating film was visually inspected. Those with no repellency were marked "◎", those with repellency on a part of the coated surface were marked "〇", and those with repellency on the entire coated surface were marked "×".

[0089] [Stability during paint formulation] 10 g of the main component of water-based high-durability two-component urethane varnish transparent (clear) (product name, manufactured by Asahi Pen Co., Ltd.) was mixed with 1.0 g of each amino-modified silicone emulsion composition obtained in the examples and comparative examples. After mixing, the mixture was stored at 25°C and the viscosity of the mixture was measured after 24 hours. Mixtures with a viscosity of 1.1 times or less compared to the viscosity of the main component of water-based high-durability two-component urethane varnish transparent (clear) (product name, manufactured by Asahi Pen Co., Ltd.) alone were marked with "◎", those with a viscosity between 1.1 times and 2.0 times were marked with "○", and those with a viscosity greater than 2.0 times were marked with "×".

[0090] [Table 1]

[0091] [Table 2]

[0092] As is clear from the above results, the amino-modified silicone emulsion of the present invention composition When mixed into paint, it produces a good coating appearance without any repellency. Furthermore, it exhibits good stability after mixing. [Industrial applicability]

[0093] The present invention provides an amino-modified silicone emulsion. composition This additive provides a good coating appearance during paint formulation and does not cause repellency. Furthermore, it exhibits good stability after paint formulation. It is suitable as a paint additive.

Claims

1. (A) The following average empirical formula (I) 【Chemistry 1】 [In the formula, R 1 These are, independently of each other, unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R 2 These are independent of each other, and the general formula (1) -R 4 -(NH-R 5 ) p -NH 2 (1) (R 4 and R 5 These are independently divalent organic groups having 1 to 6 carbon atoms, and p is 0 or 1. is a group represented by R 3 are each independently R 1 R 2 , -OH, -OCH 3 and -OC 2 H 5 is a group selected from, and a, b, c, d and e are numbers satisfying the ranges of 2 ≤ a ≤ 10, 100 ≤ b ≤ 2,000, 0 ≤ c ≤ 50, 0 ≤ d ≤ 5, and 0 ≤ e ≤ 5. However, when c = 0, R 3 is R 2 .] Amino-modified silicone, expressed as such, with a viscosity of 3,000 to 150,000 mPa·s at 25°C and an amino group equivalent of 5,000 to 30,000 g / mol: 100 parts by mass, (B) The following average composition formula (II) 【Chemistry 2】 [In the formula, R 1 These are, independently of each other, unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R 6 These are independent of each other, and the general formula (3) -C h H 2h O(C 2 H 4 O) i (C 3 H 6 O) j R 8 (3) It is a monovalent organic group represented by R 7 R 1 , R 6 -OH, -OCH 3 and -OC 2 H 5 It is a base selected from R 8 R is a group selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an acetyl group, where h is an integer from 1 to 5, i is a number from 5 to 50, and j is a number from 0 to 40. f and g are 0 ≤ f ≤ 200 and 0 ≤ g ≤ 30. However, if g = 0, R 7 is R 6 That is the case. A polyether-modified silicone expressed as such, with a viscosity of 10 to 25,000 mPa·s at 25°C: 0.5 to 15.0 parts by mass, (C) Organic solvent with an SP value of 10.0 to 16.0: 1 to 15 parts by mass, (D) Surfactant: 3 to 50 parts by mass, and (E) Water: 10 to 2,000 parts by mass An amino-modified silicone emulsion composition containing [the specified ingredient].

2. Furthermore, the amino-modified silicone emulsion composition according to claim 1 further contains (F) organic acid: 0.05 to 5 parts by mass.

3. The amino-modified silicone emulsion composition according to claim 1, wherein the average particle size of the emulsion particles is 450 nm or less.

4. (A) The content of amino-modified silicone is (Aw), (B) the content of polyether-modified silicone is (Bw), and (D) the content of surfactant is (Dw). The amino-modified silicone emulsion composition according to claim 1, wherein [(Bw) + (Dw)] / (Aw) is 0.05 to 0.

25.

5. The amino-modified silicone emulsion composition according to claim 1, wherein (A) the amino group equivalent of the amino-modified silicone is (Aae), (B) the content of the polyether-modified silicone is (Bw), and (D) the content of the surfactant is (Dw), and (Aae) / [(Bw)+(Dw)] is 1,000 or more.

6. The amino-modified silicone emulsion composition according to claim 1, wherein the pH at 25°C is 3.5 to 7.

5.

7. A paint additive comprising the amino-modified silicone emulsion composition according to any one of claims 1 to 6.

8. A paint comprising the amino-modified silicone emulsion composition according to any one of claims 1 to 6.

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