Amino-modified silicone emulsion, coating additive and coating

Abstract

The amino-modified silicone emulsion composition contains (A) 100 parts by mass of an amino-modified silicone having a viscosity at 25 DEG C of 3000-150000 mPa.s and an amino equivalent of 5000-30000 g / mol, (B) 0.5-15 parts by mass of a polyether-modified silicone having a viscosity at 25 DEG C of 10-250000 mPa.s, (C) 1.0-15 parts by mass of an organic solvent having an SP value of 10.0-16.0, (D) 3-50 parts by mass of a surfactant, and (E) 10-2000 parts by mass of water, and can be applied to an aqueous resin. The resin composition can suppress shrinkage, has a good appearance after coating, and has excellent stability when blended in a coating material.

Description

Technical Field

[0001] The present invention relates to an amino-modified silicone emulsion, a coating additive, and a coating. Background Art

[0002] In various applications such as furniture, electrical products, transportation equipment such as automobiles and trains, and even various daily necessities, coating with a coating is carried out for the purpose of improving appearance, imparting gloss, and preventing dirt. In coatings, in order not to impair the appearance after coating, coating additives such as a leveling agent and an antifoaming agent are blended. As a coating excellent in leveling property and antifouling property, a composition using an additive containing fluorine in the molecule is generally known (Patent Document 1), but the price of the material is high, and from the viewpoint of environmental problems, a fluorine-free additive is required.

[0003] As a fluorine-free coating additive, polyether-modified silicone is widely used as a coating additive for the purpose of surface leveling property, defoaming property, etc. (Patent Documents 2 and 3). In the coating field, in recent years, in consideration of the environment, a shift from solvent-based resins to water-soluble resins and water-dispersible resins is underway. In water-based resins, compared with solvent-based resins, there are problems that shrinkage and pinholes are likely to occur in appearance. When the compatibility with the resin component in the coating is low, shrinkage occurs during coating and the appearance becomes poor. On the other hand, in order to prevent shrinkage, if a silicone component having a high compatibility with the resin component in the coating is used, the reactivity with the resin increases, and the stability of the coating may be reduced.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2018-070683

[0007] Patent Document 2: Japanese Unexamined Patent Application Publication No. 2013-166830

[0008] Patent Document 3: Japanese Unexamined Patent Application Publication No. 2021-080333 Summary of the Invention

[0009] Problems to be Solved by the Invention

[0010] In view of the above problems of the prior art, an object of the present invention is to provide an amino-modified silicone emulsion, a coating additive, and a coating that can be applied to a water-based resin, can suppress shrinkage, have a good appearance after coating, and are excellent in stability when blended in a coating.

[0011] Means for Solving the Problems

[0012] The inventor of the present invention conducted in-depth research to achieve the above object, and as a result, found that: an amino-modified silicone emulsion composition containing the following components (A) to (E) can solve the above problems, and thus completed the present invention.

[0013] Therefore, the present invention provides the following inventions.

[0014] 1. An amino-modified silicone emulsion composition, comprising:

[0015] (A) 100 parts by mass of an amino-modified silicone represented by the following average composition formula (I), having a viscosity at 25 °C of 3000 to 150000 mPa·s and an amino equivalent of 5000 to 30000 g / mol:

[0016] [Chemical Formula 1]

[0017]

[0018] [In the formula, R 1 are each independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R 2 are each independently a group represented by the general formula (1), R 3 are each independently selected from R 1 , R 2 , -OH, -OCH3, and -OC2H5, and a, b, c, d, and e are numbers within the ranges of 2 ≤ a ≤ 10, 100 ≤ b ≤ 2000, 0 ≤ c ≤ 50, 0 ≤ d ≤ 5, and 0 ≤ e ≤ 5. However, when c = 0, R 3 is R 2 .

[0019] -R 4 -(NH-R 5 ) p -NH2(1)

[0020] R 4 and R 5 are each independently a divalent organic group having 1 to 6 carbon atoms, and p is 0 or 1.]

[0021] (B) 0.5 to 15.0 parts by mass of a polyether-modified silicone represented by the following average composition formula (II), having a viscosity at 25 °C of 10 to 25000 mPa·s:

[0022] [Chemical Formula 2]

[0023]

[0024] [In the formula, R 1 are each independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R 6are each independently a monovalent organic group represented by the general formula (3),

[0025] -C h H 2h O(C2H4O) i (C3H6O) j R 8 (3)

[0026] R 7 is selected from R 1 、R 6 、-OH, -OCH3 and -OC2H5, R 8 is selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and an acetyl group, h is an integer of 1 to 5, i is a number of 5 to 50, and j is a number of 0 to 40. f and g are 0 ≤ f ≤ 200, 0 ≤ g ≤ 30. However, when g = 0, R 7 is R 6 .]

[0027] (C) An organic solvent having an SP value of 10.0 to 16.0: 1 to 15 parts by mass,

[0028] (D) A surfactant: 3 to 50 parts by mass, and

[0029] (E) Water: 10 to 2000 parts by mass.

[0030] 2. The amino-modified silicone emulsion composition according to 1, which further contains (F) an organic acid: 0.05 to 5 parts by mass.

[0031] 3. The amino-modified silicone emulsion composition according to 1 or 2, wherein the average particle diameter of the emulsion particles is 450 nm or less.

[0032] 4. The amino-modified silicone emulsion composition according to any one of 1 to 3, wherein when the content of (A) the amino-modified silicone is (Aw), the content of (B) the polyether-modified silicone is (Bw), and the content of (D) the surfactant is (Dw), [(Bw)+(Dw)] / (Aw) is 0.05 to 0.25.

[0033] 5. The amino-modified silicone emulsion composition according to any one of 1 to 4, wherein when the amino equivalent of (A) the amino-modified silicone is (Aae), the content of (B) the polyether-modified silicone is (Bw), and the content of (D) the surfactant is (Dw), (Aae) / [(Bw)+(Dw)] is 1000 or more.

[0034] 6. The amino-modified silicone emulsion composition according to any one of 1 to 5, wherein the pH at 25 °C is 3.5 to 7.5.

[0035] 7. A coating additive comprising the amino-modified silicone emulsion according to any one of 1 to 6.

[0036] 8. A coating comprising the amino-modified silicone emulsion according to any one of 1 to 6.

[0037] Effects of the Invention

[0038] The amino-modified silicone emulsion composition of the present invention inhibits shrinkage after coating, has a good appearance after coating, and is excellent in stability when compounded in a coating, and is suitable as an aqueous coating additive and for use in compounding with a coating. Detailed Description of the Invention

[0039] The present invention will be described in detail below. Hereinafter, the "amino-modified silicone emulsion composition" will sometimes be simply referred to as "composition".

[0040] [Component (A)]

[0041] Component (A) of the present invention is an amino-modified silicone represented by the following average composition formula (I), having a viscosity of 3000 to 150000 mPa·s at 25°C and an amino equivalent of 5000 to 30000 g / mol, and one kind can be used alone or two or more kinds can be used in combination.

[0042] [Chemical Formula 3]

[0043]

[0044] [In the formula, R 1 are each independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 2 are each independently a group represented by the general formula (1)

[0045] -R 4 -(NH-R 5 ) p -NH2 (1)

[0046] (R 4 and R 5 are each independently a divalent organic group having 1 to 6 carbon atoms, and p is 0 or 1.)

[0047] represents a group, and R 3 are each independently a group selected from R 1 , R 2 , -OH, -OCH3, and -OC2H5, and a, b, c, d, and e are numbers within the range of 2 ≤ a ≤ 10, 100 ≤ b ≤ 2000, 0 ≤ c ≤ 50, 0 ≤ d ≤ 5, and 0 ≤ e ≤ 5. However, when c = 0, R 3 is R2 .]

[0048] R 1 are each independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. As R 1 , for example, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, tetradecyl, octadecyl; alkenyl groups such as vinyl, allyl, 5-hexenyl, oleyl; aryl groups such as phenyl, tolyl, naphthyl, etc. Among them, methyl, long-chain (6 to 20 carbon atoms) alkyl groups, and phenyl groups are preferred, and methyl and phenyl are more preferred.

[0049] R 2 are each independently a group represented by the general formula (1)

[0050] -R 4 -(NH-R 5 ) p -NH2(1)

[0051] (wherein R 4 and R 5 are each independently a divalent organic group having 1 to 6 carbon atoms, and p is 0 or 1).

[0052] Examples of the divalent organic group having 1 to 6 carbon atoms include

[0053] divalent hydrocarbon groups such as alkylene, alkenylene, and arylene. Examples of the group represented by the general formula (1) include 2-aminoethyl, 3-aminopropyl, 6-aminohexyl, N-(2-aminoethyl)-3-aminopropyl, N-(3-aminopropyl)-3-aminopropyl, N-(2-aminoethyl)-6-aminohexyl, etc. Among them, 3-aminopropyl or N-(2-aminoethyl)-3-aminopropyl is preferred from the viewpoint of ease of obtaining raw materials, etc.

[0054] R 3 are each independently a group selected from R 1 , R 2 , -OH, -OCH3, and -OC2H5, provided that when c = 0, R 3 is R 2 .

[0055] a satisfies 2 ≤ a ≤ 10, preferably 2 ≤ a ≤ 5, and more preferably a = 2. If a is greater than 10, the viscosity of the amino-modified silicone is excessively reduced and the emulsifiability is reduced.

[0056] b is in the range of 100 ≤ b ≤ 2000, preferably 300 ≤ b ≤ 1800, more preferably 500 ≤ b ≤ 1600. If b is less than 100, the gloss after coating decreases when making the coating additive. If b exceeds 2000, the viscosity of the amino-modified silicone increases excessively and the emulsifiability decreases.

[0057] c is in the range of 0 ≤ c ≤ 50, preferably 1 ≤ c ≤ 30, more preferably 1 ≤ c ≤ 20, and further 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 coating decreases. However, in the case of R 3 = R 2 , when c is less than 1, c can be 0. On the other hand, if c is greater than 50, the amount of amino groups in the amino-modified silicone is too large and the stability when mixed with the coating decreases.

[0058] d is in the range of 0 ≤ d ≤ 5, preferably d = 0. If d is greater than 5, the viscosity of the amino-modified silicone decreases excessively and the emulsifiability deteriorates.

[0059] e is in the range of 0 ≤ e ≤ 5, preferably e = 0. If e is greater than 5, the viscosity of the amino-modified silicone decreases excessively and the emulsifiability deteriorates.

[0060] The viscosity of the component (A) at 25°C is 3000 to 150000 mPa·s, preferably 5000 to 120000 mPa·s, more preferably 6000 to 110000 mPa·s, and further preferably 10000 to 100000 mPa·s. If the viscosity is less than the lower limit value above, the gloss after coating decreases when making the coating additive. If the viscosity is 6000 mPa·s or more, the shrinkage after coating is further suppressed. In addition, if it exceeds the upper limit value above, the emulsifiability deteriorates. It should be noted that in the present invention, the viscosity is the value measured at 25°C using a BM-type viscometer (for example, manufactured by Tokyo Keiki Co., Ltd.). Furthermore, according to the viscosity, the rotor, rotation speed, and rotation time are appropriately selected based on conventional methods.

[0061] (A) The amino equivalent weight of the component 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 equivalent weight is less than the above lower limit value, the amount of amino groups is excessive, and the stability during mixing with the coating decreases. On the other hand, if the amino equivalent weight exceeds the above upper limit value, since the amount of amino groups is too small, the hydrophilicity that should be imparted by the amino-modified silicone is insufficient, and thus the emulsifiability deteriorates. It should be noted that the amino equivalent weight in the present invention is the number of grams of the amino-modified silicone that can be neutralized by 1 mole of hydrochloric acid. Theoretically, it is the molecular weight / number of nitrogen atoms. The amino equivalent weight can be measured by a neutralization titration method, for example, using an automatic titrator manufactured by Hiranuma Sangyo Co., Ltd. More specifically, it can be measured by the following method. Dissolve the target amino-modified silicone in a solvent in which toluene / IPA is mixed at a mass ratio of 1 / 1, and titrate with hydrochloric acid using an automatic titrator until the end point of pH = 7 to measure the amino equivalent weight. Calculate the amino equivalent weight as the molecular weight of the silicone per 1 mole of amino group, and calculate using the following formula.

[0062] Amino equivalent weight (g / mol) = {[Sample amount (g)] × 1000} / {[Hydrochloric acid equivalent concentration (N)] × [Hydrochloric acid titration volume (mL)] × [Hydrochloric acid titration factor (F)]}

[0063] (A) The amino-modified silicone can be easily obtained by a known synthesis method. For example, as described in the examples of International Publication WO2021 / 1320571, in the presence of a catalyst such as alkali metal hydroxide and tetramethylammonium hydroxide, cyclic siloxanes such as octamethylcyclotetrasiloxane, and 3-aminopropyldiethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane, or their hydrolyzates, and a compound selected from hexamethyldisiloxane, dimethylorganosilicon represented by the following formula (2), etc. are subjected to an equilibration reaction to obtain it.

[0064] [Chemical formula 4]

[0065]

[0066] (In the formula, x is 1 to 100.)

[0067] Furthermore, x is 1 to 100, preferably 3 to 50, and more preferably 3 to 20.

[0068] [Component (B)]

[0069] The component (B) of the present invention has the following average compositional formula (II)

[0070] [Chemical formula 5]

[0071]

[0072] [In the formula, R 1 independently represents an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 6 independently represents a monovalent organic group represented by the general formula (3)

[0073] -C h H 2h O(C2H4O) i (C3H6O) j R 8 (3)

[0074] ; R 7 is a group selected from R 1 , R 6 , -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; h is an integer of 1 to 5, i is a number of 5 to 50, and j is a number of 0 to 40. f and g satisfy 0 ≤ f ≤ 200 and 0 ≤ g ≤ 30. However, when g = 0, R 7 is R 6 .]

[0075] represents a polyether-modified silicone having a viscosity of 10 to 25000 mPa·s at 25°C, and one kind can be used alone or two or more kinds can be used in combination.

[0076] R 1 independently represents an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. For example, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, tetradecyl, and octadecyl can be mentioned; alkenyl groups such as vinyl, allyl, 5-hexenyl, and oleyl; aryl groups such as phenyl, tolyl, and naphthyl. Among them, methyl, long-chain (6 to 20 carbon atoms) alkyl groups, and phenyl groups are preferred, and methyl and phenyl groups are more preferred.

[0077] R 6 independently represents a monovalent organic group represented by the general formula (3)

[0078] -C h H 2h O(C2H4O) i (C3H6O) j R 8 (3)

[0079] ; R 8 is a hydrogen atom or a group selected from an alkyl group having 1 to 6 carbon atoms and an acetyl group. As R 8Specific examples thereof are alkyl groups such as hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group or acetyl group. In addition, h is an integer of 1 to 5, preferably 2 to 4, i is a number of 5 to 50, preferably 5 to 35, more preferably 5 to 30. The j / i of component (B) is preferably 0 to 2.0, more preferably 0.05 to 1.5, further preferably 0.25 to 1.3, and particularly preferably 0.50 to 1.2.

[0080] The HLB value of component (B) is preferably 3 to 15, more preferably 4 to 13, and further preferably 4.5 to 10. In addition, the HLB value in the present invention is a value calculated by the Griffin method.

[0081] R 7 is selected from R 1 、R 6 、-OH, -OCH3 and -OC2H5. When g = 0, R 7 is R 6 .

[0082] f is 0 ≤ f ≤ 200, preferably 0 ≤ f ≤ 100, more preferably 0 ≤ f ≤ 70. g is 0 ≤ g ≤ 30, preferably 0 ≤ g ≤ 20, more preferably 0 ≤ g ≤ 10. However, when g = 0, R 7 is R 6 .

[0083] The viscosity of component (B) at 25°C is 10 to 25000 mPa·s, preferably 100 to 20000 mPa·s, more preferably 200 to 10000 mPa·s.

[0084] The content of component (B) is 0.1 to 15.0 parts by mass, preferably 0.2 to 10 parts by mass, more preferably 0.4 to 5.0 parts by mass, and further preferably 0.6 to 4.0 parts by mass with respect to 100 parts by mass of component (A). If the amount of component (B) is too small, shrinkage is likely to occur after coating. If the amount of component (B) is too large, the stability during coating compounding decreases.

[0085] [(C) component]

[0086] Component (C) of the present invention is an organic solvent with an SP value of 10.0 to 16.0, and one kind can be used alone or two or more kinds can be used in combination. The so-called SP value is the solubility parameter, which is a characteristic value proposed by Hildebrand that represents the solubility coefficient and is a measure of the miscibility between liquids. As such an organic solvent, alcohol compounds, ketone compounds, ester compounds, ether compounds, diol compounds, etc. can be cited. Specifically, 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-pentanediol monoisobutyrate, ethylene glycol, propylene glycol, 1,3-butanediol, etc. can be exemplified. Among them, propylene glycol monomethyl ether, ethylene glycol, and 1,3-butanediol are preferred.

[0087] The SP value of component (C) is more preferably 11.0 to 15.5, and further preferably 12.0 to 15.0. When the SP value is less than 10.0 or greater than 16.0, it is difficult to prepare the emulsion, or the emulsion stability during emulsification decreases, and the appearance and stability during paint compounding deteriorate.

[0088] The content of component (C) is 1 to 15 parts by mass, preferably 1.0 to 15 parts by mass, more preferably 1.5 to 12 parts by mass, and further preferably 2.0 to 10 parts by mass based on 100 parts by mass of component (A). If the amount of component (C) is too small, the compatibility with the resin component in the paint decreases, and poor appearance after coating is likely to occur. If the amount of component (C) is too large, the emulsion stability decreases.

[0089] [Component (D)]

[0090] Component (D) of the present invention is a surfactant, and one kind can be used alone or two or more kinds can be used in combination. There is no particular limitation on the surfactant, and nonionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants, etc. can be cited.

[0091] As nonionic surfactants, for example, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerol fatty acid esters, polyoxyethylene glycerol fatty acid esters, polyglycerol fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid esters, polyoxyethylene alkyl amines, polyoxyethylene fatty acid amides, polyoxyethylene modified organopolysiloxanes, polyoxyethylene polyoxypropylene modified organopolysiloxanes, etc. can be cited.

[0092] As an anionic surfactant, examples include alkyl sulfates such as sodium dodecyl sulfate, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl benzene sulfonates, polyoxyethylene alkyl phenyl ether sulfonates, alkyl diphenyl ether disulfonates, alkane sulfonates, N-acyl taurates, dialkyl sulfosuccinates, monoalkyl sulfosuccinates, polyoxyethylene alkyl ether sulfosuccinates, fatty acid salts, polyoxyethylene alkyl ether carboxylates, N-acyl amino acid salts, monoalkyl phosphate salts, dialkyl phosphate salts, polyoxyethylene alkyl ether phosphate salts, etc.

[0093] As a cationic surfactant, examples include alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, polyoxyethylene alkyl dimethyl ammonium salts, dioxyethylene alkyl methyl ammonium salts, trioxyethylene alkyl ammonium salts, alkyl benzyl dimethyl ammonium salts, alkyl pyridinium salts, monoalkyl amine salts, monoalkyl amide amine salts, etc.

[0094] As an amphoteric surfactant, examples include alkyl dimethyl amine oxides, alkyl dimethyl carboxybetaines, alkyl acylaminopropyl dimethyl carboxybetaines, alkyl hydroxy sulfobetaines, alkyl carboxymethyl hydroxyethyl imidazolinium betaines, etc.

[0095] As the component (D), a nonionic surfactant is more preferably used, and polyoxyethylene alkyl ether and polyoxyethylene polyoxypropylene alkyl ether are further preferably used. Poly(oxyethylene) secondary alkyl ether in which an EO chain is added to the hydroxyl group of a linear secondary alcohol is particularly preferably used.

[0096] The HLB value of the nonionic surfactant as the component (D) is preferably 9.0 to 17.0, more preferably 11.0 to 16.0, and further preferably 12.0 to 15.0.

[0097] The content of the component (D) is 3 to 50 parts by mass, preferably 5 to 30 parts by mass, more preferably 6 to 15 parts by mass, and further preferably 7 to 10 parts by mass with respect to 100 parts by mass of the component (A). If the amount of the component (D) is too small, shrinkage is likely to occur after coating. If the amount of the component (D) is too large, the stability during coating compounding decreases.

[0098] [Component (E)]

[0099] In the composition of the present invention, (E) water is compounded. The content of water is 10 to 2000 parts by mass, preferably 30 to 1000 parts by mass with respect to 100 parts by mass of the component (A).

[0100] [Component (F) Organic acid]

[0101] (F) The component is an organic acid, and one kind or two or more kinds can be appropriately combined and used alone. Specifically, monocarboxylic acids, dicarboxylic acids, hydroxycarboxylic acids, aromatic carboxylic acids, acidic amino acids, etc. can be cited. More specifically, monocarboxylic acids such as acetic acid, propionic acid, and octanoic 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; acidic amino acids such as glutamic acid and aspartic acid.

[0102] When compounding the (F) component, the content is 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass, more preferably 0.2 to 1 part by mass, relative to 100 parts by mass of the (A) component.

[0103] From the aspects of emulsion stability and suppression of separation, it is preferred that the average particle diameter of the emulsified particles of the composition of the present invention is 450 nm or less, more preferably 400 nm or less, and further preferably 350 nm or less. If the average particle diameter is larger than 450 nm, the emulsion stability is low, and separation may occur immediately. There is no limitation on the lower limit of the average particle diameter. For example, it can be set to 80 nm. Furthermore, the average particle diameter of the emulsified particles in the present invention is the particle diameter at the volume cumulative value of 50% in the particle size distribution obtained by the laser diffraction scattering method. As long as it is a device using the laser diffraction scattering method, there is no particular limitation. For example, LA960 manufactured by HORIBA can be used.

[0104] When the content of the (A) amino-modified silicone in the composition of the present invention is set as (Aw), the content of the (B) polyether-modified silicone is set as (Bw), and the content of the (D) surfactant is set as (Dw), [(Bw)+(Dw)] / (Aw) is preferably 0.05 to 0.25. More preferably 0.07 to 0.20, and further preferably 0.08 to 0.15. By making [(Bw)+(Dw)] / (Aw) 0.05 or more, the emulsion stability is further improved. By making it 0.25 or less, the stability during compounding in the coating is further improved. Furthermore, w is mass.

[0105] When the amino equivalent of the (A) amino-modified silicone is set as (Aae), the content of the (B) polyether-modified silicone is set as (Bw), and the content of the (D) surfactant is set as (Dw), (Aae) / [(Bw)+(Dw)] is preferably 1000 or more, more preferably 1200 or more, and further preferably 1600 or more. By making (Aae) / [(Bw)+(Dw)] 1000 or more, the stability during compounding in the coating is further improved. There is no particular limitation on the upper limit. For example, it can be set to 4000 or less, preferably 3000 or less. Furthermore, w is mass.

[0106] The pH of the composition of the present invention at 25°C is preferably 3.5 to 7.5, more preferably 3.7 to 7.0, and still more preferably 4.0 to 6.5. Further, in the present invention, the pH is the value measured with a pH meter (LAQUA manufactured by HORIBA) for the emulsion at 25°C.

[0107] [Manufacturing Method]

[0108] The composition of the present invention can be prepared, for example, by mixing the component (E) with the components (A), (B), (C), and (D) and emulsifying and dispersing them according to a conventional method. Among them, an oil-in-water droplet (O / W type) emulsion is preferred. In addition, by further diluting with water in the emulsion, it can be used for the uses described later. The amount of water used for dilution is not particularly limited and can be appropriately adjusted according to the use.

[0109] As a method for obtaining an emulsion containing an amino-modified silicone, there is also a so-called emulsion polymerization method in which the raw material of the amino-modified silicone is emulsified and dispersed in water using a surfactant, then a catalyst is added and polymerization is carried out in the emulsion. However, in the present invention, it is preferred to carry out an equilibration reaction of a cyclic silicone such as octamethylcyclotetrasiloxane, and 3-aminopropyldiethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane, or a hydrolyzate thereof, and a compound selected from hexamethyldisiloxane, dimethyl silicone represented by the above formula (2), etc. as other raw materials, so as to obtain the component (A), and then mix it with the components (B), (C), (D), and optionally the component (F), and emulsify and disperse it in water according to a conventional method to prepare an emulsion composition.

[0110] An example of the details of the emulsification formulation is as follows. For example, in a mixing device: COMBI MIX (PRIMIX Corporation), the component (A) amino-modified silicone, the component (B) polyether-modified silicone, the component (C) organic solvent, the component (D) surfactant, and a part of the component (E) water are compounded, and emulsification is carried out at 500 to 5000 rpm with a homogeneous mixer (a stirrer using the rotation of a rotor inside a stator) or DISPER (a stirrer using the rotation of a toothed blade) at 500 to 5000 rpm and a rotor at 5 to 50 rpm. After all emulsification, it is stirred at 500 to 5000 rpm with DISPER and a rotor at 5 to 50 rpm for 15 to 180 minutes until a specified particle size is obtained, then the remaining component (E) water is added, and it is diluted at 2000 to 3000 rpm with a homogeneous mixer to prepare an emulsion of the amino-modified silicone of the present invention.

[0111] The temperature during emulsification is not particularly limited, preferably 0 to 80 °C, more preferably 10 to 60 °C. Emulsification is easier at a temperature of 10 to 60 °C, and the resulting emulsion tends to be more stable. If the amino-modified silicone emulsion is heated at 70 to 80 °C for 1 to 30 hours, the particle size may sometimes decrease or the viscosity may decrease. Therefore, in the production of the amino-modified silicone emulsion, a heating step at 70 to 80 °C can be introduced according to the target particle size and viscosity. During emulsification, the pressure can be not only normal pressure, but also reduced pressure or increased pressure. When emulsification is carried out under reduced pressure or increased pressure, air bubbles are less likely to be mixed in, and effective emulsification can be achieved. The pressure in the case of reduced pressure is preferably higher than the vapor pressure of the raw materials that do not volatilize. In addition, the emulsification time is not particularly specified and can be set to the time required to achieve the target particle size. Generally, it is appropriately selected within 30 to 360 minutes.

[0112] There is no particular limitation on the emulsifier used during emulsification as long as it can stir the raw materials and the emulsification composition. It is possible to use a colloid mill (IKA, PUC, Nippon Seiki Seisakusho, IWAKI CO., LTD) having a stirring section composed of a rotor and a stator, a high-shear mixer (Silverson, PRIMIX), a homogeneous mixer (PRIMIX), HOMODISPER (PRIMIX), AGI-HOMO MIXER (PRIMIX), COMBIMIX (PRIMIX), which is a three-screw type dispersion kneader combining HOMO MIXER, HOMO DISPER, and ANCHOR MIXER, HAAKE Mini LabII (Thermo scientific), MC15, MC5 (Leo-Lab), etc.

[0113] In the composition of the present invention, in addition to the above components (A) to (F), various optional components can be blended in an appropriate amount as needed within the scope that does not impair the object of the present invention. Examples of such optional components include silicone components other than components (A) and (B), additives, and the like.

[0114] Specific examples of the silicone components other than components (A) and (B) include silicone oils such as dimethyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, and alkyl-modified silicone oil. When blending silicone components other than components (A) and (B), the amount is preferably 0.5 to 10 parts by mass relative to 100 parts by mass of component (A).

[0115] As additives, for example, protective colloid agents, thickeners, antifreezing agents, preservatives, rust inhibitors, antioxidants, fragrances, ultraviolet absorbers, antibacterial agents, curing catalysts, organic powders, inorganic powders, dyes, fillers, etc. can be cited. One of them can be used alone or an appropriate amount of two or more of them can be used in combination. Even without fluorine, the desired effects can be achieved. When these are added, the amount is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 1 part by mass, based on 100 parts by mass of the component (A).

[0116] [Coating Additives and Coatings]

[0117] In addition, the emulsion of the amino-modified organosilicon of the present invention can also be used as a coating additive. For example, the emulsion of the amino-modified organosilicon can be preferably compounded in the coating in an amount of 0.1 to 30% by mass, more preferably 0.5 to 20% by mass. If the content is above the above lower limit value, leveling properties can be imparted. On the other hand, if the content is below the above upper limit value, the effect of leveling properties is small and the appearance may be poor after coating. In addition, a coating compounded with the emulsion of the above amino-modified organosilicon can be prepared.

[0118] Examples

[0119] Examples and comparative examples are shown below to specifically illustrate the present invention, but the present invention is not limited by the following examples. It should be noted that when the compounding amount of a compounded product name is described, it is the compounding amount of the compounded product.

[0120] The following shows the measurement methods.

[0121] Average particle size: The value measured by diluting the amino-modified organosilicon emulsion with water about 10 times and using a laser diffraction particle size analyzer (LA960 manufactured by HORIBA, Ltd.) (volume cumulative value 50% in the particle size distribution).

[0122] pH: The value measured by using a pH meter (LAQUA manufactured by HORIBA, Ltd.) for the amino-modified organosilicon emulsion at 25°C.

[0123] Viscosity: The value measured by using a BM type viscometer (manufactured by Tokyo Keiki Co., Ltd.) under the condition of 25°C.

[0124] Amino equivalent: The value measured by using an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd.) by the following method.

[0125] Dissolve the target amino-modified organosilicon in a solvent in which toluene / IPA is mixed at a mass ratio of 1 / 1, and titrate with hydrochloric acid using an automatic titrator to the end point of pH = 7, thereby measuring the amino equivalent. The amino equivalent is calculated as the molecular weight of the organosilicon per 1 mole of amino group and calculated by the following formula.

[0126] Amino equivalent (g / mol) = {([Sample amount (g)] × 1000)} / {[Hydrochloric acid equivalent concentration (N)] × [Hydrochloric acid titration volume (mL)] × [Hydrochloric acid titration factor (F)]}

[0127] The following substances were used for each component.

[0128] (A) Amino-modified silicone

[0129] (A) Amino-modified silicone represented by the following average composition formula

[0130] (A-1)

[0131] [Chemical formula 6]

[0132]

[0133] Viscosity: 74000 mPa·s, amino equivalent: 20000 g / mol

[0134] (A-2)

[0135] [Chemical formula 7]

[0136]

[0137] Viscosity: 32000 mPa·s, amino equivalent: 19000 g / mol (A-3)

[0138] [Chemical formula 8]

[0139]

[0140] Viscosity: 5000 mPa·s, amino equivalent: 12000 g / mol (B) Polyether-modified silicone

[0141] Polyether-modified silicone (B-1) represented by the following average composition formula

[0142] [Chemical formula 9]

[0143]

[0144] X = C3H6O(C2H4O) 23 (C3H6) 23 C4H9

[0145] Viscosity: 15000 mPa·s

[0146] HLB: 5.8

[0147] (B-2)

[0148] [Chemical formula 10]

[0149]

[0150] X = C3H6O(C2H4O) 23 (C3H6O) 23 C4H9

[0151] Viscosity: 1600 mPa·s

[0152] HLB: 6.2

[0153] (B - 3)

[0154] [Chemical formula 11]

[0155]

[0156] Y = C3H6O(C2H4O) 24 (C3H6O)6CH3

[0157] Viscosity: 1300 mPa·s

[0158] HLB: 9.5

[0159] (C) Component

[0160] (C - 1): Ethylene glycol, SP value: 14.2

[0161] (C - 2): 1,3 - Butanediol, SP value: 14.2

[0162] (C - 3): Butyl acetate, SP value: 8.5, Comparative product

[0163] (D) Surfactant

[0164] (D - 1): Poly(oxyethylene) secondary alkyl ether [Softanol 90 (trade name): manufactured by Nippon Shokubai Co., Ltd.], HLB value 13.3

[0165] (D - 2): Polyoxyethylene tridecyl ether [Newcol 1310 (trade name): manufactured by Nippon Emulsion Co., Ltd.], HLB value 13.7

[0166] (F) Organic acid

[0167] (F - 1): Acetic acid

[0168] [Example 1]

[0169] (A-1) Amino-modified silicone: 100 parts by mass, (B-1) Polyether-modified silicone: 2.78 parts by mass, (C-1) Ethylene glycol: 5.56 parts by mass, (D-1) Softanol 90: 10.56 parts by mass, (E) Ion-exchanged water: 158.58 parts by mass, (F-1) Acetic acid: 0.31 part by mass were mixed using a homogeneous mixer, emulsified and dispersed to obtain an amino-modified silicone emulsion composition (I-1). The average particle size of the emulsion particles was 310 nm and the pH was 4.4.

[0170] [Example 2]

[0171] (A-2) Amino-modified silicone: 100 parts by mass, (B-1) Polyether-modified silicone: 2.78 parts by mass, (C-1) Ethylene glycol: 5.56 parts by mass, (D-1) Poly(oxyethylene) secondary alkyl ether: 10.56 parts by mass, (E) Ion-exchanged water: 158.58 parts by mass, (F-1) Acetic acid: 0.31 part by mass were mixed using a homogeneous mixer, emulsified and dispersed to obtain an amino-modified silicone emulsion composition (I-2). The average particle size of the emulsion particles was 320 nm and the pH was 4.7.

[0172] [Example 3]

[0173] (A-1) Amino-modified silicone: 100 parts by mass, (B-3) Polyether-modified silicone: 1.11 parts by mass, (C-1) Ethylene glycol: 6.11 parts by mass, (D-1) Poly(oxyethylene) secondary alkyl ether: 9.17 parts by mass, (E) Ion-exchanged water: 161.08 parts by mass, (F-1) Acetic acid: 0.31 part by mass were mixed using a homogeneous mixer, emulsified and dispersed to obtain an amino-modified silicone emulsion composition (I-3). The average particle size of the emulsion particles was 300 nm and the pH was 4.5.

[0174] [Example 4]

[0175] (A-1) Amino-modified silicone: 100 parts by mass, (B-2) Polyether-modified silicone: 0.97 part by mass, (C-1) Ethylene glycol: 5.56 parts by mass, (D-1) Poly(oxyethylene) secondary alkyl ether: 8.33 parts by mass, (E) Ion-exchanged water: 162.53 parts by mass, (F-1) Acetic acid: 0.39 part by mass were mixed using a homogeneous mixer, emulsified and dispersed to obtain an amino-modified silicone emulsion composition (I-4). The average particle size of the emulsion particles was 300 nm and the pH was 4.3.

[0176] [Example 5]

[0177] (A-1) Amino-modified silicone: 100 parts by mass, (B-2) Polyether-modified silicone: 1.39 parts by mass, (C-2) 1,3-Butanediol: 5.56 parts by mass, (D-1) Poly(oxyethylene) secondary alkyl ether: 9.17 parts by mass, (E) Ion-exchanged water: 161.36 parts by mass, (F-1) Acetic acid: 0.31 part by mass were mixed using a homogeneous mixer, emulsified and dispersed to obtain an amino-modified silicone emulsion composition (I-5). The average particle size of the emulsion particles was 290 nm and the pH was 4.4.

[0178] [Example 6]

[0179] (A-3) Amino-modified silicone: 100 parts by mass, (B-2) Polyether-modified silicone: 2.80 parts by mass, (C-1) Ethylene glycol: 5.56 parts by mass, (D-1) Poly(oxyethylene) secondary alkyl ether: 10.00 parts by mass, (E) Ion-exchanged water: 161.36 parts by mass, (F-1) Acetic acid: 0.50 part by mass were mixed using a homogeneous mixer, emulsified and dispersed to obtain an amino-modified silicone emulsion composition (I-6). The average particle size of the emulsion particles was 320 nm and the pH was 4.3.

[0180] [Example 7]

[0181] (A-3) Amino-modified silicone: 100 parts by mass, (B-2) Polyether-modified silicone: 0.95 part by mass, (C-1) Ethylene glycol: 5.56 parts by mass, (D-1) Poly(oxyethylene) secondary alkyl ether: 3.50 parts by mass, (E) Ion-exchanged water: 161.36 parts by mass, (F-1) Acetic acid: 0.50 part by mass were mixed using a homogeneous mixer, emulsified and dispersed 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.

[0182] [Comparative Example 1]

[0183] (A-2) Amino-modified silicone: 100 parts by mass, (D-2) Polyoxyethylene tridecyl ether: 18.67 parts by mass, (E) Ion-exchanged water: 214.33 parts by mass, (F-1) Acetic acid: 0.33 part by mass were mixed using a homogeneous mixer, emulsified and dispersed to obtain an amino-modified silicone emulsion composition (II-1). The average particle size of the emulsion particles was 270 nm and the pH was 4.9.

[0184] [Comparative Example 2]

[0185] (A-1) Amino-modified silicone: 100 parts by mass, (C-1) Ethylene glycol: 5.56 parts by mass, (D-1) Poly(oxyethylene) secondary alkyl ether: 10.56 parts by mass, (E) Ion-exchanged water: 161.36 parts by mass, (F-1) Acetic acid: 0.31 parts by mass were mixed using a homogeneous mixer, emulsified and dispersed to obtain an amino-modified silicone emulsion composition (II-2). The average particle size of the emulsified particles was 330 nm and the pH was 4.5.

[0186] [Comparative Example 3]

[0187] (A-3) Amino-modified silicone: 100 parts by mass, (C-1) Ethylene glycol: 5.56 parts by mass, (D-1) Poly(oxyethylene) secondary alkyl ether: 10.56 parts by mass, (E) Ion-exchanged water: 161.17 parts by mass, (F-1) Acetic acid: 0.50 parts by mass were mixed using a homogeneous mixer, emulsified and dispersed to obtain an amino-modified silicone emulsion composition (II-3). The average particle size of the emulsified particles was 330 nm and the pH was 4.7.

[0188] [Comparative Example 4]

[0189] (A-1) Amino-modified silicone: 100 parts by mass, (B-1) Polyether-modified silicone: 15.28 parts by mass, (C-1) Ethylene glycol: 5.56 parts by mass, (D-1) Poly(oxyethylene) secondary alkyl ether: 10.56 parts by mass, (E) Ion-exchanged water: 146.08 parts by mass, (F-1) Acetic acid: 0.31 parts by mass were mixed using a homogeneous mixer, emulsified and dispersed to obtain an amino-modified silicone emulsion composition (II-4). The average particle size of the emulsified particles was 310 nm and the pH was 4.3.

[0190] [Comparative Example 5]

[0191] (A-2) Amino-modified silicone: 100 parts by mass, (B-1) Polyether-modified silicone: 15.28 parts by mass, (C-1) Ethylene glycol: 5.56 parts by mass, (D-1) Poly(oxyethylene) secondary alkyl ether: 10.56 parts by mass, (E) Ion-exchanged water: 146.08 parts by mass, (F-1) Acetic acid: 0.31 parts by mass were mixed using a homogeneous mixer, emulsified and dispersed to obtain an amino-modified silicone emulsion composition (II-5). The average particle size of the emulsified particles was 300 nm and the pH was 4.4.

[0192] [Comparative Example 6]

[0193] (A-1) Amino-modified silicone: 100 parts by mass, (B-2) Polyether-modified silicone: 15.23 parts by mass, (C-1) Ethylene glycol: 5.56 parts by mass, (D-1) Poly(oxyethylene) secondary alkyl ether: 4.76 parts by mass, (E) Ion-exchanged water: 163.33 parts by mass, (F-1) Acetic acid: 0.31 parts by mass were mixed using a homogeneous mixer, emulsified and dispersed to obtain an amino-modified silicone emulsion composition (II-6). The average particle size of the emulsified particles was 320 nm and the pH was 4.3.

[0194] [Comparative Example 7]

[0195] (A-1) Amino-modified silicone: 100 parts by mass, (B-2) Polyether-modified silicone: 1.39 parts by mass, (C-3) Butyl acetate: 5.56 parts by mass, (D-1) Poly(oxyethylene) secondary alkyl ether: 9.17 parts by mass, (E) Ion-exchanged water: 161.36 parts by mass, (F-1) Acetic acid: 0.31 parts by mass were mixed using a homogeneous mixer, emulsified and dispersed to obtain an amino-modified silicone emulsion composition (II-7). The average particle size of the emulsified particles was 300 nm and the pH was 4.4.

[0196] For the obtained silicone emulsion compositions, the following methods were used to evaluate "emulsion stability", "turbidity after coating", "shrinkage after coating", and "stability during paint compounding". The results are listed in the table together.

[0197] [Emulsion Stability]

[0198] 100 g 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, and then the non-volatile components (105 °C, 3 hours) of the upper layer and the lower layer were measured. The value obtained by dividing the non-volatile component of the upper layer by the non-volatile component of the lower layer is closer to 1, indicating less separation and higher stability, and a value farther from 1 indicates more separation and lower stability.

[0199] [Appearance after Coating]

[0200] 0.2 g of each amino-modified silicone emulsion composition obtained in the examples and comparative examples was mixed into 10 g of the main agent of the waterborne high-durability two-component urethane clear varnish transparent (transparent) (trade name, manufactured by Asahipen Corporation). Further, 2 g of the curing agent of the waterborne high-durability two-component urethane clear varnish transparent (transparent) (trade name, manufactured by Asahipen Corporation) was added and mixed to prepare a coating liquid for evaluation.

[0201] For the coating liquid for evaluation prepared above, after coating an uncoated cardboard (15 cm × 7 cm) with a No. 20 rod coater, it was dried at 25°C for 3 hours. After drying, visually observe the state of the coating film, mark the transparent sample as "○", and mark the sample with confirmed turbidity as "×".

[0202] [Shrinkage after coating]

[0203] 0.2 g of each amino-modified silicone emulsion composition obtained in the examples and comparative examples was mixed in 10 g of the main agent of the water-based high-durability two-component urethane clear varnish transparent (transparent) (trade name, manufactured by Asahipen Corporation). Further, 2 g of the curing agent of the water-based high-durability two-component urethane clear varnish transparent (transparent) (trade name, manufactured by Asahipen Corporation) was added and mixed to prepare a coating liquid for evaluation.

[0204] For the coating liquid for evaluation prepared above, after coating an uncoated cardboard (15 cm × 7 cm) with a No. 20 rod coater, it was dried at 25°C for 3 hours.

[0205] After drying, visually observe the state of the coating film, mark the sample without confirmed shrinkage as "◎", mark the sample with shrinkage confirmed in a part of the coated surface as "〇", and mark the sample with shrinkage confirmed on the entire coated surface as "×".

[0206] [Stability during coating compounding]

[0207] 1.0 g of each amino-modified silicone emulsion composition obtained in the examples and comparative examples was mixed in 10 g of the main agent of the water-based high-durability two-component urethane clear varnish transparent (transparent) (trade name, manufactured by Asahipen Corporation). After mixing, it was stored at 25°C, and the viscosity of the mixed solution was measured after 24 hours. Mark the sample whose viscosity of the mixed solution is 1.1 times or less compared to the viscosity of the main agent of the water-based high-durability two-component urethane clear varnish transparent (transparent) (trade name, manufactured by Asahipen Corporation) alone as "◎", mark the sample in the range greater than 1.1 times and 2.0 times or less as "○", and mark the sample greater than 2.0 times as "×".

[0208] [Table 1]

[0209]

[0210] [Table 2]

[0211]

[0212] As can be seen from the above results, the amino-modified silicone emulsion of the present invention has good coating appearance during coating compounding and does not produce shrinkage. In addition, the stability after coating compounding is also good.

[0213] Industrial applicability

[0214] The amino-modified silicone emulsion of the present invention has good coating appearance during coating compounding and does not produce shrinkage. In addition, the stability after coating compounding is also good. It is suitable as a coating additive.

Claims

1. An amino-modified silicone emulsion composition, comprising: (A) 100 parts by mass of an amino-modified silicone represented by the following average compositional formula (I), having a viscosity at 25 °C of 3,000 to 150,000 mPa·s and an amino equivalent of 5,000 to 30,000 g / mol; [Chemical formula 1] In the formula, R 1 independently represents an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R 2 independently represents a group represented by the general formula (1), R 3 independently represents a group selected from R 1 , R 2 , -OH, -OCH3, and -OC2H5, and a, b, c, d, and e are numbers within the ranges satisfying 2 ≤ a ≤ 10, 100 ≤ b ≤ 2000, 0 ≤ c ≤ 50, 0 ≤ d ≤ 5, and 0 ≤ e ≤ 5. However, when c = 0, R 3 is R 2 . -R 4 -(NH-R 5 ) p -NH2 (1) R 4 and R 5 each independently represents a divalent organic group having 1 to 6 carbon atoms, p is 0 or 1, (B) 0.5 to 15.0 parts by mass of a polyether-modified silicone represented by the following average compositional formula (II), having a viscosity at 25 °C of 10 to 25,000 mPa·s; [Chemical formula 2] In the formula, R 1 independently represents an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 6 independently represents a monovalent organic group represented by the general formula (3). -C h H 2h O(C2H4O) i (C3H6O) j R 8 (3) R 7 is selected from R 1 , R 6 , -OH, -OCH3 and -OC2H5, R 8 is selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and an acetyl group, h is an integer of 1 to 5, i is a number of 5 to 50, j is a number of 0 to 40, f and g are 0 ≤ f ≤ 200, 0 ≤ g ≤ 30, provided that when g = 0, R 7 is R 6 , (C) 1 to 15 parts by mass of an organic solvent having an SP value of 10.0 to 16.0; (D) 3 to 50 parts by mass of a surfactant; and (E) 10 to 2,000 parts by mass of water.

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

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

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

25.

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

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

5.

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

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

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