Waterproof agent composition and fiber treatment agent

Abstract

The present invention is a water repellent composition containing: (A) 100 parts by mass of an organohydrogenpolysiloxane having a viscosity of 5-1,000 mPa * s at 25 DEG C represented by the following average compositional formula (1); (B) 10-100 parts by mass of an organopolysiloxane represented by the following average compositional formula (2) and having a viscosity at 25 DEG C of 300,000 mPa * s or more; (C) 0.5 to 50 parts by mass of a surfactant; (D) 5-100 parts by mass of a condensation reaction catalyst; and (E) 50 to 3,000 parts by mass of water; the ratio (X / Y) of X to Y is within the range of 0.30 < = (X / Y) < = 4.50, where X (mL / g) is the amount of hydrogen generated in terms of the standard state of the component (A), and Y is the ratio (g / h) of g to h of the component (B). Consequently, provided is a water-repellent composition which has an excellent water-repellency imparting effect, is capable of imparting good softness / texture to treated fibers, and is capable of maintaining good water repellency and softness even after washing. # imgabs0 # imgabs1 #

Description

Technical Field

[0001] The present invention relates to a waterproofing agent composition. More specifically, it relates to a waterproofing agent composition that imparts high waterproofness to fibers and a fiber treatment agent containing the composition. Background Art

[0002] Conventionally, as a method for imparting waterproofness to natural fibers, synthetic fibers, leather, paper, etc., fluorine-based compounds have been used. Fiber products treated with a waterproofing agent containing a fluorine compound as a main component have the following characteristics: They have very excellent waterproofness and excellent durability. However, fluorine-based compounds are expensive and require high-temperature treatment to exhibit high waterproofness, so their application range is limited. In addition, since fluorine compounds form a very stable structure, they are not easily decomposed in the environment and also have an accumulative property, so there are environmental problems, and their application has been gradually restricted at home and abroad. Due to the above background, research and development of a waterproofing agent that does not contain fluorine compounds are underway (Patent Document 1).

[0003] As a waterproofing agent that does not contain fluorine compounds, a composition mainly composed of a silicon-based compound such as silicone has been studied. Patent Document 2 studied a composition mainly composed of modified silica, and Patent Document 3 studied a composition formed from organosilane alkoxy oligomers and polyorganosilsesquioxane.

[0004] Silicon-based compounds can impart good softness and handle to fiber products and can also impart waterproofness. Regarding the above-mentioned prior art documents, the waterproofness imparting effect has been improved by optimizing the composition of the silicon-based compound and each component, and the treated fibers exhibit excellent waterproofness. However, there is no description of softness and handle in Patent Documents 1 to 3 above, and there remains a technical problem to be solved of achieving both high waterproofness and softness / handle. In addition, when a waterproofing agent composition is used for a fiber product, it is desired to maintain the waterproofness even after washing. However, the waterproofness after washing is not described in Patent Documents 1 to 3 above.

[0005] In addition, in recent years, cyclic low-molecular-weight siloxanes (octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane) are a concern as environmental load substances, and restrictions are being gradually strengthened in various countries. Therefore, there is a need for a product that suppresses the content of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.

[0006] In addition to the above-mentioned patent documents, Patent Documents 4 and 5 describe the use of a composition containing an amino-modified silicone as a silicon compound as a waterproofing agent, and the waterproofness can be maintained even after repeated washing. However, it is known that amino-modified silicone turns yellow upon heating or long-term storage, and there is a technical problem that the fiber product after treatment with a waterproofing agent containing amino-modified silicone may turn yellow.

[0007] Prior art documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Publication No. 2960304

[0010] Patent Document 2: Japanese Unexamined Patent Application Publication No. 2018-104866

[0011] Patent Document 3: Japanese Patent Publication No. 6573548

[0012] Patent Document 4: Japanese Unexamined Patent Application Publication No. 2016-204565

[0013] Patent Document 5: International Publication No. 2019 / 131456 Summary of the invention

[0014] (1) Technical problem to be solved

[0015] The present invention has been completed in view of the above problems of the prior art, and an object thereof is to provide a waterproofing agent composition having excellent waterproofing effect and capable of imparting good softness / hand feeling to the treated fiber, and maintaining good waterproofness and softness even after washing.

[0016] (2) Technical solution

[0017] To solve the above technical problems, the present invention provides a waterproofing agent composition, characterized by containing:

[0018] (A) An organohydrogenpolysiloxane represented by the following average composition formula (1) and having a viscosity at 25°C of 5 to 1,000 mPa·s, which is 100 parts by mass;

[0019] [Chemical formula 1]

[0020]

[0021] In formula (1), R 1 are each independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R 2 is a hydrogen atom, and R 3 are each independently R 1 , R 2 and a group selected from -OH, -OCH3 and -OC2H5, and a, b, c, d and e are numbers within the range of 0≤a≤10, 0≤b≤100, 0≤c≤500, 0≤d≤5 and 0≤e≤5; wherein, when c = 0, one or more of R 3 are R 2 ;

[0022] (B) An organopolysiloxane having a viscosity of 300,000 mPa·s or more at 25°C represented by the following average compositional formula (2), which is 10 to 100 parts by mass;

[0023] [Chemical formula 2]

[0024]

[0025] In formula (2), R 5 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may be substituted or unsubstituted, and R 6 are each independently a group selected from the above options of R 5 , a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms. f, g, h, and i are values that satisfy the viscosity of the organopolysiloxane being 300,000 mPa·s or more at 25°C, f ≥ 2, h ≥ 1, i ≥ 0, and the ratio of g to h (g / h) is 50 ≤ (g / h) ≤ 1,000;

[0026] (C) A surfactant, which is 0.5 to 50 parts by mass;

[0027] (D) A condensation reaction catalyst, which is 5 to 100 parts by mass; and

[0028] (E) Water, which is 50 to 3,000 parts by mass; and,

[0029] When the hydrogen generation amount of the component (A) converted to 0°C and 101.325 kPa is set as X (mL / g) and the ratio of g to h (g / h) of the component (B) is set as Y, the ratio of X to Y (X / Y) is in the range of 0.30 ≤ (X / Y) ≤ 4.50.

[0030] If it is the waterproofing agent composition of the present invention, the effect of imparting waterproofness is excellent and good softness / hand feeling can be imparted to the treated fiber, and good waterproofness and softness can also be maintained after washing.

[0031] At this time, it is preferable that more than 10% of all the substituents represented by R 1 , R 2 and R 3 of the component (A) are R 2 .

[0032] If it is such a waterproofing agent composition, better waterproofness and softness can be achieved.

[0033] In addition, it is preferable that the ratio of g to h (g / h) of the component (B) is 70 ≤ (g / h) ≤ 950.

[0034] If it is such a waterproofing agent composition, it can have more excellent waterproofness and softness.

[0035] In addition, it is preferable that the component (D) is a compound of one or more metals selected from tin, zinc, bismuth, titanium, iron, zirconium, and aluminum.

[0036] These metal compounds have high catalytic activity as the component (D) and are easily obtained.

[0037] In addition, it is preferable that the contents of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in the waterproofing agent composition are less than 3,000 ppm with respect to 100 parts by mass of the component (B).

[0038] If it is such a waterproofing agent composition, the environmental load is reduced.

[0039] It is preferable that the (C) surfactant contains a cationic surfactant, and more preferably the cationic surfactant is a cationic surfactant represented by the following formulas (C-1) and (C-2):

[0040] (C-1)Q 1 3(CH3)N + ·X - The cationic surfactant represented by,

[0041] (C-2)Q 2 (CH3)3N + ·X - The cationic surfactant represented by,

[0042] wherein Q 1 is a monovalent organic group having 6 to 30 carbon atoms, which may be the same or different, and Q 2 is a monovalent organic group having 17 to 30 carbon atoms, and X is independently a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms.

[0043] If it is such a waterproofing agent composition, the organohydrogenpolysiloxane and the organopolysiloxane can be emulsified and dispersed well in water.

[0044] Preferably: with respect to 100 parts by mass of the component (A), the waterproofing agent composition of the present invention further contains 1 to 50 parts by mass of an (F) polyfunctional isocyanate compound.

[0045] If it is such a waterproofing agent composition, the waterproofness is maintained more excellently.

[0046] In the waterproofing agent composition of the present invention, it is preferable that the content of the fluorine compound is less than 1 part by mass with respect to 100 parts by mass of the component (A).

[0047] From the perspective of reducing environmental load, it is preferably such a waterproofing agent composition.

[0048] In addition, the present invention provides a fiber treatment agent, which is characterized by containing the above waterproofing agent composition.

[0049] If it is such a fiber treatment agent, the effect of imparting waterproofness is excellent, and it can impart good softness / handle to the treated fiber, and can also maintain good waterproofness and softness after washing.

[0050] (III) Beneficial effects

[0051] The waterproofing agent composition of the present invention can impart high waterproofness to the fiber while also imparting good softness / handle to the fiber. In addition, good waterproofness and softness can also be maintained after washing. Detailed implementation manners

[0052] The inventors of the present application and the like conducted earnest research to achieve the above object, and as a result, found that a composition containing the following components (A) to (E) can impart high waterproofness to the fiber while also imparting good softness / handle to the fiber, and thus completed the present invention.

[0053] In particular, (i) by using an organohydrogenpolysiloxane having a reactive group (a hydrogen atom directly bonded to a silicon atom) in the molecule as component (A), the reactive group chemically reacts with the substrate in the presence of a catalyst (component (D)) and bonds firmly; (ii) by setting both the ratio (g / h) of the amount of D units to the amount of T units in component (B) and the ratio (X / Y) of the hydrogen gas generation amount X (mL / g) of component (A) in terms of standard state to this ratio (set as Y) within appropriate ranges, softness and waterproofness can be taken into account. This technical idea was first discovered by the inventors of the present application and the like.

[0054] That is, the present invention is a waterproofing agent composition, which is characterized by containing:

[0055] (A) 100 parts by mass of an organohydrogenpolysiloxane represented by the following average compositional formula (1) and having a viscosity of 5 to 1,000 mPa·s at 25°C;

[0056] [Chemical formula 3]

[0057]

[0058] In formula (1), R 1 are independently unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, R 2 is a hydrogen atom, and R 3 are independently R1 , R 2 and a group selected from -OH, -OCH3 and -OC2H5, where a, b, c, d and e are numbers within the ranges of 0 ≤ a ≤ 10, 0 ≤ b ≤ 100, 0 ≤ c ≤ 500, 0 ≤ d ≤ 5, 0 ≤ e ≤ 5; wherein when c = 0, at least one of the Rs in 3 is R 2 ;

[0059] (B) An organopolysiloxane represented by the following average composition formula (2) and having a viscosity of 300,000 mPa·s or more at 25°C, which is 10 to 100 parts by mass;

[0060] [Chemical formula 4]

[0061]

[0062] In formula (2), the Rs 5 are each independently a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, and the Rs 6 are each independently a group selected from the options of the above Rs 5 , a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms, and f, g, h, and i are values that satisfy the viscosity of this organopolysiloxane being 300,000 mPa·s or more at 25°C, f ≥ 2, h ≥ 1, i ≥ 0, and the ratio of g to h (g / h) is 50 ≤ (g / h) ≤ 1,000;

[0063] (C) A surfactant, which is 0.5 to 50 parts by mass;

[0064] (D) A condensation reaction catalyst, which is 5 to 100 parts by mass; and

[0065] (E) Water, which is 50 to 3,000 parts by mass; and,

[0066] When the hydrogen generation amount of the component (A) converted at 0°C and 101.325 kPa is set as X (mL / g) and the ratio of g to h (g / h) of the component (B) is set as Y, the ratio of X to Y (X / Y) is within the range of 0.30 ≤ (X / Y) ≤ 4.50.

[0067] The present invention will be described in detail below, but the present invention is not limited thereto.

[0068] The waterproofing agent composition of the present invention is characterized in that it contains (A) a specific organohydrogenpolysiloxane, (B) a specific organopolysiloxane, (C) a surfactant, (D) a condensation reaction catalyst, and (E) water. When the hydrogen generation amount of the component (A) converted to 0 °C and 101.325 kPa is set as X (mL / g), and the ratio of g to h (g / h) of the component (B) is set as Y, the ratio of X to Y (X / Y) is in the range of 0.30 ≤ (X / Y) ≤ 4.50. Hereinafter, these components will be described.

[0069] [Component (A)]

[0070] The component (A) of the present invention is an organohydrogenpolysiloxane represented by the following average compositional formula (1) and having a viscosity of 5 to 1,000 mPa·s at 25 °C. One kind can be used alone or two or more kinds can be used in combination.

[0071] [Chemical formula 5]

[0072]

[0073] In formula (1), R 1 are each independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R 2 is a hydrogen atom, and R 3 are each independently R 1 , R 2 and a group selected from -OH, -OCH3, and -OC2H5. a, b, c, d, and e are numbers satisfying the range of 0 ≤ a ≤ 10, 0 ≤ b ≤ 100, 0 ≤ c ≤ 500, 0 ≤ d ≤ 5, and 0 ≤ e ≤ 5; provided that when c = 0, at least one of R 3 is R 2 .

[0074] R 1 are each independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, examples of which include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, tetradecyl, and octadecyl; alkenyl groups such as vinyl, allyl, 5-hexenyl, and oleyl; aryl groups such as phenyl, tolyl, and naphthyl. Among them, methyl, long-chain (having 6 to 20 carbon atoms) alkyl groups, and phenyl are preferred, and methyl is more preferred.

[0075] R 2 is a hydrogen atom, and R 3 are each independently R 1 , R 2 and a group selected from -OH, -OCH3, and -OC2H5. Among them, when c = 0, at least one of R 3 is R 2 . Preferably, R1 and R 2 and R 3 More than 10% of all substituents represented by 2 are R 2 (hydrogen atom), more preferably more than 20% are R 2 (hydrogen atom), still more preferably more than 30% are R

[0076] a is 0 ≤ a ≤ 10, preferably 2 ≤ a ≤ 5, more preferably 2 ≤ a ≤ 3. If a is greater than 10, the viscosity of the organohydrogen polysiloxane will be excessively reduced and the water repellency will deteriorate.

[0077] b is 0 ≤ b ≤ 100, preferably 10 ≤ b ≤ 100, more preferably 20 ≤ b ≤ 90, still more preferably 30 ≤ b ≤ 80. If b is greater than 100, the viscosity of the organohydrogen polysiloxane will be excessively increased and the emulsion stability will deteriorate.

[0078] c is 0 ≤ c ≤ 500, preferably 10 ≤ c ≤ 400, more preferably 20 ≤ c ≤ 200, still more preferably 30 ≤ c ≤ 100. If c is greater than 500, the viscosity of the organohydrogen polysiloxane will be excessively increased and the emulsion stability will deteriorate.

[0079] d is 0 ≤ d ≤ 5, preferably d = 0. If d is greater than 5, the viscosity of the organohydrogen polysiloxane will be excessively reduced and the water repellency will deteriorate.

[0080] e is 0 ≤ e ≤ 5, preferably e = 0. If e is greater than 5, the viscosity of the organohydrogen polysiloxane will be excessively reduced and the water repellency will deteriorate.

[0081] The viscosity of component (A) at 25 °C is 5 to 1,000 mPa·s, more preferably 10 to 250 mPa·s. In addition, the viscosity is a value measured by a BM type viscometer (manufactured by, for example, TOKYO KEIKI INC.). In addition, the rotor, rotation speed, and rotation time are appropriately selected according to the viscosity by a conventional method.

[0082] The hydrogen generation amount of component (A) converted to 0 °C, 101.325 kPa (standard state) is preferably 200 mL / g or more, more preferably 220 mL / g or more, and particularly preferably 250 mL / g or more.

[0083] The hydrogen generation amount is measured in the following manner.

[0084] (Measurement method)

[0085] After weighing 1 g of the sample to be measured into an Erlenmeyer flask, 10 mL of 1-butanol was added and mixed. Then, 20 wt% aqueous NaOH solution was added dropwise, and the amount of hydrogen gas generated at this time (Si-H + H2O → Si-OH + H2↑) was measured.

[0086] The hydrogen gas generation amount X (mL / g) was calculated by the following calculation formula.

[0087] X = [(measured value of hydrogen gas generation amount (mL)) × 273] ÷ [(sample amount (g)) × (273 + temperature at the time of measurement (°C))]

[0088] As the component (A), compounds represented by the following average composition formula can be cited.

[0089] [Chemical formula 6]

[0090]

[0091] In the formula, a to e are the same as a to e above.

[0092] [Chemical formula 7]

[0093]

[0094] Specifically, compounds represented by the following average composition formula can be cited.

[0095] [Chemical formula 8]

[0096]

[0097] The above-mentioned component (A) is an organohydrogenpolysiloxane, which has a reactive group (a hydrogen atom directly bonded to a silicon atom) in its molecule. It is considered that this reactive group reacts with a substrate such as a fiber through the catalyst of the following component (D) and is firmly chemically bonded, thereby enabling the imparting of waterproofness with excellent durability.

[0098] [(Component (B))]

[0099] The component (B) of the present invention is an organopolysiloxane represented by the following average composition formula (2) and having a viscosity of 300,000 mPa·s or more at 25°C.

[0100] [Chemical formula 9]

[0101]

[0102] In formula (2), R 5 are each independently a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, and R 6 are each independently selected from the above R 5groups, hydroxyl groups, or alkoxy groups having 1 to 20 carbon atoms in the options, where f, g, h, and i are values that satisfy the viscosity of the organopolysiloxane at 25 °C being 300,000 mPa·s or more, f ≥ 2, h ≥ 1, i ≥ 0, and the ratio of g to h (g / h) is 50 ≤ (g / h) ≤ 1,000.

[0103] (B) The viscosity of the component is the measured value when measured using a BM-type or BH-type rotational viscometer at 25 °C. For this viscosity, if it is a substance that can be measured in a liquid state, it is directly measured. If it is a substance with too high viscosity to be measured, the 5% or 10% toluene-soluble viscosity is measured. The viscosities of substances that are still too viscous to be measured after dilution with toluene, substances that entangle the rotor of a BM-type or BH-type rotational viscometer and cannot be measured, or substances that are insoluble in toluene and cannot be measured are all 300,000 mPa·s or more.

[0104] R 5 Each independently is a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms. The monovalent organic group having 1 to 20 carbon atoms can be any of linear, branched, or cyclic, and specifically, examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, cycloheptyl, etc.; aryl groups such as phenyl, tolyl, naphthyl, etc.; alkenyl groups such as vinyl, allyl, etc.; or groups obtained by substituting a part of the hydrogen atoms in the structures of these organic groups with halogen atoms or organic groups containing polar groups such as amino, acryloyloxy, methacryloyloxy, epoxy, mercapto, etc. Among them, industrially and in terms of properties, it is desired that more than 80% of R 5 is methyl, and preferably at least one of R 5 contains a phenyl group.

[0105] R 6 Each independently is a group selected from the options of the above R 5 groups, a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms.

[0106] As the alkoxy group having 1 to 20 carbon atoms, it can be any of linear, branched, or cyclic. Specifically, examples include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, decyloxy, dodecyloxy, 2-ethylhexyloxy, etc. Methoxy, ethoxy, propoxy, butoxy, and pentyloxy are preferred, and methoxy, ethoxy, and propoxy are more preferred.

[0107] When there are reactive functional groups in the above average compositional formula (2), these reactive functional groups can react with other compounds. Specifically, when there is an amino group in the above average compositional formula (2), ring-opening reactions can occur with polyoxyalkylene compounds containing an epoxy group and alkyl compounds containing an epoxy group, and acetylation reactions can occur with carboxylic anhydrides such as acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, and benzoic anhydride. In addition, when there is an epoxy group in the above average compositional formula (2), ring-opening reactions can occur with amino group-containing compounds. Additionally, the reactions with the reactive functional groups represented above are not limited to these.

[0108] In the above average compositional formula (2), f, g, h, and i are values that satisfy the condition that the viscosity of the organosiloxane at 25 °C is 300,000 mPa·s or more. For this viscosity, if it is a substance that can be measured in a liquid state, it is directly measured. If it is a substance with too high a viscosity to be measured, the 5% toluene solution viscosity is measured. There are also substances that still have too high a viscosity to be measured after dilution with 5% toluene, substances that entangle the rotor of a BM type or BH type rotational viscometer and cannot be measured, or substances that are insoluble in toluene and cannot be measured. It is more preferable to satisfy the value of 3.5 mPa·s or more for the 5% toluene solution viscosity, and it is further preferable that the viscosity cannot be measured even in the state of a 5% toluene solution. In addition, f ≥ 2, h ≥ 1, i ≥ 0, and the ratio of g to h (g / h) is 50 ≤ (g / h) ≤ 1,000. (g / h) is preferably 70 to 950, more preferably 70 to 500, and particularly preferably 100 to 400.

[0109] Typically, g in the above average compositional formula (2) is 50 or more, preferably 100 or more. However, when the value of h + i is large, the number of crosslinking units increases, so even if g is less than 50, there are cases where the viscosity is 300,000 mPa·s or more.

[0110] The above ratio (g / h) is a parameter that affects softness and water repellency after washing. In the present invention, by setting (g / h) within an appropriate range, both softness and water repellency after washing can be taken into account. If the value of (g / h) is less than 50, the crosslinking density of the component (B) will be excessively increased, resulting in a decrease in the feel and softness when treating the substrate. On the contrary, if the value of (g / h) is greater than 1,000, the water repellency after washing will decrease.

[0111] The component (B) can be obtained, for example, by emulsifying an organopolysiloxane having an OH group at the terminal in the presence of a surfactant and water as described in Japanese Patent Application Laid-Open No. 2016-166324, and further adding a catalyst to cause polymerization.

[0112] As specific examples of the component (B), the following average compositional formulas can be cited, but are not limited thereto. In the following average compositional formulas, f, g, h, i, j, and k are values that satisfy the condition that the viscosity of the organopolysiloxane at 25 °C is 300,000 mPa·s or more, f ≥ 2, h + k ≥ 1, i ≥ 0, and the ratio (g + j) / (h + k) satisfies the relationship 50 ≤ (g + j) / (h + k) ≤ 1,000. In addition, f, g, h, i, j, and k in the following average compositional formulas are defined to be applicable only here.

[0113] [Chemical formula 10]

[0114]

[0115] Specifically, substances represented by the following average compositional formulas can be cited.

[0116] [Chemical formula 11]

[0117]

[0118] In the present invention, it is preferable that: with respect to 100 parts by mass of the component (B), the contents of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) are each less than 3,000 ppm. More preferably less than 2,000 ppm, and particularly preferably less than 1,000 ppm. The lower limit value can be set to 0 ppm.

[0119] There are concerns about these cyclic low-molecular-weight siloxanes as environmental load substances, and thus countries are gradually strengthening restrictions. Therefore, the above-mentioned composition is desired.

[0120] The amounts of D4, D5, and D6 can be determined, for example, in the following manner.

[0121] (Quantitative method)

[0122] Add 0.1 g of the measurement sample to 10 mL of acetone, extract the cyclic low-molecular-weight siloxane into the acetone solution by shaking, and then measure the supernatant acetone solution by gas chromatography. The gas chromatography column used is D8-5MS (manufactured by Agilent Technologies), the column temperature during measurement is 300 °C, and tetradecane is used as the internal standard substance.

[0123] With respect to 100 parts by mass of the component (A), the blending amount of the component (B) is 10 to 100 parts by mass, preferably 20 to 80 parts by mass, more preferably 30 to 75 parts by mass, and further preferably 40 to 70 parts by mass. If it is less than 10 parts by mass, the waterproof property after washing decreases, and if it is more than 100 parts by mass, the feel of the fiber decreases.

[0124] In the present invention, when the hydrogen generation amount of component (A) converted at 0 °C and 101.325 kPa is X (mL / g) and the ratio of g to h of component (B) (g / h) is Y, X / Y is in the range of 0.30 ≤ (X / Y) ≤ 4.50. X / Y is preferably 0.30 ≤ (X / Y) ≤ 3.50, more preferably 0.35 ≤ (X / Y) ≤ 3.40, and particularly preferably 0.50 ≤ (X / Y) ≤ 3.00.

[0125] If (X / Y) is outside the above range, the waterproof property after washing deteriorates, or the softness of the fiber after treatment deteriorates.

[0126] The hydrogen generation amount X of component (A) corresponds to the amount of hydrogen atoms (Si-H groups) directly bonded to silicon atoms in component (A). The hydrogen atoms react with reactive functional groups on the object to be treated such as fibers, and component (A) is chemically bonded to the object to be treated. In addition, Y corresponds to the ratio of the number of D units to the number of T units (D / T ratio) of the organopolysiloxane of component (B).

[0127] In the present invention, by setting the above ratio (X / Y) within an appropriate range, softness and waterproof property can be taken into account. If the value of (X / Y) is less than 0.30, the waterproof property is poor. If the value of (X / Y) is greater than 4.50, the softness and feel during the treatment of substrates such as fibers deteriorate. As described above, in the present invention, by obtaining the balance between the amount of Si-H groups in component (A) and the D / T ratio of the organopolysiloxane of component (B), the waterproof property imparting effect is excellent and good softness / feel can be imparted to the treated fiber.

[0128] [Component (C)]

[0129] The surfactant as component (C) of the present invention is not particularly limited, and examples thereof include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and the like. These can be used alone or in appropriate combination of two or more.

[0130] Examples of the nonionic surfactant include 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 alkylamines, polyoxyethylene fatty acid amides, polyoxyethylene modified organopolysiloxanes, polyoxyethylene polyoxypropylene modified organopolysiloxanes, and the like.

[0131] From the perspective of the stability of the emulsion, when using non-ionic surfactants, it is preferably within the range of HLB value (when using multiple surfactants, it is the HLB value of the whole mixture) of 8.0 to 20.0, more preferably within the range of HLB value of 11.0 to 17.0, and further preferably within the range of HLB value of 12.0 to 16.0. In addition, HLB is the value calculated by the Griffin method.

[0132] When using two surfactants with different HLB values, the HLB value is calculated by the following formula.

[0133] N = N1×W1 + N2×W2

[0134] N: HLB value when using two surfactants with different HLB values

[0135] N1, N2: HLB values of each surfactant

[0136] W1, W2: Mass fractions of each surfactant (W1 + W2 = 1)

[0137] Examples of anionic surfactants include, for example, alkyl sulfates such as sodium lauryl 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.

[0138] Examples of cationic surfactants include, for example, 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.

[0139] Examples of amphoteric surfactants include, for example, alkyl dimethyl amine oxides, alkyl dimethyl carboxybetaines, alkyl amide propyl dimethyl carboxybetaines, alkyl hydroxy sulfobetaines, alkyl carboxymethyl hydroxyethyl imidazolinium salt betaines, etc.

[0140] In the present invention, it is preferred that the (C) surfactant contains a cationic surfactant, and it is particularly preferred that the (C) surfactant contains the cationic surfactants represented by the following formulas (C-1) and (C-2):

[0141] (C-1)Q 1 3(CH3)N + ·X- The cationic surfactant represented by

[0142] (C-2)Q 2 (CH3)3N + ·X - The cationic surfactant represented by

[0143] Q 1 is a monovalent organic group having 6 to 30 carbon atoms, either the same or different. Q 2 is a monovalent organic group having 17 to 30 carbon atoms, and X is independently a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms.

[0144] As specific examples of Q 1 , alkyl groups such as hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, docosyl, cyclohexyl, cycloheptyl, etc. can be mentioned; aryl groups such as phenyl, benzyl, tolyl, naphthyl, etc.; alkenyl groups such as oleyl, etc. Among them, octyl, dodecyl, hexadecyl, and octadecyl are preferred.

[0145] In addition, X - is a halogen ion or a monovalent carboxyl ion having 1 to 6 carbon atoms. Specifically, halogen ions such as Cl - , Br - , I - can be mentioned; carboxyl ions such as HCOO - , CH3COO - , C2H5COO - . Among them, Cl - , Br - , HCOO - , CH3COO - are preferred.

[0146] Q 2 is a monovalent organic group having 17 to 30 carbon atoms, preferably a monovalent organic group having 18 to 28 carbon atoms. When the number of carbon atoms of Q 2 is 17 or more, the compatibility with the cationic surfactant represented by (B-1) is good and the stability of the emulsion is good. When the number of carbon atoms of Q 2 is 30 or less, the emulsifying power as a surfactant is sufficient and a stable emulsion can be obtained, similar to the case of Q 1 . The X 2 of Q - is the same as the X 1 of the above-mentioned Q - .

[0147] (C-1) component specific examples include trihexylmethylammonium chloride, triheptylmethylammonium chloride, trioctylmethylammonium chloride, trinonylmethylammonium chloride, tridecylmethylammonium chloride, trilaurylmethylammonium chloride, trioctylmethylammonium acetate, trilaurylmethylammonium acetate, etc., but are not limited to these.

[0148] As specific examples of the (C-2) component, stearyltrimethylammonium chloride, eicosyltrimethylammonium chloride, docosyltrimethylammonium chloride, stearyltrimethylammonium acetate, eicosyltrimethylammonium acetate, docosyltrimethylammonium acetate, etc. can be cited, but are not limited to these.

[0149] Since the (C-1) component has higher hydrophobicity than the (C-2) component, the contact frequency with the polyorganosiloxane of the (A) and (B) components is high, and an effect of further improving dispersibility can be expected. On the other hand, it is also possible that the hydrophobicity is too high and the emulsifying ability is insufficient. Therefore, it is considered that by simultaneously using the (C-2) component having a higher emulsifying ability than the (C-1) component, the stability of the emulsion can be improved.

[0150] The blending amount of the (C) component is 0.5 to 50.0 parts by mass, preferably 1.0 to 25 parts by mass, more preferably 1.5 to 20 parts by mass, and further preferably 5.0 to 15.0 parts by mass with respect to 100 parts by mass of the (A) component. If the (C) component is too little, emulsification is difficult, and if too much, the waterproof property decreases.

[0151] [(D) component]

[0152] The (D) component of the present invention is a condensation reaction catalyst for promoting the reaction between the hydrogen atom directly bonded to the silicon atom of the (A) component and the reactive functional group on the fiber. The (D) component can be used alone or in combination of two or more appropriately. As the condensation reaction catalyst, various metal compounds such as tin, zinc, bismuth, titanium, zirconium, aluminum, iron, and lead can be cited. Among them, from the viewpoints of high catalyst activity and easy availability, a compound of one or more metals selected from tin, zinc, bismuth, titanium, iron, zirconium, and aluminum is preferred, and a compound of one or more metals selected from tin, zinc, and titanium is more preferred. From the viewpoint of environmental load, a compound of one or more metals selected from zinc and titanium is particularly preferred.

[0153] As the metal compound of the (D) component, it is a salt and / or complex having the above metal ion as the central element, and is preferably selected from at least one of carboxylic acids, ketones, esters, chloride ions, bromide ions, and iodide ions having an alkyl group with 1 to 30 carbon atoms as the counter ion and / or ligand. Among them, as the alkyl group, methyl, isopropyl, butyl, 2-ethylhexyl, octyl, isodecyl, isostearyl, decyl, cetyl, etc. can be cited.

[0154] As specific examples of the component (D), carboxylate metal salts such as tin bis(2-ethylhexanoate), zinc bis(2-ethylhexanoate), zinc laurate, zinc acetate, zirconium acetate, zinc formate, iron bis(2-ethylhexanoate), iron tris(2-ethylhexanoate), zirconium bis(2-ethylhexanoate), zirconium tetrakis(2-ethylhexanoate), bismuth tris(2-ethylhexanoate), and tin versatate can be cited; dialkyltin dicarboxylates and silicate compounds reactants such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis(2-ethylhexanoate), dibutyltin bis(methyl maleate), dibutyltin bis(ethyl maleate), dibutyltin bis(butyl maleate), dibutyltin bis(octyl maleate), dibutyltin bis(tridecyl maleate), dibutyltin bis(benzyl maleate), dibutyltin diacetate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dibutyltin dimethoxide, dibutyltin bis(nonylphenoxide), dibutyltin oxide, dibutyltin bis(acetylacetonate), dibutyltin bis(acetoacetate), the reaction product of dibutyltin oxide and a silicate compound, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dineodecanoate, dioctyltin dineodecanoate, etc.; tetravalent organotin compounds such as the reaction product of dibutyltin oxide and a phthalate; organotitanates such as titanium tetraisopropoxide, titanium tetra-n-butoxide, diisopropoxytitanium bis(acetylacetonate), and diisopropoxytitanium bis(ethyl acetoacetate); organoaluminum compounds such as aluminum tris(acetylacetonate), aluminum tris(ethyl acetoacetate), and diisopropoxyaluminum ethyl acetoacetate; and zirconium compounds such as zirconium tetrakis(acetylacetonate).

[0155] As the component (D), a zinc compound is preferred, and zinc bis(2-ethylhexanoate), zinc laurate, zinc acetate, and zinc formate are particularly preferred.

[0156] The blending amount of the component (D) is 5 to 100 parts by mass, preferably 10 to 80 parts by mass, and more preferably 15 to 60 parts by mass with respect to 100 parts by mass of the component (A). If the amount of the component (D) is less than 5 parts by mass, the waterproof property deteriorates, and if it is more than 100 parts by mass, the flexibility / hand feeling deteriorates.

[0157] [Component (E)]

[0158] The component (E) of the present invention is water. The blending amount of water is 50 to 3,000 parts by mass, preferably 50 to 2,000 parts by mass with respect to 100 parts by mass of the component (A).

[0159] [Component (F)]

[0160] The waterproof agent composition of the present invention may further contain (F) a polyfunctional isocyanate compound.

[0161] The (F) component of the present invention is a polyfunctional isocyanate compound having two or more isocyanate groups in one molecule. As long as it is a compound having two or more isocyanate groups in one molecule, there is no particular limitation, and known substances can be used. The (F) component can be used alone or in combination of two or more. Specifically, examples include toluene diisocyanate, diphenylmethane diisocyanate, m-xylene diisocyanate, α,α,α’,α’-tetramethyl-m-xylene diisocyanate, tetramethylene-1,4-diisocyanate, pentamethylene-1,5-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene-1,6-diisocyanate, lysine diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, polymers of various diisocyanates such as 4,4-dicyclohexylmethane diisocyanate, and polyisocyanates having an isocyanurate structure composed of these. Further examples include polyisocyanates obtained by reacting various diisocyanate compounds as described above with various polyols, polyisocyanates having a biuret structure obtained by reacting a polyisocyanate with water, polyisocyanate compounds having an isocyanurate structure obtained by cyclotrimerizing the above-mentioned diisocyanate, etc., and the polyols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propylene glycol, 1,5-pentanediol, 2-methyl-2,3-butanediol, 1,6-hexanediol, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, 2-ethylhexanediol, 1,2-octanediol, 1,2-decanediol, 2,2,4-trimethylpentanediol, 2-butyl-2-ethyl-1,3-propylene glycol, 2,2-diethyl-1,3-propylene glycol, glycerol, trimethylolpropane, pentaerythritol, polyester polyol, polyether polyol, acryloyl polyol, polyolefin polyol, etc. In addition, polyisocyanates obtained by reacting the above various polyisocyanates with the various polyols as described above can also be used.

[0162] In addition, blocked isocyanate compounds obtained by blocking the isocyanate groups with a blocking agent can also be used. There is no particular limitation on the blocked isocyanate compounds, and known substances can be used. In addition, blocked polyisocyanates can be prepared by reacting various known polyisocyanate compounds with various known blocking agents. Examples of the blocking agent include alcohol-based compounds, alkylphenol-based compounds, phenol-based compounds, active vinyl-based compounds, thiol-based compounds, acid amide-based, acid imide-based, imidazole-based, urea-based compounds, oxime-based compounds, amine-based compounds, imide-based compounds, pyrazole-based compounds, etc.

[0163] With respect to 100 parts by mass of component (A), the blending amount of component (F) is preferably 1 to 50 parts by mass, more preferably 5 to 40 parts by mass, and still more preferably 10 to 40 parts by mass.

[0164] Since component (F) contains isocyanate groups, it can react with various reactive groups to crosslink. The reactive groups (hydrosilyl groups, hydroxyl groups, alkoxy groups, etc.) contained in component (A) and component (B) can react with the isocyanate groups of component (F) to crosslink (chemical bonding). Moreover, it is considered that since isocyanate groups can also react with the reactive groups contained in the substrate to be treated, when the composition contains component (F), a stronger coating film can be formed, thereby improving the waterproof property after repeated washing.

[0165] [Other components]

[0166] The waterproof agent composition of the present invention can be appropriately blended with a solvent, a thickener, a pigment, a dye, a penetrant, an antistatic agent, an antifoaming agent, a flame retardant, an antibacterial agent, a preservative, a crosslinking agent, an adhesion improver, and other silicone oils, silicone resins, acrylic resins, urethane resins, etc. as needed.

[0167] Examples of the solvent include ether solvents such as dibutyl ether, dioxane, and tetrahydrofuran; ketone solvents such as acetone and methyl ethyl ketone (MEK); alcohol solvents such as methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol, 2-methyl-2,3-butanediol, 1,6-hexanediol, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, 2-ethyl-hexanediol, 1,2-octanediol, 1,2-decanediol, 2,2,4-trimethylpentanediol, 2-butyl-2-ethyl-1,3-propanediol, and 2,2-diethyl-1,3-propanediol; and aromatic solvents such as toluene and xylene. These solvents can be used alone or two or more of them can be used simultaneously.

[0168] (Fluorine compound)

[0169] In the waterproof agent composition of the present invention, with respect to 100 parts by mass of component (A), the fluorine compound is preferably less than 1 part by mass, more preferably less than 0.5 part by mass, and still more preferably less than 0.1 part by mass. It is particularly preferred not to contain a fluorine compound, but sometimes a trace amount of fluorine compound such as an impurity contained in the raw material may be accidentally contained.

[0170] The water repellent composition of the present invention preferably contains 10 parts by mass of an amino-modified silicone, more preferably less than 5 parts by mass, and even more preferably less than 1 part by mass, relative to 100 parts by mass of the component (A). It is particularly preferred that no amino-modified silicone is contained, but it may sometimes be accidentally contained in the form of impurities contained in the raw materials. If the amino-modified silicone is within the above range, the treated fiber product and substrate will not turn yellow.

[0171] [Preparation method of the composition]

[0172] The preparation method of the water repellent composition of the present invention is not particularly limited, and it may be carried out according to the conventionally known emulsion polymerization method or phase inversion emulsification method. Each component can be emulsified separately and then mixed, or each component can be mixed and emulsified together. For example, an emulsion containing the component (A) and an emulsion containing the component (B) can be prepared separately and then mixed, or the component (A) and the component (B) can be mixed and emulsified to prepare an emulsion containing both the component (A) and the component (B).

[0173] There is no particular limitation on the emulsifier, and for example, a homomixer, a homogenizer, a colloid mill, a universal mixing stirrer, a COMBI MIX, a pipeline mixer, etc. can be used. The type of the obtained emulsion is not particularly limited and can be any one of O / W type, W / O type, etc.

[0174] In addition, when preparing the emulsion, acids such as acetic acid, lactic acid, hydrochloric acid, sulfuric acid, and citric acid; and bases such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium acetate, and triethanolamine can be used as pH regulators. In addition, silicone oil, hydrocarbon-based oil agents, etc. can be used as viscosity regulators.

[0175] [Use]

[0176] The water repellent composition of the present invention can be used for treating the surfaces of various substrates such as fibers, paper, metals, woods, rubbers, plastics, and glasses. As a coating method for the substrates, various conventionally known coating methods such as dipping method, spraying method, roll coating method, bar coating method, and brush coating method can be used.

[0177] In addition, there is no particular limitation on the coating amount of the water repellent composition. Generally, as the water repellent composition, the coating amount is 0.1 to 200 g / m 2 , preferably 1 to 100 g / m 2 The amount. After coating, an organopolysiloxane coating film can be obtained only by drying, and this drying can be carried out as long as the conditions are such that water will volatilize. When at room temperature, it can be dried for 1 to 3 days, and when heated, it can be dried at 100 to 180 °C for about 1 to 30 minutes.

[0178] [Fiber treatment agent]

[0179] The waterproofing agent composition of the present invention can be used as an active ingredient of a fiber treatment agent because the surface of the treated fiber has excellent waterproof properties. This waterproofing agent composition can be directly used as a fiber treatment agent or appropriately blended in a fiber treatment agent in a range of, for example, 0.01 to 99% by mass. Among them, as other components in the fiber treatment agent, fiber reagents such as wrinkle-proofing agents, flame retardants, antistatic agents, and heat-resistant agents, antioxidants, ultraviolet absorbers, pigments, metal powder pigments, rheology control agents, curing accelerators, deodorants, antibacterial agents, etc. can be cited.

[0180] When treating fibers, the fiber treatment agent can be diluted before use. The blending amount of the waterproofing agent composition in the diluted fiber treatment agent for treating fibers is preferably 0.01 to 10% by mass in terms of solid content, and more preferably 0.1 to 7% by mass.

[0181] The waterproofing agent composition and fiber treatment agent of the present invention are of course effective for natural fibers such as cotton, silk, hemp, cashmere, angora, and mohair, and are also effective for synthetic fibers such as polyester, nylon, acrylic, polyurethane, and spandex, as well as fiber products using these. In addition, there are no particular restrictions on their form and shape, and they are not limited to raw material shapes such as short fibers, silk, long fibers, and threads. Substances in various processed forms such as fabrics, knitted fabrics, stuffing cotton, non-woven fabrics, paper, sheets, and films can also be the objects that can be treated by the fiber treatment agent of the present invention.

[0182] In addition, the waterproofing agent composition and fiber treatment agent of the present invention can also be applied to substrates other than fibers. As substrates that can be the objects of coating the waterproofing agent composition and fiber treatment agent, inorganic porous materials such as concrete, lightweight concrete, lightweight aerated concrete (ALC), mortar, various cement boards, gypsum boards, calcium silicate boards, bricks, tiles, and stones can be cited. In addition, it can also be used for organic porous materials such as walls mainly made of diatomaceous earth, clay, and plaster, paper, wood, and leather.

[0183] [Examples]

[0184] Hereinafter, examples and comparative examples are shown to specifically illustrate the present invention, but the present invention is not limited by the following examples. In addition, in the following examples, when not specifically stated, “%” of the composition represents mass %.

[0185] [Production Example A-1]

[0186] The following components were mixed and emulsified and dispersed using a homogeneous mixer, and then subjected to high-pressure treatment under the condition of 30 MPa using a high-pressure homogenizer to obtain a silicone emulsion composition (I-1).

[0187] (A) Organohydrogenpolysiloxane represented by the following average compositional formula (A-1) (viscosity at 25°C: 20 mPa·s, hydrogen gas generation amount: 340 mL / g): 60.00 parts by mass;

[0188] [Chemical formula 12]

[0189]

[0190] (C) NONION K-204 (trade name): manufactured by NOF CORPORATION, polyoxyethylene lauryl ether, HLB value 9.7: 1.20 parts by mass;

[0191] NONION K-230 (trade name): manufactured by NOF CORPORATION, polyoxyethylene lauryl ether, HLB value 17.5: 0.30 parts by mass;

[0192] (E) Ion-exchanged water: 38.50 parts by mass.

[0193] [Production Example A-2]

[0194] The following components were mixed and emulsified and dispersed using a homogeneous mixer, and then high-pressure treatment was carried out under the condition of 30 MPa using a high-pressure homogenizer to obtain an organosilicon emulsion composition (I-2).

[0195] (A) Organohydrogenpolysiloxane represented by the following average compositional formula (A-2) (viscosity at 25°C: 120 mPa·s, hydrogen gas generation amount: 270 mL / g): 60.00 parts by mass;

[0196] [Chemical formula 13]

[0197]

[0198] (C) NONION K-204: 1.20 parts by mass;

[0199] NONION K-230: 0.30 parts by mass;

[0200] (E) Ion-exchanged water: 38.50 parts by mass.

[0201] [Production Example A-3]

[0202] The following components were mixed and emulsified and dispersed using a homogeneous mixer, and then high-pressure treatment was carried out under the condition of 30 MPa using a high-pressure homogenizer to obtain an organosilicon emulsion composition (I-3).

[0203] (A) The organohydrogenpolysiloxane represented by the following average compositional formula (A-3) (viscosity at 25 °C: 130 mPa·s, hydrogen gas generation amount: 240 mL / g): 60.00 parts by mass;

[0204] [Chemical formula 14]

[0205]

[0206] (C) NONION K-204: 1.20 parts by mass;

[0207] NONION K-230: 0.30 parts by mass;

[0208] (E) Ion-exchanged water: 38.50 parts by mass.

[0209] [Production Example A-4]

[0210] The following components were mixed and emulsified and dispersed using a homogeneous mixer, and then high-pressure treatment was performed at 30 MPa using a high-pressure homogenizer to obtain the organosilicon emulsion composition (I-4).

[0211] (A) The organohydrogenpolysiloxane represented by the following average compositional formula (A-4) (viscosity at 25 °C: 45 mPa·s, hydrogen gas generation amount: 300 mL / g): 60.00 parts by mass;

[0212] [Chemical formula 15]

[0213]

[0214] (C) NONION K-204: 1.20 parts by mass;

[0215] NONION K-230: 0.30 parts by mass;

[0216] (E) Ion-exchanged water: 38.50 parts by mass.

[0217] For the organosilicon emulsion compositions (I-1) to (I-4) mainly composed of Component A obtained in Production Examples A-1 to A-4, they are shown in Table 1 below.

[0218] [Table 1]

[0219]

[0220] [Production Example B-1]

[0221] 40.00 g of an organopolysiloxane terminated with silanol groups at both ends having a viscosity of 1,500 mPa·s at 25°C in which the cyclic low molecular weight siloxanes of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) are each reduced to less than 10 ppm (detection limit) are heated and mixed in advance under reduced pressure of 10 mmHg or less at 150°C, 0.29 g of triethoxyphenylsilane, 1.28 g of an ethanol product (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.) of trimethyl octyl ammonium chloride ((C) component) with an active ingredient of 95%, 1.20 g of an ethanol product (LIPOQUAD 22 - 80: manufactured by LION SPECIALTY CHEMICALS CO., LTD.) of dodecyl trimethyl ammonium chloride ((C) component) with an active ingredient of 80%, 3.20 g of polyoxyethylene (10) tridecyl ether ((C) component) (NEWCOL 1310: manufactured by NIPPONNYUKAZAI CO., LTD.), and 6.00 g of ion - exchanged water ((E) component) are uniformly emulsified and dispersed using a homogeneous mixer and a disperser to prepare an emulsion. Then, 37.64 g of ion - exchanged water is further added to the emulsion, and after uniformly dispersing using a homogeneous mixer, an aqueous ammonia solution prepared by diluting 0.35 g of a 30% aqueous ammonia solution with 9.65 g of ion - exchanged water is added. Then, the solution temperature is lowered to 15°C, polymerization is carried out for 24 hours, and 0.39 g of acetic acid is added for neutralization, whereby an emulsion (II - 1) mainly composed of an organopolysiloxane (B - 1) having the following average compositional formula is obtained.

[0222] [Chemical formula 16]

[0223]

[0224] [Production Example B - 2]

[0225] 40.00 g of an organopolysiloxane endblocked with silanol groups at both ends having a viscosity of 1,500 mPa·s at 25°C in which the cyclic low molecular weight siloxanes of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) are each reduced to less than 10 ppm (detection limit) are heated and mixed in advance under reduced pressure of 10 mmHg or less at 150°C. 0.08 g of triethoxyphenylsilane, 1.28 g of an ethanol product (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.) of trimethyloctylammonium chloride ((C) component) with an active ingredient of 95%, 1.20 g of an ethanol product (LIPOQUAD 22-80: manufactured by LION SPECIALTY CHEMICALS CO., LTD.) of dodecyltrimethylammonium chloride ((C) component) with an active ingredient of 80%, 3.20 g of polyoxyethylene(10) tridecyl ether ((C) component) (NEWCOL 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), and 6.00 g of ion-exchanged water ((E) component) are uniformly emulsified and dispersed using a homogeneous mixer and a disperser to prepare an emulsion. Then, 37.85 g of ion-exchanged water is further added to the emulsion, and after uniformly dispersing using a homogeneous mixer, an aqueous ammonia solution prepared by diluting 0.35 g of a 30% aqueous ammonia solution with 9.65 g of ion-exchanged water is added. Then, the solution temperature is lowered to 15°C and polymerization is carried out for 24 hours, and 0.39 g of acetic acid is added for neutralization to obtain an emulsion (II-2) mainly composed of an organopolysiloxane (B-2) represented by the following average compositional formula.

[0226] [Chemical formula 17]

[0227]

[0228] [Production Example B-3]

[0229] 40.00 g of an organopolysiloxane capped with silanol groups at both ends having a viscosity of 1,500 mPa·s at 25°C in which the cyclic low molecular weight siloxanes of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) are each reduced to less than 10 ppm (detection limit) are heated and mixed in advance under reduced pressure of 10 mmHg or less at 150°C, 0.39 g of triethoxyphenylsilane, 1.28 g of an ethanol product (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.) of trimethyloctylammonium chloride ((C) component) having an active ingredient of 95%, 1.20 g of an ethanol product (LIPOQUAD 22 - 80: manufactured by LION SPECIALTY CHEMICALS CO., LTD.) of dodecyltrimethylammonium chloride ((C) component) having an active ingredient of 80%, 3.20 g of polyoxyethylene(10) tridecyl ether ((C) component) (NEWCOL 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), and 6.00 g of ion-exchanged water ((E) component) are uniformly emulsified and dispersed using a homogeneous mixer and a disperser to prepare an emulsion. Then, 37.54 g of ion-exchanged water is further added to the emulsion, and after uniformly dispersing using a homogeneous mixer, an aqueous ammonia solution prepared by diluting 0.35 g of a 30% aqueous ammonia solution with 9.65 g of ion-exchanged water is added. Then, the solution temperature is lowered to 15°C, polymerization is carried out for 24 hours, and 0.39 g of acetic acid is added for neutralization to obtain an emulsion (II - 3) mainly composed of an organopolysiloxane (B - 3) represented by the following average compositional formula.

[0230] [Chemical formula 18]

[0231]

[0232] [Production Example B - 4]

[0233] 40.00 g of an organopolysiloxane endblocked with silanol groups at both ends having a viscosity of 1,500 mPa·s at 25°C, in which the cyclic low-molecular siloxanes of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) are each reduced to less than 10 ppm (detection limit) by heating and mixing in advance under reduced pressure of 10 mmHg or less at 150°C, 0.21 g of triethoxymethylsilane, 1.28 g of an ethanol product (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.) of trimethylammonium chloride ((C) component) with an active ingredient of 95%, 1.20 g of an ethanol product (LIPOQUAD 22-80: manufactured by LION SPECIALTY CHEMICALS CO., LTD.) of dodecyltrimethylammonium chloride ((C) component) with an active ingredient of 80%, 3.20 g of polyoxyethylene(10) tridecyl ether ((C) component) (NEWCOL 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), and 6.00 g of ion-exchanged water ((E) component) are uniformly emulsified and dispersed using a homogeneous mixer and a disperser to prepare an emulsion. Then, 37.72 g of ion-exchanged water is further added to the emulsion, and after uniformly dispersing using a homogeneous mixer, an aqueous ammonia solution prepared by diluting 0.35 g of a 30% aqueous ammonia solution with 9.65 g of ion-exchanged water is added. Then, the solution temperature is lowered to 15°C, polymerization is carried out for 24 hours, and 0.39 g of acetic acid is added for neutralization to obtain an emulsion (II-4) mainly composed of an organopolysiloxane (B-4) represented by the following average compositional formula.

[0234] [Chemical Formula 19]

[0235]

[0236] [Production Example B-5]

[0237] 40.00 g of an organopolysiloxane endblocked with silanol groups at both ends having a viscosity of 1,500 mPa·s at 25°C in which the cyclic low molecular weight siloxanes of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) are each reduced to less than 10 ppm (detection limit) are heated and mixed in advance under reduced pressure of 10 mmHg or less at 150°C. 0.04 g of triethoxyphenylsilane, 1.28 g of an ethanol product (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.) having an active ingredient of 95% of trimethyloctylammonium chloride ((C) component), 1.20 g of an ethanol product (LIPOQUAD 22 - 80: manufactured by LION SPECIALTY CHEMICALS CO., LTD.) having an active ingredient of 80% of dodecyltrimethylammonium chloride ((C) component), 3.20 g of polyoxyethylene(10) tridecyl ether ((C) component) (NEWCOL 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), and 6.00 g of ion-exchanged water ((E) component) are uniformly emulsified and dispersed using a homogeneous mixer and a disperser to prepare an emulsion. Then, 37.89 g of ion-exchanged water is further added to the emulsion, and after uniformly dispersing using a homogeneous mixer, an aqueous ammonia solution prepared by diluting 0.35 g of a 30% aqueous ammonia solution with 9.65 g of ion-exchanged water is added. Then, the solution temperature is lowered to 15°C, polymerization is carried out for 24 hours, and 0.39 g of acetic acid is added for neutralization to obtain an emulsion (II - 5) mainly composed of an organopolysiloxane (B - 5) represented by the following average compositional formula.

[0238] [Chemical formula 20]

[0239]

[0240] [Production Example B - 6]

[0241] 40.00 g of an organopolysiloxane capped with silanol groups at both ends having a viscosity of 1,500 mPa·s at 25°C, in which the cyclic low molecular weight siloxanes octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) are each reduced to less than 10 ppm (detection limit), 0.08 g of triethoxyphenylsilane, 1.20 g of polyoxyethylene lauryl ether (EO 9 moles) ((C) component) (EMULGEN 109P: manufactured by Kao Corporation), 1.80 g of sodium dodecylbenzenesulfonate ((C) component), and 2.40 g of ion-exchanged water ((E) component) were uniformly emulsified and dispersed using a homogeneous mixer and a disperser to prepare an emulsion. Then, 53.08 g of ion-exchanged water was further added to the emulsion, and after uniformly dispersing using a homogeneous mixer, 0.48 g of concentrated hydrochloric acid was added. Then, the solution temperature was lowered to 15°C and polymerization was carried out for 24 hours, and 0.96 g of triethanolamine was added for neutralization to obtain an emulsion (II-6) mainly composed of the organopolysiloxane (B-2) having the above average compositional formula.

[0242] [Production Example B-1-B]

[0243] An emulsion (II-1-B) mainly composed of the average formula (B-6) was obtained in the same manner as in Production Example B-1, except that 0.35 g of 30% aqueous ammonia solution in Production Example B-1 was changed to 1.15 g of 30% potassium hydroxide, and the ion-exchanged water for diluting the 30% aqueous ammonia solution was changed to 8.85 g of ion-exchanged water for diluting the 30% potassium hydroxide.

[0244] [Chemical Formula 21]

[0245]

[0246] [Comparative Production Example B-7]

[0247] 40.00 g of an organopolysiloxane capped with silanol groups at both ends having a viscosity of 1,500 mPa·s at 25°C, in which cyclic low molecular weight siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) are each reduced to less than 10 ppm (detection limit) by heating and mixing in advance under reduced pressure of 10 mmHg or less at 150°C, 0.03 g of triethoxyphenylsilane, 1.28 g of an ethanol product (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.) of trimethyloctylammonium chloride ((C) component) with an active ingredient of 95%, 1.20 g of an ethanol product (LIPOQUAD 22 - 80: manufactured by LION SPECIALTY CHEMICALS CO., LTD.) of dodecyltrimethylammonium chloride ((C) component) with an active ingredient of 80%, 3.20 g of polyoxyethylene(10) tridecyl ether ((C) component) (NEWCOL 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), and 6.00 g of ion - exchanged water ((E) component) are uniformly emulsified and dispersed using a homogeneous mixer and a disperser to prepare an emulsion. Then, 37.90 g of ion - exchanged water is further added to the emulsion, and after uniformly dispersing using a homogeneous mixer, an aqueous ammonia solution prepared by diluting 0.35 g of a 30% aqueous ammonia solution with 9.65 g of ion - exchanged water is added. Then, the solution temperature is lowered to 15°C and polymerization is carried out for 24 hours, and 0.39 g of acetic acid is added for neutralization, thereby obtaining an emulsion (II - 7) mainly composed of an organopolysiloxane (B - 7) represented by the following average compositional formula.

[0248] [Chemical formula 22]

[0249]

[0250] [Comparative Production Example B - 8]

[0251] 40.00 g of an organopolysiloxane with silanol groups capped at both ends having a viscosity of 1,500 mPa·s at 25°C, in which cyclic low molecular weight siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) are each reduced to less than 10 ppm (detection limit) by heating and mixing in advance under reduced pressure of 10 mmHg or less at 150°C, 0.98 g of triethoxyphenylsilane, 1.28 g of an ethanol product (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.) with an active ingredient of 95% of trioctylmethylammonium chloride ((C) component), 1.20 g of an ethanol product (LIPOQUAD 22 - 80: manufactured by LION SPECIALTY CHEMICALS CO., LTD.) with an active ingredient of 80% of dodecyltrimethylammonium chloride ((C) component), 3.20 g of polyoxyethylene(10) tridecyl ether ((C) component) (NEWCOL 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), and 6.00 g of ion-exchanged water ((E) component) are uniformly emulsified and dispersed using a homogeneous mixer and a disperser to prepare an emulsion. Then, 36.96 g of ion-exchanged water is further added to the emulsion, and after uniformly dispersing using a homogeneous mixer, an aqueous ammonia solution prepared by diluting 0.35 g of a 30% aqueous ammonia solution with 9.65 g of ion-exchanged water is added. Then, the solution temperature is lowered to 15°C, polymerization is carried out for 24 hours, and 0.39 g of acetic acid is added for neutralization to obtain an emulsion (II - 8) mainly composed of an organopolysiloxane (B - 8) represented by the following average compositional formula.

[0252] [Chemical formula 23]

[0253]

[0254] [Comparative Production Example B - 9]

[0255] An emulsion (II - 9) mainly composed of the above-mentioned average formula organopolysiloxane (B - 9) was obtained in the same manner as in Production Example B - 1, except that the polymerization time in Production Example B - 1 was changed to 20 minutes.

[0256] [Chemical formula 24]

[0257]

[0258] [Production Example B - 10]

[0259] 40.00 g of an organopolysiloxane capped with silanol groups at both ends having a viscosity of 1,500 mPa·s at 25°C, in which cyclic low-molecular-weight siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) are each reduced to less than 10 ppm (detection limit) by heating and mixing in advance under reduced pressure of 10 mmHg or less at 150°C, 0.53 g of triethoxyphenylsilane, 1.28 g of an ethanol product (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.) of trimethyloctylammonium chloride ((C) component) with an active ingredient of 95%, 1.20 g of an ethanol product (LIPOQUAD 22-80: manufactured by LION SPECIALTY CHEMICALS CO., LTD.) of dodecyltrimethylammonium chloride ((C) component) with an active ingredient of 80%, 3.20 g of polyoxyethylene(10) tridecyl ether ((C) component) (NEWCOL 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), and 6.00 g of ion-exchanged water ((E) component) are uniformly emulsified and dispersed using a homogeneous mixer and a disperser to prepare an emulsion. Then, 37.40 g of ion-exchanged water is further added to the emulsion, and after uniformly dispersing using a homogeneous mixer, an aqueous ammonia solution prepared by diluting 0.35 g of a 30% aqueous ammonia solution with 9.65 g of ion-exchanged water is added. Then, the solution temperature is lowered to 15°C, polymerization is carried out for 24 hours, and 0.39 g of acetic acid is added for neutralization, whereby an emulsion (II-10) mainly composed of an organopolysiloxane (B-10) represented by the following average compositional formula is obtained.

[0260] [Chemical formula 25]

[0261]

[0262] For the emulsions mainly composed of component B obtained in Production Examples B-1 to 10, the viscosity of the organopolysiloxane and the contents of D4, D5, and D6 are measured by the following procedure.

[0263] (Viscosity of organopolysiloxane)

[0264] 30 g of the emulsion obtained in each production example is added to 200 g of IPA (isopropyl alcohol) with stirring to break the emulsion and extract the organopolysiloxane. After drying the organopolysiloxane at 105°C for 3 hours, the viscosity is measured at 25°C using a BH-type rotational viscometer. In addition, regarding this viscosity, if the substance can be measured in a liquid state, it is measured directly. If the viscosity is too high to be measured, the viscosity of a 5% toluene solution is measured. The viscosity of substances with too high viscosity to be measured in a liquid state is 300,000 mPa·s or more.

[0265] [Amounts of D4, D5, and D6]

[0266] The contents of D4, D5, and D6 were measured as follows. 0.1 g of the measurement sample was added to 10 mL of acetone and shaken for about 2 hours. After the cyclic oligomeric siloxanes were extracted into the acetone solution by shaking, the supernatant acetone solution was measured by gas chromatography (Agilent 7890B (manufactured by Agilent Technologies Japan, Ltd.)). The chromatographic column for gas chromatography was DB-5MS (manufactured by Agilent Technologies Japan, Ltd.), the temperature inside the chromatographic column during measurement was 300 °C, and tetradecane was used as the internal standard substance.

[0267] The emulsions (II-1) to (II-10) obtained in Production Examples B-1 to 10 are shown in Tables 2 and 3 below. In addition, the contents (ppm) of D4, D5, and D6 in the tables are the contents (in mass conversion) of D4, D5, and D6 relative to 100 parts by mass of component (B).

[0268] [Table 2]

[0269]

[0270] [Table 3]

[0271]

[0272] [Production Example D-1]

[0273] The following components were mixed and dissolved in 79.50 parts by mass of (E) ion-exchanged water to obtain an aqueous solution (III-1) of a zinc compound.

[0274] (D) Zinc formate: 10.00 parts by mass;

[0275] Potassium acetate: 10.00 parts by mass;

[0276] Acetic acid 0.50 parts by mass.

[0277] [Production Example D-2]

[0278] 24.00 parts by mass of (D) zinc acetate was mixed and dissolved in 76.00 parts by mass of (E) ion-exchanged water to obtain an aqueous solution (III-2) of a zinc compound.

[0279] [Production Example D-3]

[0280] Using a homogeneous mixer, 6.90 parts by mass of zinc acetate (D) was mixed and dissolved in 26.00 parts by mass of water. Then, 3.00 parts by mass of an ethanol solution (LIPOQUAD 22-80: manufactured by LIONSPECIALTY CHEMICALS CO., LTD.) with an active ingredient of 80% of dodecyltrioctylammonium chloride ((C) component) was added and mixed.

[0281] Furthermore, a mixed solution obtained by dissolving 4.10 parts by mass of potassium laurate in 30.00 parts by mass of hot water was added, and mixed using a homogeneous mixer, so that a part of zinc acetate reacted with potassium laurate to produce an emulsion mainly composed of zinc laurate and zinc acetate.

[0282] Then, 30.00 parts by mass of water was added, and further high-pressure treatment was performed using a high-pressure homogenizer under the condition of 30 MPa to obtain an emulsion composition (III-3) mainly composed of zinc laurate and zinc acetate.

[0283] The aqueous solutions of zinc compounds or emulsions containing zinc compounds (compositions (III-1) to (III-3)) obtained in Production Examples D-1 to 3 are shown in Table 4 below.

[0284] [Table 4]

[0285]

[0286] (F) Polyfunctional isocyanate

[0287] DURANATE WL72-100 (trade name): manufactured by Asahi Kasei Chemicals Corporation, water-dispersed polyisocyanate

[0288] [Examples 1 to 13, Comparative Examples 1 to 5]

[0289] The respective compositions obtained in the above production examples were blended in the amounts shown in Tables 5 to 7 below to obtain the waterproofing agent compositions of Examples 1 to 13 and Comparative Examples 1 to 5. For the obtained waterproofing agent compositions, the following evaluation tests were performed. The results are shown in Tables 8 to 10 (each blending represents the amount of each component relative to 100 parts by mass of component (A)).

[0290] [Table 5]

[0291]

[0292] [Table 6]

[0293]

[0294] [Table 7]

[0295]

[0296] [Evaluation test]

[0297] 1. Softness

[0298] Ion-exchanged water was added to the above waterproofing agent composition and stirred to dilute it so that the component (A) was 3%, thereby preparing a test solution. Cotton broadcloth and polyester / cotton broadcloth (65% / 35%) were immersed in this test solution for 10 seconds, then wrung out using a roller under the condition of 100% wringing rate, and dried at 150 °C for 2 minutes, thereby producing a treated cloth for softness evaluation. The treated cloth was washed 10 times through a washing machine according to the method of JIS L0217 103. Three participants touched the treated cloth before washing and after 10 washes by hand, compared it with the untreated cloth, and evaluated the softness / hand feeling through the following scoring. The results were shown according to the total score of the scores of the three participants based on the following evaluation criteria.

[0299] <Scoring>

[0300] 3 points: The touch is very good compared to the untreated cloth.

[0301] 2 points: The touch is good compared to the untreated cloth.

[0302] 1 point: The touch is the same as the untreated cloth.

[0303] 0 points: The touch is poor compared to the untreated cloth.

[0304] <Evaluation criteria>

[0305] ◎◎: Total score of 9 points

[0306] ◎: Total score of 7 - 8 points

[0307] 〇: Total score of 5 - 6 points

[0308] △: Total score of 3 - 4 points

[0309] ×: Total score of 2 points or less

[0310] 2. Waterproofness

[0311] Ion-exchanged water was added to the above waterproofing agent composition and stirred to dilute it so that the component (A) was 3%, thereby preparing a test solution. Cotton lawn, polyester / cotton lawn (65% / 35%), and polyester taffeta were immersed in the test solution for 10 seconds, then wrung out using a roller under the condition of a 100% wringing rate, and dried at 150 °C for 3 minutes to produce a treated cloth for evaluating softness. Then, the treated cloth was washed 20 times through a washing machine according to the method of JIS L0217 103. Tests were conducted on the cloth without washing, the cloth after 5 washes, the cloth after 10 washes, and the cloth after 20 washes, respectively, according to the spraying method of JIS-L 1092. The results were evaluated visually according to the following grades.

[0312] Waterproofness: Condition

[0313] 5: No wetness adhered to the surface

[0314] 4: Slight wetness was shown on the surface

[0315] 3: Wetness was shown on part of the surface

[0316] 2: The surface was shown to be wet

[0317] 1: The entire surface was shown to be wet

[0318] 0: Both the front and back surfaces were completely shown to be wet

[0319] [Table 8]

[0320]

[0321] In the evaluation columns (softness, waterproofness) in the table, "cotton cloth" refers to cotton lawn, "polyester / cotton cloth" refers to polyester / cotton lawn (65% / 35%), and "polyester cloth" refers to polyester taffeta. The same applies hereinafter.

[0322] [Table 9]

[0323]

[0324] [Table 10]

[0325]

[0326] As shown in the above table, the waterproofing agent composition of the present invention (Examples 1 to 13) has an excellent waterproofing effect and the treated cloth has good softness / handfeel. In addition, the waterproofing agent composition of the present invention maintains high waterproofness and softness / handfeel even after washing.

[0327] Compared with Example 5 that does not contain component (F), Example 13 that further contains component (F) maintains softness / hand feeling even after repeated washing, and at the same time maintains excellent water repellency for a longer time. It is considered that this is the effect of component (F). That is, it is considered that by blending component (F) containing an isocyanate group, the reactive groups contained in components (A) and (B) chemically react with the isocyanate group of component (F) to enable crosslinking, and this isocyanate group can also react with the reactive groups contained in the substrate to be treated, so a stronger coating film can be formed, thereby improving the water repellency after repeated washing.

[0328] On the other hand, in Comparative Example 1 where the ratio (g / h) of component (B) is greater than the upper limit value and the ratio (X / Y) is less than the lower limit value, the water repellency could not be maintained after repeated washing. In Comparative Example 2 where the ratio (g / h) is less than the lower limit value and the ratio (X / Y) is greater than the upper limit value, the softness / hand feeling of the treated fabric could not be maintained after repeated washing. Even when the ratio (g / h) is within the scope of the present invention, in Comparative Example 4 where the ratio (X / Y) is less than the lower limit value, the water repellency could not be maintained after repeated washing. In Comparative Example 5, since the ratio (X / Y) is greater than the upper limit value, the softness / hand feeling could not be maintained after repeated washing. And even when both the ratio (g / h) and the ratio X / Y are within the scope of the present invention, in Comparative Example 3 where the viscosity (25°C) of the organopolysiloxane of component (B) is less than 300,000 mPa·s, the water repellency decreased significantly after repeated washing.

[0329] Therefore, by having all the technical features of the present invention, it will become a water repellent composition with excellent water repellency imparting effect, capable of imparting good softness / hand feeling to the treated fiber and maintaining good water repellency and softness even after washing.

[0330] Industrial Applicability

[0331] The water repellent composition of the present invention has an excellent water repellency imparting effect, good softness / hand feeling of the treated fabric, and can maintain high water repellency even after washing. And since the content of the fluorine compound is low, the environmental load is low.

[0332] This specification includes the following aspects.

[0333] [1]: A water repellent composition, characterized in that it contains:

[0334] (A) An organohydrogenpolysiloxane represented by the following average composition formula (1) and having a viscosity of 5 to 1,000 mPa·s at 25°C, which is 100 parts by mass;

[0335] [Chemical formula 26]

[0336]

[0337] In formula (1), R 1 is independently a monovalent unsubstituted hydrocarbon group having 1 to 20 carbon atoms, R 2 is a hydrogen atom, and R 3 are independently R 1 , R 2 and a group selected from -OH, -OCH3 and -OC2H5, and a, b, c, d and e are numbers satisfying the ranges of 0 ≤ a ≤ 10, 0 ≤ b ≤ 100, 0 ≤ c ≤ 500, 0 ≤ d ≤ 5, and 0 ≤ e ≤ 5; wherein when c = 0, one or more of R 3 are R 2 ;

[0338] (B) An organopolysiloxane represented by the following average composition formula (2) and having a viscosity of 300,000 mPa·s or more at 25°C, which is 10 to 100 parts by mass;

[0339] [Chemical formula 27]

[0340]

[0341] In formula (2), R 5 are independently a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, and R 6 are independently a group selected from the options of the above R 5 , a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms, and f, g, h, and i are values that satisfy the viscosity of the organopolysiloxane being 300,000 mPa·s or more at 25°C, f ≥ 2, h ≥ 1, i ≥ 0, and the ratio of g to h (g / h) is 50 ≤ (g / h) ≤ 1,000;

[0342] (C) A surfactant, which is 0.5 to 50 parts by mass;

[0343] (D) A condensation reaction catalyst, which is 5 to 100 parts by mass; and

[0344] (E) Water, which is 50 to 3,000 parts by mass; and,

[0345] When the hydrogen generation amount of the component (A) converted to 0°C and 101.325 kPa is X (mL / g) and the ratio of g to h (g / h) of the component (B) is Y, the ratio of X to Y (X / Y) is in the range of 0.30 ≤ (X / Y) ≤ 4.50.

[0346] [2]: The waterproofing agent composition according to [1], wherein R 1 , R 2 and R3 More than 10% of all substituents represented are R 2 .

[0347] [3]: The waterproofing agent composition according to [1] or [2], characterized in that the ratio (g / h) of g to h of the component (B) is 70 ≤ (g / h) ≤ 950.

[0348] [4]: The waterproofing agent composition according to any one of [1] to [3], characterized in that the component (D) is a compound of one or more metals selected from tin, zinc, bismuth, titanium, iron, zirconium and aluminum.

[0349] [5]: The waterproofing agent composition according to any one of [1] to [4], characterized in that, relative to 100 parts by mass of the component (B), the contents of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) in the waterproofing agent composition are each less than 3,000 ppm.

[0350] [6]: The waterproofing agent composition according to any one of [1] to [5], characterized in that the (C) surfactant comprises a cationic surfactant.

[0351] [7]: The waterproofing agent composition according to [6], characterized in that the cationic surfactant is a cationic surfactant represented by the following formulas (C-1) and (C-2):

[0352] (C-1) Q 1 3(CH3)N + ·X - The cationic surfactant represented,

[0353] (C-2) Q 2 (CH3)3N + ·X - The cationic surfactant represented,

[0354] Q 1 Are the same or different monovalent organic groups having 6 to 30 carbon atoms, Q 2 Is a monovalent organic group having 17 to 30 carbon atoms, and X is independently a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms.

[0355] [8]: The waterproofing agent composition according to any one of [1] to [7], characterized in that, relative to 100 parts by mass of the component (A), 1 to 50 parts by mass of an (F) polyfunctional isocyanate compound is further contained.

[0356] [9]: The waterproofing agent composition according to any one of [1] to [8], characterized in that the content of the fluorine compound is less than 1 part by mass relative to 100 parts by mass of the component (A).

[0357]

[10] : A fiber treatment agent, characterized in that it contains the waterproofing agent composition according to any one of [1] to [9].

[0358] The present invention is not limited to the above embodiments. The above embodiments are examples, and any solutions having substantially the same composition and exhibiting the same effects as the technical concept described in the claims of the present invention are included within the technical scope of the present invention.

Claims

1. A waterproofing agent composition, characterized in that, It contains: (A) 100 parts by mass of an organohydrogenpolysiloxane having a viscosity at 25 °C of 5 to 1,000 mPa·s represented by the following average compositional formula (1); [Chemical formula 1] In formula (1), R 1 is independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R 2 is a hydrogen atom, and R 3 are independently R 1 , R 2 and a group selected from -OH, -OCH3 and -OC2H5, and a, b, c, d and e are numbers within the ranges of 0 ≤ a ≤ 10, 0 ≤ b ≤ 100, 0 ≤ c ≤ 500, 0 ≤ d ≤ 5, and 0 ≤ e ≤ 5; wherein, when c = 0, one or more of R 3 are R 2 ; (B) 10 to 100 parts by mass of an organopolysiloxane having a viscosity at 25 °C of 300,000 mPa·s or more represented by the following average compositional formula (2); [Chemical formula 2] In formula (2), R 5 independently of one another is a hydrogen atom, or a monovalent organic group having 1 to 20 carbon atoms which may be substituted or unsubstituted, R 6 independently of one another is a group selected from the options of the above R 5 , a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms, f, g, h, and i are values that satisfy the viscosity of the organopolysiloxane at 25 °C to be 300,000 mPa·s or more, f ≥ 2, h ≥ 1, i ≥ 0, and the ratio of g to h (g / h) is 50 ≤ (g / h) ≤ 1,000; (C) 0.5 to 50 parts by mass of a surfactant; (D) 5 to 100 parts by mass of a condensation reaction catalyst; and (E) 50 to 3,000 parts by mass of water; and, when the hydrogen generation amount of the component (A) converted to 0 °C and 101.325 kPa is X (mL / g) and the ratio (g / h) of g to h of the component (B) is Y, the ratio (X / Y) of X to Y is in the range of 0.30 ≤ (X / Y) ≤ 4.

50.

2. The waterproofing agent composition according to claim 1, characterized in that, The R of the component (A) 1 , R 2 and R 3 More than 10% of all the substituents represented by are R 2 .

3. The waterproofing agent composition according to claim 1, wherein The ratio (g / h) of g to h of the component (B) is 70 ≤ (g / h) ≤ 950.

4. The waterproofing agent composition according to claim 1, characterized in that The component (D) is a compound of one or more metals selected from tin, zinc, bismuth, titanium, iron, zirconium, and aluminum.

5. The waterproofing agent composition according to claim 1, characterized in that, With respect to 100 parts by mass of the component (B), the contents of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in the waterproofing agent composition are less than 3,000 ppm.

6. The waterproofing agent composition according to claim 1, characterized in that, The component (C) surfactant contains a cationic surfactant.

7. The waterproofing agent composition according to claim 6, characterized in that, The cationic surfactant is a cationic surfactant represented by the following formulas (C-1) and (C-2): (C-1)Q 1 3(CH3)N + ·X - The cationic surfactant represented by (C-2)Q 2 (CH3)3N + ·X - The cationic surfactant represented by Q 1 is a monovalent organic group having 6 to 30 carbon atoms, which may be the same or different. Q 2 is a monovalent organic group having 17 to 30 carbon atoms. X is independently a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms.

8. The waterproofing agent composition according to claim 1, characterized in that, With respect to 100 parts by mass of the component (A), the waterproofing agent composition further contains 1 to 50 parts by mass of (F) a polyfunctional isocyanate compound.

9. The waterproofing agent composition according to claim 1, characterized in that, With respect to 100 parts by mass of the component (A), the content of the fluorine compound is less than 1 part by mass.

10. A fiber treating agent, characterized in that, It contains the waterproofing agent composition according to any one of claims 1 to 9.

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