Water-repellent treatment agent, water-repellent structure and method for producing the same

Abstract

To provide a water-repellency imparting technique that offers compatibility between water-repellent and antistatic properties for a treated material, distinct from techniques that use silicone compounds (such as polysiloxanes and silane coupling agents) or fluorinated compounds.SOLUTION: An ion-bonding salt represented by formula (1) is used as a water-repellent treatment agent. In formula (1), Q+ is a cation derived from a silane compound having an amino group or imino group; in formula (1), T- is a sulfate ester anion, phosphate ester anion, sulfonate anion, or carboxylate anion having an oxyalkylene chain.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a water-repellent treatment agent, a water-repellent structure, and a method for producing the same. [Background technology]

[0002] Conventionally, in the fields of paints, adhesives, pressure sensitive adhesives, textile auxiliaries, building material films, protective films such as hard coats, housings for home appliances, papermaking applications (surface coating agents, etc.), civil engineering applications (concrete admixtures, etc.), and the like, techniques for adding silicone compounds or fluorine-based compounds to impart water repellency to the surfaces of resins, fiber materials, and glass have been known (see Patent Documents 1 and 2). In this technique, silicone compounds or fluorine-based compounds are arranged on the surface of a substrate (object to be treated) and the water repellency of these compounds themselves is utilized to obtain a member with excellent stain resistance.

[0003] Fluorine-based water repellents are known as water repellents used in textiles, and textile products are known to have their surfaces imparted with water repellency by treating them with such fluorine-based water repellents. Such fluorine-based water repellents are generally produced by polymerizing or copolymerizing monomers having a fluoroalkyl group. Textile products treated with fluorine-based water repellents exhibit excellent water repellency. However, monomers having a fluoroalkyl group are expensive and therefore unsatisfactory from an economical perspective. Furthermore, monomers having a fluoroalkyl group are difficult to decompose, which is also problematic from an environmental perspective.

[0004] On the other hand, polysiloxanes and silane coupling agents are used as non-fluorine-containing water repellents, which chemically condense with surfaces that have hydroxyl groups, providing durable water repellency. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 3-249281 [Patent Document 2] Japanese Patent Application Publication No. 9-241622 Summary of the Invention [Problem to be solved by the invention]

[0006] However, when imparting water repellency to inorganic fibers made of glass or the like, it is usually necessary to perform a heat treatment at a high temperature of 250 to 290°C for a long time. In addition, organic fibers for clothing are usually treated at a high temperature of 150°C to 190°C, which is a problem of high energy load. Furthermore, water-insoluble silane coupling agents and silane coupling agents with low flash points may volatilize, causing a risk of explosion or fire. Furthermore, fibers and glass plates are often hotbeds of static electricity, and are required to have excellent antistatic properties even after being treated for water repellency.

[0007] Therefore, an object of the present invention is to provide a water-repellency imparting technology that can achieve both water repellency and antistatic properties for the treated object, which differs from conventional technologies that use silicone compounds (polysiloxanes, silane coupling agents) or fluorine-based compounds. [Means for solving the problem]

[0008] In order to solve the above problems, the present inventors have conducted extensive research and have surprisingly found that an ionically bonded salt consisting of a cation derived from a silane compound containing an amino group or an imino group and a specific anion exhibits excellent performance as a water repellent treatment agent, thereby completing the present invention.

[0009] That is, the above object can be achieved by the present invention having the following configuration, and the present invention includes the following aspects and forms.

[0010] One aspect of the present invention is 1. A water repellent treatment agent comprising an ion-bonding salt represented by the following formula (1):

[0011] [ka]

[0012] In the above formula (1), Q + is a cation derived from a silane compound containing an amino or imino group; In the above formula (1), T - is expressed by the following formula (t-1):

[0013] [ka]

[0014] In the above formula (t-1), R 1 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms; A 1 is a linear or branched alkylene group having 2 to 4 carbon atoms, s is an integer from 0 to 50; A sulfate ester anion represented by the formula: The following formula (t-2):

[0015] [ka]

[0016] In the above formula (t-2), R 2 and R 3are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, in which R 2 and R 3 is not a hydrogen atom at the same time, A 2 and A 3 are each independently a linear or branched alkylene group having 2 to 4 carbon atoms, t and u each independently represent an integer of 0 to 50. A phosphate ester anion represented by the formula: The following formula (t-3):

[0017] [ka]

[0018] In the above formula (t-3), R 4 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms; A 4 is a linear or branched alkylene group having 2 to 4 carbon atoms, v is an integer from 0 to 50; or a sulfonate anion represented by The following formula (t-4):

[0019] [ka]

[0020] In the above formula (t-4), R 5 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms; It is a carboxylate anion represented by the formula:

[0021] 2. In the water repellent treatment agent described in 1 above, in the above formula (1), Q + is expressed by the following formula (q-1):

[0022] [ka]

[0023] In the above formula (q-1), X is -CH2- or an oxygen atom (-O-), Y is -NH-, Z is -N(R 7 )2 or -N=C(R 7 )2, R 6each independently represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms (-OR 8 In this case, R 8 represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, R 7 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms (-OR 9 In this case, R 9 represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, m is an integer from 0 to 5; n is an integer from 0 to 5, q is 0 or 1; r is 0 or 1; It is preferable that the cation is derived from a compound represented by the formula: 3. In the water repellent treatment agent described in 2 above, R 6 at least one of the is preferably a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms; 4. The water repellent treatment agent according to 2 above, wherein in the formula (q-1), X is -CH2-, Z is -N(R 7 )2, R 6 each independently represents a hydrogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, R 7 is a hydrogen atom, m is an integer from 0 to 3; n is 0, q is 0 or 1; Preferably, r is 0; 5. In the water repellent treatment agent according to any one of 1. to 4. above, in the formula (1), Q + preferably does not contain a cation derived from the amino-modified polysiloxane; 6. The water repellent treatment agent according to any one of 1. to 5. above preferably functions as an antistatic agent; 7. The water repellent treatment agent described in 6 above has a surface resistivity of 8×10 11 [Ω / □] or less is preferable; 8. The water repellent treatment agent according to any one of 1. to 7. above is preferably used for treating fibers; Another aspect of the present invention is 9. A water-repellent treatment solution comprising the water-repellent treatment agent according to any one of 1. to 8. above and a liquid medium; 10. The water repellent treatment solution described in 9 above preferably does not contain a surfactant; Yet another aspect of the present invention is 11. A method for treating a water-repellent surface of a substrate, comprising: The water-repellent portion is a water-repellent structure including a structure derived from the cation constituting the ion-bonding salt contained in the water-repellent treatment agent according to any one of 1. to 8. above, or the water-repellent treatment agent solution according to 9. or 10. above; 12. In the water-repellent structure described in 11 above, it is preferable that the object to be treated has a large number of hydroxyl groups on the surface; 13. In the water-repellent structure according to 12. above, it is preferable that the object to be treated contains glass or resin; 14. In the water-repellent structure according to the above paragraph 13, it is preferable that the object to be treated contains a resin, and the hydroxy group is a hydroxy group bonded to a polymer chain of the resin; 15. In the water-repellent structure described in 13 above, it is preferable that the object to be treated contains a resin and filler particles, and the hydroxy group is a hydroxy group present on the surface of the filler particles; 16. In the water-repellent structure according to 14. or 15. above, it is preferable that the object to be treated is a fiber; Yet another aspect of the present invention is 17. A method for producing a water-repellent structure, comprising treating an object with the water-repellent treatment agent according to any one of 1. to 8. above, or the water-repellent treatment solution according to 9. or 10. above. Effect of the Invention

[0024] According to the present invention, there is provided a water-repellency imparting technology that can achieve both water repellency and antistatic properties for the treated object, which differs from conventional technologies that use silicone compounds (polysiloxanes, silane coupling agents) or fluorine-based compounds. [Brief description of the drawings]

[0025] [Figure 1] FIG. 1 is a schematic diagram showing a water-repellent structure according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] One aspect of the present invention provides a water repellent treatment agent comprising an ion-bonding salt represented by the above formula (1) (hereinafter, simply referred to as "ion-bonding salt (1)"). Thus, the ion-bonding salt (1) according to the present invention comprises a cation derived from a silane compound containing an amino group or an imino group, and a specific anion.

[0027] The ionically bonded salt (1) according to the present invention will be specifically described below.

[0028] [Ionic salts (1)] The ionic salt (1) is a cation (Q + ) and a sulfate ester anion represented by the above formula (t-1), a phosphate ester anion represented by the above formula (t-2), a sulfonate anion represented by the above formula (t-3), or a carboxylate anion represented by the above formula (t-4).

[0029] (Cation Q + ) In the above formula (1), the "cation derived from a silane compound containing an amino group or an imino group" may be a positively charged cation resulting from the addition of a proton, a carbocation, or the like to a silane compound containing an amino group or an imino group. Therefore, Q + does not need to be positively charged by addition of a proton or the like to the amino group or imino group in the silane compound containing an amino group or an imino group, and may be positively charged by addition of a proton or the like to another cationic group. However, from the viewpoint of ease of availability, it is preferable that the amino group or imino group is positively charged by addition of a proton or the like.

[0030] Here, the "silane compound containing an amino group or an imino group" may be any compound having at least one silicon atom (Si) and at least one amino group or imino group. In the above, the amino group is a substituent represented by "-N(R')2", where the substituent represented by R' is not particularly limited, and examples thereof include a hydrogen atom, an alkyl group, an aryl group, etc., each independently. The imino group is a substituent represented by "-N=C(R')2", where R' is the same as above. The above "silane compound containing an amino group or an imino group" may contain both an amino group and an imino group.

[0031] Examples of such compounds include silicone compounds having a substituent containing an amino group (amino-modified silicone compounds), silane compounds having a substituent containing an amino group (silane compounds other than amino-modified silicone compounds), and silane compounds having a substituent containing an imino group.

[0032] Here, the amino-modified silicone compound includes those in which an organic group containing an amino group is introduced into the side chain of a polysiloxane (side chain type), those in which an organic group containing an amino group is introduced into both ends of a polysiloxane (both ends type), those in which an organic group containing an amino group is introduced into one end of a polysiloxane (one end type), those in which an organic group containing an amino group is introduced into the side chain and both ends of a polysiloxane (side chain both ends type), and those in which an organic group containing an amino group is introduced into the side chain and one end of a polysiloxane (side chain one end type).

[0033] The amino-modified silicone compound is not particularly limited, but it is preferable to use one having an amine equivalent (mass (g) of a silicone compound containing 1 mole of amino groups) of 15,000 g / mol or less, and more preferably one having a range of 300 to 13,000 g / mol. In addition, the kinetic viscosity (25°C) is preferably 1 to 20,000 mm 2 It is preferable to use a material with a speed of 10 to 5000 mm / s. 2 It is more preferable to use one that is / s.

[0034] Examples of commercially available silicone compounds that can satisfy these conditions include X-22-161A, X-22-161B, KF-8010, and KF-8012 (all manufactured by Shin-Etsu Chemical Co., Ltd.), Dynasylan (registered trademark) 1122, 1124, 1146, 1161, 1189, 1411, 1505, 1506, 2627, and 2909; Dynasylan (registered trademark) SIVO210, SIVO214, DAMO-M, AMEO-T, and AMMO; and HYDROSIL (registered trademark) 1151, 2627, 2776, and 2909 (all manufactured by EVONIK). Examples of amino-modified silicone compounds include those manufactured by Dow Corning Toray Co., Ltd., BY16-871, 16-853U, 16-849, 16-872, 16-878, 16-890, 16-891, 16-893, 16-208, FZ-3705, 3785, 3789, and SF8147 (all manufactured by Dow Corning Toray Co., Ltd.).

[0035] In addition, the silane compound having a substituent containing an amino group (silane compound other than amino-modified silicone compound) may be any compound having one or more silicon atoms and an amino group as described above, and examples thereof include aminosilane, diaminosilane, triaminosilane, alkylaminosilane (N-(trimethylsilyl)diethylamine, N-(trimethylsilyl)dimethylamine, N-(triethylsilyl)diethylamine, N-(triethylsilyl)dimethylamine, etc.), alkyl(alkylamino)silane, (alkylamino)alkoxysilane, alkyl(alkylamino)alkoxysilane, cycloalkyl(alkylamino)alkoxysilane, tetrakis(alkylamino)silane, alkyltris(alkylamino)silane, dialkylbis(alkylamino)silane, trialkyl(alkylamino)silane, tris(alkylamino)alkoxysilane, bis(alkylamino)dialkoxysilane, and (alkylamino)trialkoxysilane.

[0036] In addition, the silane compound having a substituent containing an imino group may be any compound having one or more silicon atoms and an imino group as described above, and examples thereof include N-alkyl(trialkylsilyl)alkaneimines, N-alkyl(alkoxydialkylsilyl)alkaneimines, N-alkyl(dialkoxyalkylsilyl)alkaneimines, and N-alkyl(trialkoxysilyl)alkaneimines.

[0037] Furthermore, the amino-modified silicone compound and the silane compound having a substituent containing an amino group (silane compound other than silicone compound) preferably contain a primary, secondary or tertiary amino group, more preferably a primary or secondary amino group, and particularly preferably a primary amino group. From the viewpoint of simplifying the reaction process, it is preferable that the silane compound containing an amino group or an imino group contains a primary amine.

[0038] As described above, the silane compound containing an amino group or an imino group can be an amino-modified silicone compound, a silane compound having a substituent containing an amino group (a silane compound other than an amino-modified silicone compound), and a silane compound having a substituent containing an imino group. These compounds can be appropriately selected according to the silicone compound used from the viewpoint of compatibility with the silicone compound contained in the resin composition.

[0039] In the silane compound having a substituent containing an amino group (a silane compound other than an amino-modified silicone compound) or the silane compound having a substituent containing an imino group, the positions of the amino group or imino group and the silicon atom (positions in the molecule) are not particularly limited, but it is preferable that the main chain of the molecule has a silicon atom at one end and an amino group or imino group at the other end. If the distance between the amino group or imino group and the silicon atom is too close, the affinity between the object (subject to be treated) to be water-repellent treated and silicon may be inhibited by the cation derived from the amino group or imino group, but by adopting the above form, a certain distance can be maintained between the silicon atom and the amino group or imino group. As a result, the silicon end is arranged on the surface side of the subject to be treated, and the amino group (amino cation) or imino group (imino cation) is arranged at a certain distance from the surface of the subject to be treated, so that the ionically bonded salt (1) according to the present invention can stably coat the surface of the subject to be treated. Here, the term "coating" includes a form in which the ionically bondable salt (1) is adsorbed to the surface or protrudes from the surface, and a form in which a silicon atom forms a bond with a functional group of the object to be treated.

[0040] Therefore, the silane compound preferably has a certain degree of size, and its molecular weight is preferably at least 100, and more preferably at least 150. On the other hand, there is no particular upper limit, but in consideration of substantially available silane compounds, it is preferably at most 2000 (excluding amino-modified silicone compounds).

[0041] More specifically, the silane compound having a substituent containing an amino group (a silane compound other than an amino-modified silicone compound) preferably has the following structure:

[0042] That is, the ionic salt (1) is represented by the above formula (1): Q + However, the following formula (q-1):

[0043] [ka]

[0044] In the above formula (q-1), X is -CH2- or an oxygen atom (-O-), Y is -NH-, Z is -N(R 7 )2 or -N=C(R 7 )2, R 6 each independently represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms (-OR 8 In this case, R 8 represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, R 7 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms (-OR 9 In this case, R 9 represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, m is an integer from 0 to 5; n is an integer from 0 to 5, q is 0 or 1; r is 0 or 1; It is preferable that the cation is an ionically bonded salt derived from a compound represented by the formula:

[0045] In this specification, the term "substituted or unsubstituted" means that a hydrogen atom of a group may or may not be substituted with another group. There is no particular limitation on the substituent that may be substituted. For example, straight-chain or branched alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms (e.g., cyclopentyl group, cyclohexyl group), hydroxyalkyl groups having 1 to 20 carbon atoms (e.g., hydroxymethyl group, hydroxyethyl group), alkoxyalkyl groups having 2 to 20 carbon atoms (e.g., methoxyethyl group, etc.), alkoxy groups having 1 to 20 carbon atoms (e.g., methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy groups having 3 to 20 carbon atoms (e.g., cyclopentyloxy group, cyclohexyloxy group), alkenyl groups, alkynyl groups, amino groups, aryl groups, aryloxy groups having 6 to 30 carbon atoms (e.g., phenoxy group, naphthyloxy group, etc.), groups), alkylthio groups having 1 to 20 carbon atoms (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group), cycloalkylthio groups having 3 to 20 carbon atoms (for example, cyclopentylthio group, cyclohexylthio group), arylthio groups having 6 to 30 carbon atoms (for example, phenylthio group, naphthylthio group), alkoxycarbonyl groups having 1 to 20 carbon atoms (for example, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group), aryloxycarbonyl groups having 7 to 20 carbon atoms (for example, phenyloxycarbonyl group, naphthyloxycarbonyl group), hydroxy group (-OH), carboxy group (-COOH), thiol group (-SH), cyano group (-CN), and the like. In addition, the number of substituents to be further substituted for one substituent is not particularly limited, and can be appropriately selected in consideration of the desired effect (improvement of water repellency). In addition, in the above, the same substituents are not substituted. For example, a substituted alkyl group is not substituted with an alkyl group.

[0046] In the above formula (q-1), X is a divalent group directly substituted on a silicon atom, and represents -CH2- or an oxygen atom (-O-). Here, q represents the number of X, and is 0 or 1. Therefore, the substituent represented by X does not necessarily have to be included. From the viewpoint of improving the water repellency of the treated object, q=1 is preferable, and in this case, X is preferably -CH2-.

[0047] In the above formula (q-1), Y is a divalent substituent and represents -NH-. Here, r represents the number of Y and is 0 or 1. Therefore, the substituent represented by Y (-NH-) does not necessarily need to be included. From the viewpoints of improving the water repellency of the treated object, the stability of the ionic salt (1), and the ease of arrangement of the ionic salt (1) on the surface of the treated object, it is preferable that r=0, that is, Y does not exist. On the other hand, when Y is present, the substituent can become a secondary amino cation, so from the viewpoint of the stability of the amino cation itself, it is preferable that Y is present.

[0048] In the above formula (q-1), Z is a monovalent substituent, -N(R 7 )2 or -N=C(R 7 )2. Note that R 7 will be described in detail below, and a detailed description will be omitted here. In this way, since the compound represented by formula (q-1) contains an amino group or an imino group as Z, a proton or the like is added to the nitrogen atom in the amino group or imino group, and the compound represented by formula (q-1) tends to become a cation. As a result, the ionically bonded salt (1) can improve the water repellency of the treated object.

[0049] From the viewpoint of improving the water repellency of the treated object and the stability of the ionic salt (1), Z is -N(R 7 In this case, Z is preferably a stable ammonium ion ([-N(R 7 )3] + ) is easy to configure.

[0050] The above ammonium ion ([-N(R 7 )3] + ) in R 7 are each independently a hydrogen atom or another substituent (such as an alkyl group) containing a carbon atom, which will be described in detail below. From the viewpoint of achieving both improved water repellency and antistatic properties of the treated object, R 7 is preferably at least one hydrogen atom (i.e., Z is a primary to tertiary amino cation), more preferably two or more hydrogen atoms (i.e., Z is a primary and secondary amino cation), and particularly preferably all three hydrogen atoms (i.e., Z is a primary amino cation).

[0051] R in the above formula (q-1) 6 and R 7The substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, each of which is represented by the following formula (I) may be linear or branched, and examples thereof include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isoamyl group, a tert-pentyl group, a neopentyl group, an n-hexyl group, a 3-methylpentan-2-yl group, a 3-methylpentan-3-yl group, a 4-methylpentyl group, a 4-methylpentan-2-yl group, a 1,3-dimethylbutyl group, group, 3,3-dimethylbutyl group, 3,3-dimethylbutan-2-yl group, n-heptyl group, 1-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 1-(n-propyl)butyl group, 1,1-dimethylpentyl group, 1,4-dimethylpentyl group, 1,1-diethylpropyl group, 1,3,3-trimethylbutyl group, 1-ethyl-2,2-dimethylpropyl group, n-octyl group, 2-methylhexan-2-yl group, 2,4-dimethylpentan-3-yl group, 1,1-dimethylpentan-1-yl group, yl group, 2,2-dimethylhexane-3-yl group, 2,3-dimethylhexane-2-yl group, 2,5-dimethylhexane-2-yl group, 2,5-dimethylhexane-3-yl group, 3,4-dimethylhexane-3-yl group, 3,5-dimethylhexane-3-yl group, 1-methylheptyl group, 2-methylheptyl group, 5-methylheptyl group, 2-methylheptan-2-yl group, 3-methylheptan-3-yl group, 4-methylheptan-3-yl group, 4-methylheptan-4-yl group, 1-ethylhexyl group, 2-ethylhexyl group, 1-propylpentyl group group, 2-propylpentyl group, 1,1-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 1-ethyl-1-methylpentyl group, 1-ethyl-4-methylpentyl group, 1,1,4-trimethylpentyl group, 2,4,4-trimethylpentyl group, 1-isopropyl-1,2-dimethylpropyl group, 1,1,3,3-tetramethylbutyl group, n-nonyl group, 1-methyloctyl group, 6-methyloctyl group, 1-ethylheptyl group, 1-(n-butyl)pentyl group, 4-methyl-1-(n-propyl)pentyl group, 1,5,Examples of linear and branched alkyl groups include 5-trimethylhexyl group, 1,1,5-trimethylhexyl group, 2-methyloctan-3-yl group, n-decyl group, 1-methylnonyl group, 1-ethyloctyl group, 1-(n-butyl)hexyl group, 1,1-dimethyloctyl group, 3,7-dimethyloctyl group, n-undecyl group, 1-methyldecyl group, 1-ethylnonyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, 1-methyltridecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, and n-nonadecyl group. From the viewpoints of availability and water repellency of the treated object, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms is preferred, a methyl group, an ethyl group, a 2-ethylhexyl group, a tridecyl group, or a 1,2-bis(2-ethylhexyloxycarbonyl)ethyl group is more preferred, and a methyl group, an ethyl group, or a 2-ethylhexyl group is particularly preferred.

[0052] R in the above formula (q-1) 6 and R 7 The substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, each of which is represented by the following formula (I) may be linear or branched, and examples thereof include linear or branched alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, 2-ethylhexyloxy, and octyloxy. From the viewpoints of availability and water repellency of the treated object, substituted or unsubstituted alkoxy groups having 1 to 10 carbon atoms are more preferred, and methoxy, ethoxy, propoxy, isopropoxy, butoxy, and 2-ethylhexyloxy are more preferred.

[0053] R in the above formula (q-1) 6 and R 7Examples of the substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, each represented by the following formula: cyclopropyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group, etc. From the viewpoint of availability and water repellency of the treated object, substituted or unsubstituted cycloalkyl groups having 1 to 10 carbon atoms are more preferred, and cyclopropyl group, cyclopentyl group, and cyclohexyl group are more preferred.

[0054] R in the above formula (q-1) 6 and R 7 Examples of the substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, each represented by the following formula: include a cyclopropyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group. From the viewpoints of availability and water repellency of the treated object, a substituted or unsubstituted cycloalkoxy group having 1 to 10 carbon atoms is more preferred, and a cyclopropyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group are more preferred.

[0055] R in the above formula (q-1) 6 and R 7Examples of the substituted or unsubstituted aryl group having 6 to 30 carbon atoms, each of which is represented by the following formula (I) include, for example, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, a 1-pyrenyl group, a 5-naphthacenyl group, a 1-indenyl group, a 2-azulenyl group, a 9-fluorenyl group, a terphenyl group, a quaterphenyl group, a mesityl group, a pentalenyl group, a binaphthalenyl group, a ternaphthalenyl group, a heptalenyl group, a biphenylenyl group, an indacenyl group, a fluoranthenyl group, an acenaphthylenyl group, an acenaphth ... Examples of the anthrylenyl group include anthryl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quaternanthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, pleiadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl group, trinaphthylenyl group, heptaphenyl group, heptacenyl group, pyrantrenyl group, and ovalenyl group. From the viewpoints of availability and water repellency of the treated object, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms is preferred, and a phenyl group, a dimethylphenyl group (e.g., a 2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, a 3,4-dimethylphenyl group), an isopropylphenyl group (e.g., a 2-isopropylphenyl group, a 3-isopropylphenyl group, a 4-isopropylphenyl group), or a dodecylphenyl group (e.g., a 2-dodecylphenyl group, a 3-dodecylphenyl group, a 4-dodecylphenyl group) is particularly preferred.

[0056] R in the above formula (q-1) 6 and R 7 The substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms is represented by the chemical formula "-OR 8 " or "-OR 9 ", and in this case, R 8 represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. 8The explanation of is the same as for the aryl group described above, and therefore a detailed explanation will be omitted here. From the viewpoints of availability and water repellency of the treated object, a substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms is preferred, and a phenoxy group or a naphthyloxy group is particularly preferred.

[0057] In the above formula (q-1), m and n each independently represent the number of methylene groups (-CH2-), where m is an integer of 0 to 5, and n is an integer of 0 to 5. Here, m+n is an integer of 0 to 10. When Y does not exist (r=0), the number of methylene groups is the same as the value of m+n. For example, when m=1 and n=2 (m+n=3), it is substantially the same as when m=3 and n=0, when m=0 and n=3, and when m=2 and n=1.

[0058] Here, when Y does not exist (r=0), m+n=1 to 8 is preferable, and 1 to 5 is more preferable.

[0059] Furthermore, when Y is present (r=1), m+n is preferably 1 to 8, and more preferably 2 to 6. Here, it is particularly preferable that m=1 to 3 and n=1 to 3.

[0060] In the above formula (q-1), when X is present (q=1) and X is -CH2-, and when adjacent methylene groups (-CH2-: the number of which is defined by m) are also present (m=1 to 5), and the values ​​of q+m are the same, these have the same meaning. Furthermore, when X is present (q=1) and X is -CH2-, and Y is not present (r=0), and the values ​​of q+m+n are the same, these have the same meaning.

[0061] In the above formula (q-1), R substituted on the silicon atom 6At least one of the substituents R on silicon is preferably a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. 6 When is a hydroxy group, an alkoxy group, a cycloalkoxy group, or an aryloxy group, the water repellency of the treated object can be improved for a long period of time. This is believed to be because the above-mentioned substituents (hydroxy group, alkoxy group, cycloalkoxy group, aryloxy group) are hydrolyzed to condense with nearby silicon atoms to form a -(Si-O-Si)- network, or are dehydrated and condensed with the hydroxy groups present on the surface of the treated object to form a siloxane bond.

[0062] Among the compounds represented by the above formula (q-1), the following compounds are preferred from the viewpoint of being particularly effective in improving the water repellency of the treated object and maintaining that performance for a long period of time (i.e., improving durability). That is, the ion-bonding salt (1) is a compound represented by the above formula (q-1), in which X is -CH2- and Z is -N(R 7 )2, and R 6 are each independently a hydrogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, in which R 6 at least one of R is a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms; 7 is a hydrogen atom, m is an integer of 0 to 3, n is 0, q is 1, and r is 0; + It is preferable that the composition includes:

[0063] Furthermore, among the compounds represented by the above formula (q-1), all of R 6 is preferably a hydroxy group or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, and more preferably a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms. The cation Q derived from such a compound + The ionically bondable salt (1) containing the above can particularly maintain the effect of improving the water repellency of the object to be treated for a long period of time.

[0064] Specific examples of compounds that are preferably used as the silane compound containing an amino group or an imino group in the present invention include the following compounds.

[0065] For example, N-(trimethylsilyl)diethylamine, N-(trimethylsilyl)dimethylamine, N-(triethylsilyl)diethylamine, N-(triethylsilyl)dimethylamine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriisopropoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-2(-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, 3-trimethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, and the like.

[0066] In the present invention, the silane compound containing an amino group or an imino group is preferably a silane compound having a substituent containing an amino group (a silane compound other than an amino-modified silicone compound). Furthermore, in a preferred embodiment of the present invention, the silane compound containing an amino group or an imino group does not include an amino-modified polysiloxane, and more preferably does not include an amino-modified silicone compound. In other words, in one embodiment, Q +It is preferable that the compound does not contain a cation derived from the amino-modified polysiloxane, and it is more preferable that the compound does not contain a cation derived from the amino-modified silicone compound.

[0067] (Anion T - ) In the above formula (1), the anion (T - ) is a sulfate ester anion represented by the above formula (t-1), a phosphate ester anion represented by the above formula (t-2), a sulfonate anion represented by the above formula (t-3), or a carboxylate anion represented by the above formula (t-4). These anions have excellent electrical conductivity, and as a result, can greatly contribute to improving the water repellency of the treated object. In addition, these anions provide counter anions with a halogen-free structure as counter anions for the above cations, and are therefore suitable for use in applications where halogens are undesirable. The structures of these anions will be specifically described below.

[0068] A in the above formula (t-1) 1 , A in formula (t-2) 2 and A 3 , and A in formula (t-3) 4 Examples of the linear or branched alkylene group having 2 to 4 carbon atoms, respectively represented by the following formula (1), include an ethylene group, a propylene group, a butylene group, etc. From the viewpoint of availability, an ethylene group and a propylene group are particularly preferred.

[0069] R in the above formula (t-1) 1 , R in formula (t-2) 2 and R 3 , R in formula (t-3) 4 and R in formula (t-4) 5 The substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, the substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, and the substituted or unsubstituted aryl group having 6 to 30 carbon atoms, which are respectively represented by the following formula (q-1), are exemplified by the same groups as the respective substituents in the compound represented by the above formula (q-1), and therefore detailed description thereof will be omitted here.

[0070] In addition, examples of the substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms include, for example, a benzyl group, a phenylethyl group, a 3-phenylpropyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 2-(1-naphthyl)ethyl group, a 2-(2-naphthyl)ethyl group, a 3-(1-naphthyl)propyl group, and a 3-(2-naphthyl)propyl group.

[0071] Furthermore, examples of substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms include, for example, vinyl group, isopropenyl group, 2-propenyl group, 2-methyl-propenyl group, 1-methyl-1-propenyl group, 1-butenyl group, 3-butenyl group, 1-methyl-1-butenyl group, 1,1-dimethyl-3-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-ethyl-1-pentenyl group, 1-hexenyl group, 1-heptenyl group, 2,6-dimethyl-5-heptenyl group, 9-decenyl group, 1-cyclopentenyl group, 2-cyclopentenylmethyl group, cyclohexenyl group, 1-methyl-2-cyclohexenyl group, 1,4-dihydro-2-methylphenyl group, octenyl group, citronellyl group, oleyl group, geranyl group, and farnesyl group. Examples of substituted or unsubstituted cycloalkenyl groups having 3 to 30 carbon atoms include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group, and a cyclodecenyl group.

[0072] From the viewpoints of availability, water repellency, antistatic properties, etc., R 1 ~R 4is more preferably a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and is particularly preferably a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Furthermore, taking into consideration the availability and ease of handling such as viscosity, etc., preferred are n-butyl, n-hexyl, 2-ethylhexyl, dimethylphenyl, isopropylphenyl, and dodecylphenyl groups. From the same viewpoint, R 5 is more preferably a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted linear or branched alkenyl group having 2 to 20 carbon atoms, even more preferably a substituted or unsubstituted linear or branched alkyl group having 1 to 18 carbon atoms or a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, and even more preferably an unsubstituted linear or branched alkyl group having 1 to 18 carbon atoms or an unsubstituted linear alkenyl group having 2 to 20 carbon atoms. Among these, an alkyl group selected from the group consisting of an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-hexylnonan-1-yl group, and an n-hexylundecan-1-yl group, or an alkenyl group selected from the group consisting of a 9-decenyl group, a (Z)-8-heptadecenyl group, a (8Z,11Z)-8,11-heptadecadienyl group, and a (8Z,11Z,14Z)-8,11,14-heptadecatrienyl group is particularly preferred, with an n-heptadecyl group being the most preferred.

[0073] s in the above formula (t-1), t and u in the formula (t-2), and v in the formula (t-3) each represent a divalent substituent -(OA 1~4)-, which is an integer of 0 to 50. From the viewpoint of ease of handling due to a decrease in viscosity, etc., or interface properties, the above s, t, u, and v are each independently preferably an integer of 1 to 40, more preferably an integer of 2 to 30. Here, when the above s, t, u, and v are 1 or more, the ionic salt (1) has an oxyalkylene chain. And, since the oxyalkylene chain has excellent electrical conductivity, the ionic salt (1) containing such an anion further enhances the effect of improving the water repellency of the treated object. Therefore, the above s, t, u, and v are more preferably 1 or more, and particularly preferably 2 or more. On the other hand, when the oxyalkylene chain is too long, the viscosity becomes high, so in consideration of handleability, the above s, t, u, and v are preferably 50 or less, more preferably 40 or less, and particularly preferably 30 or less.

[0074] In the ion-bonding salt (1), the sulfate ester anion represented by formula (t-1), the phosphate ester anion represented by formula (t-2), the sulfonate anion represented by formula (t-3) or the carboxylate anion represented by formula (t-4) is appropriately selected depending on the application. For example, when heating is required in the process of use, sulfonate anions and carboxylates are preferred, and when heating is not required, other anions are preferred.

[0075] (Specific examples of ionic salt (1)) More preferred compounds of the ionically bonded salt (1) represented by the above formula (1) include ionically bonded salts represented by the following chemical formulas (101) to (149).

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082] [ka]

[0083] [ka]

[0084] (Method for producing ionic salt (1)) The method for producing the ionic salt (1) is not particularly limited, and any method can be adopted as long as it can produce an ionic salt having the structure of formula (1). For example, an anion exchange method, a neutralization method, an acid ester method, etc. can be mentioned. In addition, the following deammonification method, etc. can be preferably used.

[0085] That is, the ammonium salt of the sulfate ester anion represented by the above formula (t-1) ([t-1] - [NH4] + ), the ammonium salt of the phosphate ester anion represented by formula (t-2) ([t-2] - [NH4] + ), the ammonium salt of the sulfonate anion represented by the formula (t-3) ([t-3] - [NH4] + ) or the ammonium salt of the carboxylate anion represented by formula (t-4) ([t-4]- [NH4] + ) with the silane compound containing an amino group or an imino group, an ionic salt (1) can be obtained. Here, the ammonium salt of sulfate ester, ammonium salt of phosphoric ester, ammonium salt of sulfonic acid, or ammonium salt of carboxylate may be a commercially available product or may be synthesized in advance. There is no particular restriction on the synthesis method, and for example, the ammonium salt of sulfate ester can be produced by a conventionally known method such as a method of reacting alcohols, phenols, or (poly)oxyalkylene alkyl ethers with sulfamic acid.

[0086] The reaction conditions for producing the ionically bonded salt (1) are not particularly limited, but the following conditions are preferred.

[0087] The molar ratio (feed ratio) of the ammonium salt of sulfate, ammonium salt of phosphoric acid, ammonium salt of sulfonic acid, or ammonium salt of carboxylate to the silane compound containing an amino group or an imino group is preferably 1:1 to 1:2, more preferably 1:1.2 to 1:1.6. If it is within such a range, the reaction proceeds efficiently.

[0088] The reaction solvent that can be used is not particularly limited, and examples thereof include toluene, xylene, ethanol, and the like.

[0089] The reaction atmosphere is not particularly limited, and may be, for example, air or an inert gas atmosphere such as nitrogen or argon, but from the viewpoint of preventing coloration, an inert gas atmosphere such as nitrogen or argon is preferred. Under such conditions, the by-product ammonia is distilled off simultaneously with the reaction.

[0090] The reaction proceeds simultaneously with the production of ammonia as a by-product, and the reaction temperature is preferably 20 to 150° C., more preferably 50 to 130° C. The reaction time is preferably 1 to 6 hours, more preferably 2 to 5 hours.

[0091] After the reaction is completed, a solution containing the ionic salt (1), the unreacted raw material silane compound containing an amino group or an imino group, and the reaction solvent is obtained, and the ionic salt (1) is obtained by distilling off the silane compound containing an amino group or an imino group and the reaction solvent under reduced pressure. The temperature range during this distillation under reduced pressure is preferably 40 to 170°C, more preferably 50 to 160°C. The time period for distillation under reduced pressure is preferably 0.5 to 5 hours, more preferably 1 to 2 hours. The degree of vacuum during distillation under reduced pressure is preferably 0.66 to 6.67 kPa (5 to 50 mmHg), more preferably 1.07 to 2.00 kPa (8 to 15 mmHg).

[0092] [Water repellent treatment agent] The above-mentioned ionically bonded salt (1) is a non-halogenated compound with a small environmental impact, and yet it exhibits an extremely excellent effect as a water repellent treatment agent. In particular, it can be suitably used as a water repellent treatment agent for fibers that have been difficult to impart water repellency to in the past.

[0093] Here, a general silane coupling agent exhibits water repellency by reacting its (alkoxy)silyl group with a hydroxy group present on the surface of the treated object, and the hydrophobic functional group is oriented on the surface. Therefore, if the coupling reaction does not proceed, water repellency is not exhibited, and high-temperature treatment or the like is required. In contrast, the water repellent treatment agent according to the present embodiment can impart water repellency under milder (lower temperature) conditions. In addition, since the water repellent treatment agent according to the present embodiment can form a water repellent portion chemically bonded to the treated object, the water repellent structure formed by treatment using the water repellent treatment agent according to the present embodiment maintains sufficient water repellency even after washing or the like. Furthermore, the water repellent structure formed by treatment using the water repellent treatment agent according to the present embodiment also has high antistatic properties. That is, the water repellent treatment agent according to the present embodiment also has a function as an antistatic agent. There is no particular restriction on the specific performance as an antistatic agent, but it is preferable that the water repellent treatment agent according to the present embodiment has a function as an antistatic agent when the surface resistivity of the treated object is 8×10 11 [Ω / □] or less is preferable, and 1×10 11 [Ω / □] or less is more preferable, and 1×10 10 [Ω / □] or less is more preferable, and 1×10 9 [Ω / □] or less is even more preferable, and 1×10 8 [Ω / □] or less is particularly preferable, and 1×10 7 It is most preferable that the surface resistivity of the object to be treated is equal to or less than [Ω / □]. Note that the value of the surface resistivity of the object to be treated is a value measured by the method described in the Examples section below.

[0094] The reason why the water repellent treatment agent according to this embodiment exhibits the above-mentioned excellent performance is not necessarily clear, but the following reasons are thought to be the reasons. First, the ionic bond salt (1), which is the active ingredient of the water repellent treatment agent, has a hydrophilic part (ionic bond part) and a hydrophobic part in its chemical structure. Therefore, (alkoxy)silyl groups can be regularly oriented toward the surface of the object to be treated, improving reactivity. In addition, the hydrophilic part (ionic bond part) is advantageous for forming silanol bonds since it easily attracts water, and the ionic interaction by the ionic bond part causes the reactive species HO + OH -As a result, the condensation reaction between the (alkoxy)silyl group and the hydroxy group on the surface of the treated object proceeds efficiently. It is believed that this results in high water repellency and its durability. Furthermore, after being fixed to the surface of the treated object through the condensation reaction, the hydrophobic functional groups face the outermost surface to exhibit hydrophobicity (water repellency), and the ionic bonding layer (hydrophilic layer) on the inner layer contributes to electrical conductivity. It is believed that this can reduce the surface resistivity of the surface of the treated object, and can exhibit high antistatic properties to prevent the generation of static electricity.

[0095] The form of the water repellent treatment agent is not particularly limited, and may be in the form of a powder (water repellent treatment agent powder) or in the form of a solution (water repellent treatment agent solution) dissolved or dispersed in a liquid medium. From the viewpoint of excellent handling, ease of operation for imparting water repellency, and uniformity of imparting water repellency, the form of a solution is preferable. Examples of the liquid medium contained in the water repellent treatment agent solution include water, alcohols, a mixed solution of water and alcohols, toluene, xylene, and other aromatic hydrocarbons. Examples of alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and t-butanol. Among these, from the viewpoint of excellent action and effect of the present invention, methanol, ethanol, or isopropanol is preferable as the alcohol, more preferably methanol or isopropanol, and particularly preferably isopropanol. Also, from the viewpoint of excellent action and effect of the present invention, water, alcohols, or a mixed solution of water and alcohols is preferable as the liquid medium, more preferably water or a mixed solution of water and alcohols, and particularly preferably water.

[0096] The content of the liquid medium in the water repellent treatment agent is not particularly limited, and may be, for example, 500 parts by mass or more, or 1000 parts by mass or more, relative to 100 parts by mass of the ionically bonded salt (1). The content of the liquid medium may be, for example, 100,000 parts by mass or less, or 10,000 parts by mass or less, relative to 100 parts by mass of the ionically bonded salt (1).

[0097] From the viewpoint of improving the handleability of the water repellent treatment agent, the liquid medium is preferably a liquid medium having a boiling point of 70° C. or more, and more preferably a liquid medium having a boiling point of 80° C. or more. Moreover, from the viewpoint of facilitating treatment with the water repellent treatment agent, the liquid medium is preferably a liquid medium having a boiling point of 203° C. or less, and more preferably a liquid medium having a boiling point of 110° C. or less.

[0098] In addition, when actually used, the water repellent may be further diluted. That is, the water repellent may be diluted, for example, 3 to 100 times, preferably 3 to 30 times, with a dilution medium and used as a diluted water repellent. The dilution medium may be the same liquid medium as the liquid medium in the water repellent, or may be a liquid medium different from the liquid medium in the water repellent. From the viewpoint of excellent workability and safety, the dilution medium is preferably water.

[0099] The water repellent treatment agent according to this embodiment may further contain other components other than those described above. Examples of other components include polysiloxane compounds, dispersants, stabilizers, compatibilizers, organic acids, and the like. However, it is preferable that the water repellent treatment agent does not contain a polysiloxane compound. It is also preferable that the water repellent treatment agent does not contain a surfactant. It is more preferable that the water repellent treatment agent does not contain any of these other components. That is, the water repellent treatment agent according to a preferred embodiment is composed of an ion-bonding salt (1) and water.

[0100] [Water-repellent structure] The water-repellent treatment agent according to the above-mentioned embodiment is used for the purpose of performing water-repellent treatment on a treated object. The treated object thus treated with water-repellent treatment is referred to as a "water-repellent structure" in this specification. That is, according to another embodiment of the present invention, there is also provided a water-repellent structure including a treated object and a water-repellent portion formed on the treated object. Here, it is preferable that the water-repellent portion in the water-repellent structure includes a structure derived from a cation constituting the ion-bonding salt (1) contained in the water-repellent treatment agent (preferably a water-repellent treatment agent solution) according to the above-mentioned embodiment.

[0101] Fig. 1 is a schematic diagram showing a water-repellent structure according to one embodiment of the present invention. As shown in Fig. 1, the water-repellent structure 10 includes a treatment target 1 and a water-repellent portion 2 on the treatment target 1 (on the treatment surface of the treatment target). Here, the water-repellent portion 2 contains a dried product of a water-repellent treatment agent, or contains a structure derived from a cation constituting an ion-bonding salt (1) contained in the water-repellent treatment agent (preferably a water-repellent treatment agent solution).

[0102] The material of the workpiece is not particularly limited, but examples thereof include metal, ceramics, glass, resin, and combinations thereof (composite materials, laminated materials, etc.). The form of the workpiece may be a plate-like or block-like bulk body, fiber, particle, etc. The workpiece may be a fiber aggregate (woven or nonwoven fabric), particle aggregate, etc.

[0103] Examples of metals include stainless steel, aluminum, copper, galvanized steel sheet, and iron. Examples of ceramics include alumina, barium titanate, boron nitride, and silicon nitride. Examples of glass include normal soda lime glass, borosilicate glass, alkali-free glass, quartz glass, and aluminosilicate glass. Resins may be either thermosetting resins or thermoplastic resins. Examples of thermosetting resins include phenolic resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, urethane resins, and thermosetting polyimide resins. Examples of thermoplastic resins include (meth)acrylic resins, styrene resins, polyester resins, polycarbonate resins, olefin resins (polyethylene, polypropylene, etc.; also including cyclic olefin resins), polyamide resins, halogen-containing resins (polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, etc.), polyvinyl ester resins such as polyvinyl acetate, acrylonitrile-butadiene-styrene copolymers (ABS resins), acrylonitrile-styrene copolymers (AS resins), polyacetal resins, etc. When the thermosetting resins or thermoplastic resins are copolymers, the form of the copolymer may be any of block copolymers, random copolymers, graft copolymers, and alternating copolymers.

[0104] As described above, when a hydroxy group is present on the surface of the object to be treated, the (alkoxy)silyl group of the ionic salt (1) undergoes a condensation reaction with the hydroxy group and bonds to the surface of the object to be treated, thereby exhibiting excellent water repellency and antistatic properties. From this viewpoint, the object to be treated is preferably one having a large number of hydroxy groups on the surface. From this viewpoint, examples of objects having a large number of hydroxy groups on the surface of the object to be treated include glass, resin, stone, carbon fiber composite materials (e.g., gas diffusion electrodes and gas diffusion supports of fuel cells), paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, and plaster, but it is preferable that the object contains glass or resin. Among these forms, when the object to be treated is a resin, the large number of hydroxy groups present on the surface of the object to be treated may be bonded to the polymer chain of the resin contained in the object to be treated. Examples of methods for imparting hydroxy groups to the resin include a method of copolymerizing a monomer having a hydroxyl group into the structure and a monomer that generates a hydroxy group by reaction. Examples of monomers containing a hydroxy group include acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate, caprolactone-modified monomers such as caprolactone-modified 2-hydroxyethyl (meth)acrylate, oxyalkylene-modified monomers such as diethylene glycol (meth)acrylate and polyethylene glycol (meth)acrylate, primary hydroxy group-containing monomers such as 2-acryloyloxyethyl-2-hydroxyethyl phthalate, N-methylol (meth)acrylamide, and hydroxyethyl acrylamide, secondary hydroxy group-containing monomers such as 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 3-chloro 2-hydroxypropyl (meth)acrylate, and hydroxy group-containing monomers such as 2,2-dimethyl 2-hydroxyethyl (meth)acrylate. These may be used alone or in combination of two or more.Examples of monomers that generate a hydroxy group upon reaction include monomers having an epoxy group, a glycidyl group, an alkoxysilyl group, and the like.

[0105] However, without being limited to such a form, when the treated object contains filler particles in addition to the resin, even if the hydroxyl groups present on the surface of the treated object are the hydroxyl groups present on the surface of the filler particles, excellent water repellency and antistatic properties can be exhibited by the same mechanism. Examples of such filler particles include silicon-based inorganic compounds such as silica, quartz, glass, and silicon; metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; silicate compounds such as talc, mica, aluminosilicates, and kaolin; metal oxides such as zinc oxide, tin oxide, aluminum oxide, magnesium oxide, iron oxide, titanium oxide, and chromium oxide; carbonates such as calcium carbonate and magnesium carbonate, gypsum, barium sulfate, and the like. Examples of fillers include sulfates such as sodium, carbons such as graphite, carbon nanotubes, carbon black, and carbon fibers, cellulose fibers, resin fillers (for example, resin fillers having a hydroxyl group in the structure), aluminum nitride, boron nitride, silicon carbide, and silicon nitride.

[0106] Since the water repellent treatment agent according to the present embodiment is suitable as a water repellent treatment agent for fibers, the material of the agent to be treated is not limited, and the shape of the object to be treated is preferably fiber. That is, in a preferred embodiment, the water repellent treatment agent according to the present embodiment is for fiber treatment. Examples of fibers include natural fibers of animal and plant origin such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyacetal, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers, cellulose fibers, and mixtures thereof. These fibers also have many hydroxyl groups on their surfaces, and can exhibit excellent water repellency and antistatic properties by being treated for water repellency using the water repellent treatment agent according to one embodiment of the present invention.

[0107] The thickness of the water-repellent portion is not particularly limited, and may be, for example, 0.1 nm to 10 μm, or 0.2 nm to 1 μm, from the viewpoint of maintaining the texture. The water-repellent structure may have a water contact angle (25° C.) of 110° or more with respect to a 2 μL droplet of ultrapure water in the water-repellent portion. This water contact angle is preferably 120° or more, more preferably 130° or more, and even more preferably 140° or more. The value of the water contact angle (25° C.) is a value measured by the method described in the Examples section below.

[0108] [Method of manufacturing water-repellent structure] According to yet another aspect of the present invention, there is also provided a method for producing a water-repellent structure, which includes treating a target object with the water-repellent treatment agent (preferably a water-repellent treatment solution) according to the above-mentioned aspect (water-repellent treatment step). Here, the water-repellent treatment step may include the following contact step and treatment step.

[0109] (contact process) The contact step is a step of contacting the object to be treated with the water repellent treatment agent. At this time, the entire object to be treated may be contacted with the water repellent treatment agent, or only a part of the object to be treated may be selectively contacted with the water repellent treatment agent.

[0110] The method for carrying out the contact step is not particularly limited, and examples thereof include coating methods such as spin coating, dip coating, spray coating, flow coating, bar coating, and gravure coating. In addition, as a simpler method, a method of immersing or impregnating the treated object in a water repellent treatment agent in the form of a solution (water repellent treatment agent solution) may be adopted. The temperature of the water repellent treatment agent used in the contact step is not particularly limited, and may be, for example, 20 to 80°C, or 25 to 60°C. In addition, the contact time with the water repellent treatment agent may be, for example, 30 seconds to 4 hours, or 1 to 10 minutes.

[0111] (Processing) In the treatment step, the object to be treated to which the water repellent agent and the liquid medium are attached in the contact step is heated and / or dried, etc., to form a water repellent part on the object to be treated, and at the same time, the liquid medium is volatilized. The liquid medium can be volatilized, for example, by leaving it at room temperature, but from the viewpoint of productivity, it is preferable to volatilize it by heating. Here, the treatment temperature in the heating and / or drying step is not particularly limited, and may be, for example, 60 to 250°C or 70 to 180°C, although it varies depending on the heat resistance temperature of the object to be treated. As described above, the water repellent agent according to this embodiment can impart water repellency under milder (lower temperature) conditions. From this viewpoint, the above-mentioned treatment temperature is preferably 80 to 150°C, more preferably 80 to 130°C, and even more preferably 80 to 110°C. EXAMPLES

[0112] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. In the following, the terms "parts" or "%" may be used, but they represent "parts by mass" or "% by mass" unless otherwise specified.

[0113] [Examples of synthesis of ionic salts] (Synthesis Example 1: Synthesis of [APM-Si] [EHDG-S]) 150.0 parts by mass of diethylene glycol mono 2-ethylhexyl ether (trade name: 2-ethylhexyl diglycol, abbreviation: EHDG, manufactured by Nippon Nyukazai Co., Ltd.) was added with 150.0 parts by mass of toluene, and the temperature was raised to 110°C. 80.2 parts by mass of sulfamic acid was added thereto and reacted for 3 hours. After the reaction, the excess sulfamic acid was filtered off, and diethylene glycol mono 2-ethylhexyl ether sulfate ester ammonium salt (abbreviation: EHDG-SF; ammonium ion is NH4 + ) in toluene was obtained.

[0114] To 100.0 parts by mass of a 50% toluene solution of EHDG-SF obtained above, 42.7 parts by mass of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name KBM-903, abbreviation: APM-Si) was added and reacted at 120°C for 3 hours (the molar ratio of EHDG-SF to APM-Si was 1:1.5).

[0115] After the reaction was completed, toluene and unreacted APM-Si were distilled off under reduced pressure (temperature: 150°C, degree of vacuum: 1.33 kPa (10 mmHg)), and 72.3 parts by mass of the target ionic salt (1) (abbreviation: [APM-Si][EHDG-S]; the compound represented by the above chemical formula (101)) was obtained.

[0116] (Synthesis Example 2: Synthesis of [MEM][EHDG-S]) The target ionic salt (2) (abbreviation: [MEM][EHDG-S]) was obtained in the same manner as in Synthesis Example 1 above, except that N-ethylethanolamine (manufactured by Nippon Nyukazai Co., Ltd., trade name: Aminoalcohol MEM, abbreviation: MEM) was used instead of APM-Si. Note that the molar ratio of EHDG-SF to MEM was 1:1.5.

[0117] (Synthesis Example 3: Synthesis of [APM-Si] [HeDG-S]) 130.7 parts by mass of diethylene glycol hexyl ether (manufactured by Nippon Nyukazai Co., Ltd., product name: hexyl diglycol, abbreviation: HeDG) was added to 130.7 parts by mass of toluene, and the temperature was raised to 110°C. 80.2 parts by mass of sulfamic acid was added thereto and reacted for 3 hours. After the reaction, the excess sulfamic acid was filtered off, and diethylene glycol hexyl ether sulfate ester ammonium salt (abbreviation: HeDG-SF; ammonium ion is NH4 + )'s Torue A solution was obtained.

[0118] To 100.0 parts by mass of a 50% toluene solution of HeDG-SF obtained above, 46.8 parts by mass of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name KBM-903, abbreviation: APM-Si) was added and reacted at 120°C for 3 hours (the molar ratio of HeDG-SF to APM-Si was 1:1.5).

[0119] After the reaction was completed, toluene and unreacted APM-Si were distilled off under reduced pressure (temperature: 150° C., degree of vacuum: 1.33 kPa (10 mmHg)), and 74.8 parts by mass of the target ionic salt (3) (abbreviation: [APM-Si][HeDG-S]; the compound represented by the above chemical formula (117)) was obtained.

[0120] (Synthesis Example 4: Synthesis of [APM-Si][Und-COOH]) 179.3 parts by mass of APM-Si was added dropwise to 186.2 parts by mass of undecylenic acid (manufactured by Ito Oil Mills, Ltd., product name: undecylenic acid, abbreviation: Und-COOH) and the mixture was allowed to react for 1 hour, thereby obtaining 365.5 parts by mass of the target ionic liquid (abbreviation: [APM-Si][Und-COOH]; the compound represented by the above chemical formula (118)).

[0121] (Synthesis Example 5: Synthesis of [TEA][Und-COOH]) To 186.2 parts by mass of undecylenic acid (manufactured by Ito Oil Mills, product name: undecylenic acid, abbreviation: Und-COOH), 101.2 parts by mass of TEA (triethylamine, reagent: Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise and reacted for 1 hour to obtain the desired ionic liquid (abbreviation: 287.2 parts by mass of the product (name: [TEA][Und-COOH]) was obtained.

[0122] (Synthesis Example 6: Synthesis of [APM-Si][OLE-COOH]) 179.3 parts by mass of APM-Si was added dropwise to 282.5 parts by mass of oleic acid (manufactured by Kao Corporation, product name: Lunac OV, abbreviation: OLE-COOH) and reacted for 1 hour to obtain the desired product. As a result, 461.8 parts by mass of an ionic liquid (abbreviation: [APM-Si][OLE-COOH]; a compound represented by the above chemical formula (119)) was obtained.

[0123] (Synthesis Example 7: Synthesis of [APM-Si][DOSS]) Dioctyl fumarate 200.0 parts by mass, 50% ammonium hydrogen sulfite aqueous solution 116.4 parts by mass of ethanol, 37.0 parts by mass of methanol, and 15.6 parts by mass of water were charged into an autoclave. The temperature was raised to 120° C. and the reaction was carried out for 24 hours. The maximum pressure during this reaction was 0.25 MPa.

[0124] The above obtained ammonium dioctyl sulfosuccinate (abbreviation: DOSS-NH4) After 140.0 parts by mass of the solvent was replaced with toluene by reflux dehydration, 61.1 parts by mass of APM-Si was added (the molar ratio of DOSS-NH4 to APM-Si was 1:1.5).

[0125] After the charging, the mixture was reacted for 3 hours at 90° C. After the reaction was completed, the toluene and unreacted APM-Si were distilled off under reduced pressure (temperature: 90° C., degree of vacuum: 1.33 kPa (10 mmHg)), and 123.2 parts by mass of the target ionic liquid (abbreviation: [APM-Si][DOSS]; the compound represented by the above chemical formula (109)) was obtained.

[0126] (Synthesis Example 8: Synthesis of [MEM] [DOSS]) Without replacing the solvent in 140.0 parts by mass of ammonium dioctylsulfosuccinate (abbreviation: DOSS-NH4) obtained above, 30.4 parts by mass of MEM was added (the molar ratio of DOSS-NH4 to MEM was 1:1.5).

[0127] After the charging, the mixture was reacted for 3 hours at 80° C. After the reaction was completed, methanol, water and unreacted MEM were distilled off under reduced pressure (temperature: 125° C., degree of vacuum: 1.33 kPa (10 mmHg)), and 115.0 parts by mass of the target ionic liquid (abbreviation: [MEM][DOSS]) was obtained.

[0128] (Synthesis Example 9: Synthesis of [APM-Si][Lau-COOH]) 179.3 parts by mass of APM-Si was added dropwise to 200.3 parts by mass of lauric acid (manufactured by Kao Corporation, product name: Lunac L-98, abbreviation: Lau-COOH), and the mixture was allowed to react for 1 hour to obtain 379.6 parts by mass of the desired ionic liquid (abbreviation: [APM-Si][Lau-COOH]).

[0129] (Synthesis Example 10: Synthesis of [APM-Si][iso-Pal-COOH]) 179.3 parts by mass of APM-Si was added dropwise to 256.4 parts by mass of isopalmitic acid (manufactured by Nissan Chemical Industries, Ltd., product name: isopalmitic acid KS, abbreviation: iso-Pal-COOH) and the mixture was allowed to react for 1 hour to obtain 435.7 parts by mass of the desired ionic liquid (abbreviation: [APM-Si][iso-Pal-COOH]).

[0130] (Synthesis Example 11: Synthesis of [APM-Si][Ste-COOH]) 179.3 parts by mass of APM-Si was added dropwise to 284.5 parts by mass of stearic acid (manufactured by Kao Corporation, product name: Lunac S-90V, abbreviation: Ste-COOH) and the mixture was allowed to react for 1 hour to obtain 463.8 parts by mass of the desired ionic liquid (abbreviation: [APM-Si][Ste-COOH]).

[0131] (Synthesis Example 12: Synthesis of [APM-Si][iso-Ste-COOH]) 179.3 parts by mass of APM-Si was added dropwise to 284.5 parts by mass of isostearic acid (manufactured by Nissan Chemical Industries, Ltd., product name: Isostearic acid T, abbreviation: iso-Ste-COOH), and the mixture was allowed to react for 1 hour to obtain 463.8 parts by mass of the desired ionic liquid (abbreviation: [APM-Si][iso-Ste-COOH]).

[0132] [Water-repellent treatment of textiles] By treating pieces of fiber with the solution containing the ion-bonding salt or other compounds prepared above in the following manner, water-repellent treatment of the fibers was performed as in the examples and comparative examples shown in Table 1 below. Note that, for the examples and comparative examples other than the experimental examples described below, water-repellent treatment of the fibers was performed using the same method as the experimental examples described below, except that at least one of the type of water-repellent treatment agent, dilution concentration, type of dilution solvent, type of fiber, and treatment temperature was changed.

[0133] Example 1 One part by mass of [APM-Si][EHDG-S] prepared in Synthesis Example 1 above was dissolved in 19 parts by mass of pure water to prepare a 5% aqueous solution. Next, a 5 cm square fiber piece (manufactured by Iwatsuki Co., Ltd., product name: Iwatsuki Bleached, material: 100% cotton, 20 count cotton yarn) was impregnated with this solution for 10 minutes. The impregnated fiber piece was then dried at 110°C for 30 minutes to obtain a water-repellent treated fiber piece.

[0134] Example 2 2 parts by mass of [APM-Si][EHDG-S] prepared in Synthesis Example 1 above was dissolved in 18 parts by mass of pure water to prepare a 10% aqueous solution. Next, a 5 cm square fiber piece (manufactured by Iwatsuki Co., Ltd., product name: Iwatsuki Bleached, material: 100% cotton, 20 count cotton yarn) was impregnated with this solution for 10 minutes. The impregnated fiber piece was then dried at 110°C for 30 minutes to obtain a water-repellent treated fiber piece.

[0135] Example 5 2 parts by mass of [APM-Si][EHDG-S] prepared in the above Synthesis Example 1 was dissolved in 18 parts by mass of a mixed solvent of isopropanol (IPA) (reagent: Fujifilm Wako Pure Chemical Industries, Ltd.) and pure water (mixture weight ratio 1:1) to obtain a 10% aqueous solution. Next, a 5 cm square fiber piece (manufactured by Iwatsuki Co., Ltd., product name: Iwatsuki Bleached, material: 100% cotton, 20 count cotton yarn) was impregnated with this solution for 10 minutes. The impregnated fiber piece was then dried at 110°C for 30 minutes to obtain a water-repellent treated fiber piece.

[0136] Example 7 4 parts by mass of [APM-Si][EHDG-S] prepared in Synthesis Example 1 above was dissolved in 16 parts by mass of methanol (reagent: Fujifilm Wako Pure Chemical Industries, Ltd.) to prepare a 20% aqueous solution. Next, a 5 cm square fiber piece (manufactured by Iwatsuki Corporation, product name: Iwatsuki Bleached, material: 100% cotton, 20 count cotton yarn) was impregnated with this solution for 10 minutes. The impregnated fiber piece was then dried at 110°C for 30 minutes to obtain a water-repellent treated fiber piece.

[0137] Example 9 2 parts by mass of [APM-Si][EHDG-S] prepared in Synthesis Example 1 above was dissolved in 18 parts by mass of pure water to prepare a 10% aqueous solution. Next, a 5 cm square fiber piece (manufactured by Daio Paper Corporation, product name: Elleair Rakurakukku, material: 100% pulp) was immersed in this solution for 10 minutes. The impregnated fiber piece was then dried at 110°C for 30 minutes to obtain a water-repellent treated fiber piece.

[0138] Example 10 2 parts by mass of [APM-Si][EHDG-S] prepared in Synthesis Example 1 above was dissolved in 18 parts by mass of pure water to prepare a 10% aqueous solution, and a 5 cm square fiber piece (workwear piece manufactured by Midori Anzen Co., Ltd., material: 65% polyester, 35% cotton) was immersed in this solution for 10 minutes. The impregnated fiber piece was then dried at 110°C for 30 minutes to obtain a water-repellent treated fiber piece.

[0139] [Evaluation of water repellent treatment agents] The water repellent treatment agents (solutions) used in the examples and comparative examples were evaluated for flammability and appearance according to the following indices. The results are shown in Table 1 below: (Flammability rating) The flash point was measured using a Cleveland open-cup automatic flash point measuring device in accordance with JIS K 2265-4. As a result, the flash point was evaluated as "x" when the flash point was less than 100°C, and as "○" when the flash point was 100°C or higher: (Appearance evaluation) The appearance of the water repellent treatment agent (solution) was evaluated according to the following criteria. Note that "x" indicates that the liquid was separated into layers during impregnation and therefore evaluation was not possible: 〇:Transparent △: Cloudy ×: split layer.

[0140] [Evaluation of water-repellent treated fabric pieces] The water repellency (water contact angle) and antistatic property (surface resistivity) of the fiber pieces treated for water repellency as described above were evaluated by the following method. The results are shown in Table 1 below. In Examples 3 and 4, the fiber pieces treated for water repellency as described in Example 2 were evaluated after being subjected to simple washing once or twice by the following method.

[0141] (Simple washing method) A 100 mL beaker was charged with 0.25 parts by weight of a neutral laundry detergent (Kao Corporation, product name: Attack ZERO) and 49.75 parts by weight of tap water, and a stirring bar was added and the mixture was stirred and mixed at 200 rpm using a magnetic stirrer. The water-repellent treated test piece was placed in this detergent solution and stirred for 30 seconds, and then rinsed under running water until no more bubbles were produced. The test piece was squeezed to dehydrate it, and then dried at room temperature for 12 hours.

[0142] (Evaluation of water repellency) Water droplets of 0.03 g were dropped onto three locations on the surface of the water-repellent treated fabric piece, and the state of the fabric after 10 seconds was evaluated according to the following criteria: ○: All water remains as droplets on the fibers (water repellent) ×: Water is absorbed into the fiber in one or more places (not water repellent).

[0143] (Water contact angle measurement) The water contact angle (25°C) was measured for some of the fibers that showed water repellency in the above water repellency evaluation. Specifically, a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., model number: CA-XP) was used to create a droplet of about 2 μL using pure water as the liquid on the tip of a needle in a dry state (25°C / 50%RH), and this was brought into contact with the surface of the test piece to create a droplet on the surface of the test piece. The angle on the side containing the liquid among the angles formed by the tangent to the liquid surface and the test piece surface at the point where the test piece and the liquid come into contact was measured as the water contact angle. Note that the distinction between hydrophilicity and water repellency is relative, but if the water contact angle value is 90° or more, it can be said that the water-repellent treated fiber piece is particularly excellent in water repellency, and especially if it is 110° or more, it can be said to be highly water repellent. In addition, the water contact angle of fibers that did not show water repellency can be considered to be 0°.

[0144] (Measurement of surface resistivity) The surface resistivity (Ω / □) of a portion of the water-repellent treated fiber piece was measured using a high resistivity meter, Hirester UP (manufactured by Mitsubishi Chemical Analytech Co., Ltd.), at a measurement temperature of 25°C, humidity of 50% RH, and applied voltage of 10 V. The surface resistivity value was 8×10 11 If the resistance is [Ω / □] or less, it can be said that the water-repellent treated fiber piece also has excellent antistatic properties.

[0145] [Table 1-1]

[0146] [Table 1-2]

[0147] From the results shown in Table 1, it can be seen that the fiber pieces treated with the water repellent treatment agent of each Example exhibit water repellency even when dried at a low temperature (110°C), and also exhibit excellent antistatic properties. In contrast, in Comparative Example 7 and Comparative Example 11, the water repellent treatment agent was separated into layers, and water repellency could not be performed. In Comparative Examples 13 to 15, which were not treated with a water repellent treatment agent, Comparative Examples 1 to 3, which were treated with a water repellent treatment agent containing an ion-bonding salt other than the ion-bonding salt (1) of the present invention, and Comparative Examples 4 to 5, 8 to 9, and 12, which were treated with a water repellent treatment agent containing a silane compound, the fiber pieces did not exhibit water repellency when dried at a low temperature (110°C), and in Comparative Example 10, the fiber pieces did not exhibit water repellency even when dried at a high temperature (160°C). Furthermore, in Comparative Example 6, water repellency was exhibited when dried at a high temperature, but antistatic properties were lost.

[0148] [Water-repellent treatment of glass surface] The surface of a glass plate was treated with a solution containing the ion-bonding salt prepared above or other compound by the following method, thereby performing a water-repellent treatment on the surface of the glass plate as in the Examples and Comparative Examples shown in Table 2 below. Note that for the Examples and Comparative Examples other than the Experimental Examples described below, the water-repellent treatment on the surface of the glass plate was performed using the same method as the Experimental Examples described below, except that at least one of the type of water-repellent agent and the type of dilution solvent was changed.

[0149] (Example 30) 2 parts by mass of [APM-Si][EHDG-S] prepared in the above Synthesis Example 1 was dissolved in 18 parts by mass of a mixed solvent of isopropanol (reagent: Fujifilm Wako Pure Chemical Industries, Ltd.) and pure water (mixture weight ratio 1:1) to obtain a 10% aqueous solution. Next, this solution was applied to a glass plate in a film thickness of 15 μm and dried in a dryer at 110° C. for 30 minutes to obtain a water-repellent treated test piece.

[0150] For the other examples and comparative examples, test pieces were obtained that were water-repellent treated in the same manner as in the above examples, except that the type of water-repellent agent and the dilution solvent were changed.

[0151] [Evaluation of water-repellent treated glass sheets] The water repellency (water contact angle) and (surface resistivity) of the glass plate subjected to the water repellency treatment described above were evaluated by the following methods. The results are shown in Table 2 below.

[0152] (Water contact angle measurement) The water contact angle (25°C) of the water-repellent treated test piece was measured. Specifically, a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., model number: CA-XP) was used to make a droplet of about 2μL using pure water as the liquid at a dry state (25°C / 50%RH) on the tip of a needle, which was then brought into contact with the surface of the test piece to make a droplet on the surface of the test piece. The angle on the side containing the liquid among the angles made by the tangent to the liquid surface and the test piece surface at the point where the test piece and the liquid come into contact was measured as the contact angle. Note that the distinction between hydrophilicity and water repellency is relative, but if the value of this water contact angle is 75° or more, it can be said that the surface of the water-repellent treated glass plate has excellent water repellency. In addition, the value of this water contact angle is more preferably 80° or more, even more preferably 85° or more, particularly preferably 90° or more, and most preferably 100° or more.

[0153] (Measurement of surface resistivity) The surface resistivity (Ω / □) of the water-repellent treated test piece was measured using a high resistivity meter Hirester UP (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) at a measurement temperature of 25°C, humidity of 50% RH, and applied voltage of 10 V. The surface resistivity value was 8×10 11 If the resistivity is [Ω / □] or less, it can be said that the surface of the water-repellent treated glass plate also has excellent antistatic properties.

[0154] [Table 2]

[0155] From the results shown in Table 2, it can be seen that the surfaces of the glass plates treated with the water repellent treatment agents of Examples 30 to 34 all exhibit water repellency even when dried at a low temperature (110°C), and also exhibit excellent antistatic properties. In contrast, water repellency was not obtained in Comparative Example 18, which was not treated with a water repellent treatment agent. Moreover, in Comparative Examples 16 to 17, which were treated with a water repellent treatment agent containing a silane compound, it was not possible to achieve both water repellency and antistatic properties when dried at a low temperature (110°C).

Claims

1. A water repellent treatment agent comprising an ionically bonded salt represented by the following formula (1): 【Chemistry 1】 In the above formula (1), Q ＋ is a cation derived from a silane compound containing an amino group or an imino group; In the above formula (1), T － is expressed by the following formula (t-1): 【Chemistry 2】 In the above formula (t-1), R １ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms; A １ is a linear or branched alkylene group having 2 to 4 carbon atoms, s is an integer from 0 to 50; A sulfate ester anion represented by the formula: The following formula (t-2): 【Chemistry 3】 In the above formula (t-2), R ２ and R ３ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, in which R ２ and R ３ is not a hydrogen atom at the same time, A ２ and A ３ are each independently a linear or branched alkylene group having 2 to 4 carbon atoms, t and u are each independently an integer from 0 to 50; A phosphate ester anion represented by the formula: The following formula (t-3): 【Chemistry 4】 In the above formula (t-3), R ４ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms; A ４ is a linear or branched alkylene group having 2 to 4 carbon atoms, v is an integer from 0 to 50; or a sulfonate anion represented by The following formula (t-4): 【Chemistry 5】 In the above formula (t-4), R ５ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms; It is a carboxylate anion represented by the formula:

2. In the above formula (1), Q ＋ is represented by the following formula (q-1): 【Chemistry 6】 In the above formula (q-1), X is -CH ２ - or an oxygen atom (-O-), Y is -NH-, Z is -N(R ７ ) ２ Or -N=C(R ７ ) ２ and R ６ are each independently a hydrogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms (-OR ８ In this case, R ８ represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; R ７ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms (-OR ９ In this case, R ９ represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; m is an integer from 0 to 5; n is an integer from 0 to 5, q is 0 or 1; r is 0 or 1; 2. The water repellent treatment agent according to claim 1, wherein the cation is derived from a compound represented by the formula:

3. R ６ The water repellent treatment agent according to claim 2, wherein at least one of the above is a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.

4. In the formula (q-1), X is -CH ２ - and Z is -N(R ７ ) ２ and R ６ each independently represents a hydrogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms; R ７ is a hydrogen atom, m is an integer from 0 to 3; n is 0, q is 0 or 1; The water repellent treatment agent according to claim 2 , wherein r is 0.

5. In the above formula (1), Q ＋ The water repellent treatment agent according to claim 1 , which does not contain a cation derived from the amino-modified polysiloxane.

6. The water repellent treatment agent according to claim 1 , which has a function as an antistatic agent.

7. The surface resistivity of the treated object using the water repellent treatment agent is 8×10 １１ The water repellent treatment agent according to claim 6, having a water repellency of [Ω / □] or less.

8. The water repellent treatment agent according to claim 1, which is for treating fibers.

9. A water repellent treatment solution comprising the water repellent treatment agent according to claim 1 and a liquid medium.

10. The water repellent treatment solution according to claim 9, which does not contain a surfactant.

11. The method includes: The water-repellent portion includes a structure derived from the cation constituting the ion-bonding salt (1) contained in the water-repellent treatment agent according to any one of claims 1 to 8, or the water-repellent treatment agent solution according to claim 9 or 10. A water-repellent structure.

12. The water-repellent structure according to claim 11, wherein the object to be treated has a large number of hydroxyl groups on the surface thereof.

13. The water-repellent structure according to claim 12 , wherein the object to be treated comprises glass or resin.

14. The water-repellent structure according to claim 13 , wherein the object to be treated contains a resin, and the hydroxy group is a hydroxy group bonded to a polymer chain of the resin.

15. The water-repellent structure according to claim 13 , wherein the object to be treated contains a resin and filler particles, and the hydroxyl groups are hydroxyl groups present on the surfaces of the filler particles.

16. The water-repellent structure according to claim 14, wherein the object to be treated is a fiber.

17. A method for producing a water-repellent structure, comprising treating an object with the water-repellent treatment agent according to any one of claims 1 to 8 or the water-repellent treatment solution according to claim 9 or 10.

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