Water-repellent agent composition and method for producing same

Abstract

Provided is a water-repellent agent composition comprising: a polymer (A) including a repeating unit derived from a hydrocarbon group-containing monomer (a) that has a hydrocarbon group having 2-40 carbon atoms; and a silicone compound (B) formed of a non-resin-based silicone and a resin-based silicone. In a GPC chart of the silicone compound (B), a peak top exists in a molecular weight range of not less than 1500. Components having a molecular weight not less than 1500 in the silicone compound include a non-resin-based silicone other than an amino-modified silicone. The amount of the silicone compound (B) with respect to the total of the amount of the polymer (A) and the amount of the silicone compound (B) is 51-99 wt%. The present disclosure can provide a water-repellent agent composition that can impart good chalk marking resistance and good water repellency to a base material (in particular, fiber products).

Description

Water-repellent composition and method for producing the same

[0001] This disclosure relates to a water-repellent composition and a method for producing the same.

[0002] Development of non-fluorine-based water repellents is underway to impart water repellency to base materials (especially textile products).

[0003] Japanese Patent Publication No. 2024-3104, Japanese Patent Publication No. 2023-85382

[0004] When water-repellent agents are used on textile products, not only water repellency but also resistance to chalk marks and seam slippage are required. Conventional water-repellent agents have not focused on or suggested resistance to chalk marks and seam slippage.

[0005] The present disclosure aims to provide a water-repellent composition that can impart good water repellency, chalk mark resistance, and seam slip resistance to a substrate (particularly textile products).

[0006] This disclosure includes the following embodiments: [Claim 1] A water-repellent composition comprising a polymer (A) having repeating units derived from a hydrocarbon group-containing monomer (a) having hydrocarbon groups having 2 to 40 carbon atoms, and a silicone compound (B) consisting of resin-based silicone and non-resin-based silicone, wherein in the GPC chart of the silicone compound (B), a peak top exists in the region of molecular weight 1500 or more, and the component of the silicone compound with a molecular weight of 1500 or more includes a non-resin-based silicone other than an amino-modified silicone, and the amount of the silicone compound (B) is 51 to 99% by weight of the sum of the amount of the polymer (A) and the amount of the silicone compound (B). [Claim 2] The water-repellent composition according to Claim 1, wherein the hydrocarbon group in the hydrocarbon group-containing monomer (a) is a linear alkyl group having 10 or more carbon atoms. [Claim 3] The hydrocarbon group-containing monomer (a) is of the formula: CH ２ = C(-X) ａ ) - C (= O) - Y ａ (R ａ ) ｋ [In the formula, R ａ Each of these is independently a hydrocarbon group having 2 to 40 carbon atoms, and X ａis a hydrogen atom, a monovalent organic group or a halogen atom, and Y ａ is a divalent to tetravalent hydrocarbon group having 1 carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ - or -NH- and is a group composed of at least one or more selected therefrom, and k is 1 to 3. ] The water repellent composition according to claim 1 or 2, which is a monomer represented by. [Claim 4] The amount of the silicone compound (B) is 55 to 85% by weight based on the total amount of the polymer (A) and the silicone compound (B). The water repellent composition according to any one of claims 1 to 3. [Claim 5] The water repellent composition according to any one of claims 1 to 4, which contains a surfactant. [Claim 6] The water repellent composition according to claim 5, wherein the surfactant contains a nonionic surfactant. [Claim 7] The water repellent composition according to any one of claims 1 to 6, which further contains an isocyanate derivative. [Claim 8] The water repellent composition according to any one of claims 1 to 7, which is an aqueous dispersion. [Claim 9] A method for producing a fiber product, which includes applying the water repellent composition according to any one of claims 1 to 8 to a fiber substrate. [Claim 10] Before applying the water repellent composition to the fiber substrate, -SO ３ M １ (where M １ represents a monovalent cation), a monovalent group represented by -COOM ２ (where M ２ [[ID=ID=18]]represents a monovalent cation), and -O-P(O)(OX １ )(OX ２ (where X １ and X ２ each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms)), and the method for producing a fiber product according to claim 9, which includes a step of imparting one or more functional groups selected from the group consisting of monovalent groups represented by. [Claim 11] A fiber product in which the polymer (A) and the silicone compound (B) in the water repellent composition according to any one of claims 1 to 8 are adhered to a fiber substrate. [Claim 12] -SO ３ M １ (where M １ represents a monovalent cation), a monovalent group represented by -COOM ２ (where M２ A monovalent group represented by (where represents a monovalent cation), and -O-P(O)(OX １ ) (OX ２ ) (wherein, X １ and X ２ The textile product according to claim 11, wherein a compound having one or more functional groups selected from the group consisting of monovalent groups (each independently representing a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) is attached to it.

[0007] The water-repellent compositions in this disclosure can impart good water repellency, chalk mark resistance, and seam slip resistance to substrates (especially textile products).

[0008] <Definition of Terms> As used herein, "n-valent group" means a group having n bonds, that is, a group that forms n bonds. Also, "n-valent organic group" means an n-valent group containing carbon. Such organic groups are not particularly limited, but may be hydrocarbon groups or derivatives thereof. A hydrocarbon group derivative means a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc. at the terminal or molecular chain of a hydrocarbon group.

[0009] As used herein, "hydrocarbon group" means a group containing carbon and hydrogen, obtained by removing a hydrogen atom from a hydrocarbon. Such hydrocarbon groups are not particularly limited, but include C １－２０ Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The above-mentioned "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may also contain one or more ring structures. If explicitly stated, the hydrocarbon group may be substituted with one or more substituents.

[0010] In this specification, unless otherwise stated, whether or not the phrases "independently in each occurrence," "independently of each other," "independently of each other," or similar expressions are explicitly stated, when a term (symbol) that may appear multiple times in a chemical structure is defined, the definition shall apply independently to each occurrence.

[0011] The chemical structures described herein should be understood to exclude any chemical structures that would be considered chemically impossible or extremely unstable by those skilled in the art.

[0012] <Water-repellent composition> The water-repellent composition in this disclosure comprises a polymer (A) containing repeating units derived from a hydrocarbon group-containing monomer (a) having hydrocarbon groups having 2 to 40 carbon atoms, and a silicone compound (B) consisting of resin-based silicone and non-resin-based silicone. The silicone compound (B) consists of resin-based silicone and non-resin-based silicone. In the GPC chart of the silicone compound (B), a peak top exists in the region of molecular weight 1500 or more, and the component of the silicone compound with a molecular weight of 1500 or more includes non-resin-based silicone other than amino-modified silicone. The amount of silicone compound (B) is 51 to 99% by weight of the sum of the amount of polymer (A) and the amount of silicone compound (B).

[0013] The water-repellent compositions in this disclosure, having the above-described characteristics, can impart liquid repellency (water repellency, oil repellency, oil resistance, and / or water resistance) to substrates (e.g., textile substrates, paper substrates). The polymer (A) in this disclosure can function as at least one selected from the group consisting of water repellents, oil repellents, oil-resistant agents, and water-resistant agents. The water-repellent compositions in this disclosure can effectively impart oil resistance (oil repellency) and / or water resistance (water repellency) to substrates, and can effectively impart both oil resistance and water resistance, for example.

[0014] The water-repellent composition in this disclosure, having the above-described characteristics, can adhere to a substrate (especially a textile product) and impart good water repellency, chalk mark resistance, and seam slip resistance to the substrate (especially a textile product).

[0015] [(A) Polymer] Polymer (A) of the present disclosure will be described. Polymer (A) contains repeating units derived from hydrocarbon group-containing monomer (a) having hydrocarbon groups having 2 to 40 carbon atoms. Polymer (A) is a polymer obtained by polymerizing monomers and exhibits water repellency. Here, the monomer may be any compound having a polymerizable carbon-carbon double bond (ethylenically unsaturated double bond) (>C=C<), and may be a monomer containing a vinyl group, vinylene group, vinylidene group, acryloyl group, methacryloyl group, or derivative groups thereof.

[0016] The polymer (A) of the present disclosure adheres to a substrate (particularly a fibrous substrate) and imparts to the substrate liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, particularly oil resistance.

[0017] [Characteristics, etc.] The properties, etc. that the polymer (A) of this disclosure may have are shown below.

[0018] The HD (n-hexadecane) contact angle of polymer (A) may be 10° or more, 20° or more, 25° or more, 30° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 60° or more, or 65° or more, preferably 25° or more, more preferably 30° or more, and may also be 100° or less, 90° or less, or 75° or less. By having an HD contact angle of the lower limit above, polymer (A) can impart good liquid repellency (especially oil repellency) to the substrate. The HD contact angle is the static contact angle of polymer (A) with respect to the spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film at room temperature (25°C) and measuring the contact angle 1 second after dropping.

[0019] The water contact angle of polymer (A) is 35° or higher, 40° or higher, 45° or higher, 50° or higher, 55° or higher, 65° or higher, 75° or higher, 85° or higher, 90° or higher, or 100° or higher, and may also be 160° or lower, 140° or lower, 130° or lower, 120° or lower, 110° or lower, 100° or lower, or 90° or lower. By having a water contact angle of the above lower limit or higher, polymer (A) can impart good liquid repellency (especially water repellency) to the substrate. The water contact angle is the static contact angle of polymer (A) with respect to the spin-coated film, and is obtained by dropping 2 μL of water onto the spin-coated film at room temperature (25°C) and measuring the contact angle 1 second after the drop.

[0020] The polymer (A) is preferably a compound having bio-based carbon. The bio-basedness is measured in accordance with ASTM D6866. The bio-basedness of polymer (A) may be 20% or more, preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example 100%. A high bio-basedness means that the amount of fossil resource-based materials, such as petroleum, used is small, and from this viewpoint, a higher bio-basedness of polymer (A) is preferable.

[0021] The biodegradability of polymer (A) after 180 days is preferably 5% or more. Since this reduces the environmental burden, a higher biodegradability is preferable. The biodegradability of polymer (A) after 180 days may be, for example, 10% or more, 20% or more, 30% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, preferably 30% or more, more preferably 50% or more, even more preferably 70% or more, and most preferably 80% or more. The biodegradability of polymer (A) after 60 days is preferably 5% or more. Since this reduces the environmental burden, a higher biodegradability is preferable. The biodegradability of polymer (A) after 60 days may be, for example, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, or 45% or more, preferably 10% or more, and more preferably 30% or more. Such biodegradability may be as defined in JIS K 6953-1 or ASTM D6400.

[0022] The melting point of polymer (A) may be 30°C or higher, 40°C or higher, 60°C or higher, 80°C or higher, 100°C or higher, or 120°C or higher, preferably 40°C or higher, and may also be 250°C or lower, 225°C or lower, 200°C or lower, 150°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, 80°C or lower, or 50°C or lower.

[0023] [Structure, etc.] Polymer (A) in this disclosure does not necessarily have to contain any of the group selected from the group consisting of a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, and a fluorine atom. Even if polymer (A) does not contain these fluorine-containing groups, it can impart liquid repellency to the substrate.

[0024] The polymer (A) in this disclosure is not limited to fatty acid esters having glycosidic bonds. Fatty acid esters having glycosidic bonds are typically compounds in which a fatty acid is added via an ester bond to the hydroxyl group of a compound having a glycosidic bond (typically sugars (monosaccharides or polysaccharides)).

[0025] Polymer (A) in this disclosure may be a compound having at least one group selected from the group consisting of hydrocarbon groups having 2 to 40 carbon atoms and polysiloxane groups. In particular, polymer (A) may be a compound having at least one group selected from the group consisting of monovalent hydrocarbon groups having 2 to 40 carbon atoms and monovalent polysiloxane groups.

[0026] (Polysiloxane group) Polymer (A) may have a polysiloxane group. Similar to hydrocarbon groups having 2 or more carbon atoms which may have substituents, the polysiloxane group can impart liquid repellency to the substrate.

[0027] A polysiloxane group is a group having a polysiloxane structure. In this specification, when the term "polysiloxane" is used, unless otherwise specified, it refers to an organopolysiloxane modified with an organic group.

[0028] The silicon number of the polysiloxane group may be 3 or more, 5 or more, 6 or more, 10 or more, 30 or more, 50 or more, 1000 or more, 1000 or more, 2000 or more, or 3000 or more, preferably 10 or more, and may also be 50000 or less, 25000 or less, 10000 or less, 7500 or less, 5000 or less, 3000 or less, 1500 or less, 1000 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less, for example, 500 or less.

[0029] The polysiloxane group may be monovalent and located at the end of the molecule, or it may be divalent or polyvalent and located inside the molecule, but it is preferably monovalent.

[0030] The polysiloxane group is represented by the following formula: -[-Si(R ｓ ) ２ -O-] ａ - [wherein, R ｓ In each occurrence, independently, is a hydrocarbon group or reactive group having 1 to 40 carbon atoms, and a is an integer between 5 and 10000. It may also be represented as [ ].

[0031] R ｓ This is a hydrocarbon group having 1 to 40 carbon atoms, or a reactive group.

[0032] Examples of hydrocarbon groups having 1 to 40 carbon atoms include hydrocarbon groups having 1 to 5 carbon atoms and hydrocarbon groups having 6 to 40 carbon atoms.

[0033] Examples of hydrocarbon groups having 1 to 5 carbon atoms include methyl, ethyl, propyl, butyl, and pentyl groups (especially aliphatic hydrocarbon groups, especially alkyl groups, such as methyl or ethyl groups, especially methyl groups).

[0034] The hydrocarbon group having 2 to 40 carbon atoms may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, and particularly preferably a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be cyclic, linear, or branched, preferably linear. The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, preferably 10 or more, more preferably 12 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, more preferably 25 or less.

[0035] Examples of reactive groups are groups having a functional group (e.g., hydroxyl group, amino group, mercapto group, epoxy group, carboxyl group, halogen-substituted alkyl group, vinyl group, (meth)acrylic group, (meth)acryloyloxy group, and (meth)acrylamide group, hydrogen atom directly bonded to a silicon atom, etc.). These functional groups may be directly bonded to a silicon atom or to an organic group directly bonded to a silicon atom. The organic group may be a hydrocarbon group, for example, an alkylene group or a divalent aromatic group. The hydrocarbon group may have 2 to 12 carbon atoms, and for alkylene groups, those with 2 to 10 carbon atoms are preferred. For divalent aromatic groups, those with 6 to 12 carbon atoms are preferred. The reactive group may be a group selected from the group consisting of hydroxyl group, epoxy ring, carboxyl group, (meth)acrylic group, and amino group, for example, at least one selected from the group consisting of epoxy ring, hydroxyl group, (meth)acrylic group, and carboxyl group.

[0036] a may be 3 or more, 5 or more, 6 or more, 10 or more, 30 or more, 50 or more, 100 or more, 500 or more, 1000 or more, 2000 or more, or 3000 or more, preferably 10 or more, and may also be 10000 or less, 7500 or less, 5000 or less, 3000 or less, 1500 or less, 1000 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less, preferably 500 or less.

[0037] R is a hydrocarbon group having 1 to 5 carbon atoms in the polysiloxane group. ｓ The amount is R ｓ The amount of the total may be 20 mol% or more, 40 mol% or more, 60 mol% or more, or 80 mol% or more, preferably 50 mol% or more, and may also be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less. For example, R ｓ It is also possible that 50 mol% or more of the total number of groups are methyl groups or ethyl groups (especially methyl groups).

[0038] R is a hydrocarbon group having 2 to 40 carbon atoms in the polysiloxane group. ｓ The amount is R ｓ The amount of the total may be 3 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more, and may also be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less.

[0039] In the polysiloxane group, the reactive group R ｓ The amount is R ｓ The total amount may be 5 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more, and may also be 50 mol% or less, 40 mol% or less, 30 mol% or less, or 20 mol% or less. The polysiloxane group is a reactive group R ｓ It does not have to be included.

[0040] R ｓ The elements may be introduced randomly or in blocks, but random is preferred.

[0041] The terminal structure of the polysiloxane group described above is not limited to -R ｓ , -OR ｓ , -Si(Rｓ ) ３ It may be, etc. R of the terminal structure ｓ It may or may not have one or more reactive groups. Examples of reactive groups are as described above, and may be at least one selected from the group consisting of epoxy rings, hydroxyl groups, (meth)acrylic groups, and carboxyl groups.

[0042] The polysiloxane group may have a linker, and the parent structure and the polysiloxane group may be bonded via the linker. Such a linker is not limited to but may be a hydrocarbon group having 1 to 40 (e.g., 1 to 20) carbon atoms that may be interrupted by an oxygen atom, for example, a (poly)oxyalkylene group having 1 to 40 (e.g., 1 to 20) carbon atoms.

[0043] Examples of polysiloxane groups include -[-Si(R ｓ ) ２ -O-] ａ -Si(R ｓ ) ３ -L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -Si(R ｓ ) ３ -L ｓ１ -O-L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -R ｓ -L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -Si(R ｓ ) ３ -L ｓ１ -O-L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -R ｓ -L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -Si(R ｓ ) ３、 -L ｓ１ -[-Si(R ｓ) ２ —O— ａ —R ｓ [In the formula, R ｓ is, independently at each occurrence, a hydrocarbon group or a reactive group having 1 to 40 carbon atoms, and for the total of the R ｓ groups, 50 mol% or more is a methyl group, and L ｓ１ is, independently at each occurrence, a hydrocarbon group having 1 to 20 carbon atoms, and a is 5 or more and 10,000 or less.], [In the formula, a represents an integer of 0 to 150, b represents an integer of 1 to 150, (a + b) is 5 to 200, and n is an integer of 0 to 36.] and the like can be mentioned.

[0044] The polysiloxane group may form a branched structure (silicone resin structure) by having a silsesquioxane structure or a silica structure. For example, —O—Si(R ｓ )(—O—) ２ —O—Si(—O—) ３ A branched structure may be formed by a branched structure such as this.

[0045] The weight average molecular weight of the polymer (A) may be 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more, and may also be 5,000,000 or less, 3,000,000 or less, 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, or 5,000 or less. The weight average molecular weight may be the polystyrene equivalent molecular weight measured by GPC.

[0046] (a) Hydrocarbon group-containing monomer The polymer (A) of the present disclosure contains a repeating unit derived from a hydrocarbon group-containing monomer (a) having a hydrocarbon group having 2 to 40 carbon atoms.

[0047] The monomer (a) preferably has a (meth)acryl group as a group having an ethylenically unsaturated double bond. For example, it may have a (meth)acrylate group or a (meth)acrylamide group as an ethylenically unsaturated double bond.

[0048] Monomer (a) has a hydrocarbon group having 2 to 40 carbon atoms. The hydrocarbon group having 2 to 40 carbon atoms may have substituents, but it is preferable that it does not. Here, the hydrocarbon group is a monovalent group.

[0049] (Hydrogen group having 2 to 40 carbon atoms) The hydrocarbon group of monomer (a) may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group is branched or linear, and is more preferably linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl group).

[0050] Hydrocarbon groups are typically monovalent and may be located at the end of the molecule, and may have one or more methyl groups at the end of the hydrocarbon group. In this specification, hydrocarbon compounds (e.g., hydrocarbon waxes) are understood to consist only of a monovalent hydrocarbon group and one hydrogen atom, and for example, a C20 n-alkane (eicosane) is understood to consist only of a C20 alkyl group and one hydrogen atom.

[0051] The number of carbon atoms in the hydrocarbon group may be 2 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 10 or more, 12 or more, 14 or more, or 16 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, 25 or less, or 20 or less. Typically it is between 2 and 40, but for example, if polymer (A) is a hydrocarbon compound (hydrocarbon wax), it may be greater than 40.

[0052] The hydrocarbon group may have substituents, but it is preferable that it be unsubstituted. Examples of substituents include -OR' and -N(R'). ２, -COOR', and halogen atoms, etc. (wherein, R' is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, the hydrocarbon group may have 1 to 3 (e.g., 1) -OR' (especially -OH) as substituents (e.g., other than at the terminal).

[0053] The hydrocarbon group-containing monomer (a) has the formula: CH ２ =C(-X ａ )-C(=O)-Y ａ (R ａ ) ｋ [wherein, R ａ are each independently a hydrocarbon group having 2 or more and 40 or less carbon atoms, X ａ is a hydrogen atom, a monovalent organic group or a halogen atom, Y ａ is a divalent to tetravalent hydrocarbon group having 1 carbon atom (especially, -CH ２ -, -CH(-) ２ ), -C ６ H ４ -, -O -, -C(=O) -, -S(=O) ２ - or -NH - and is a group composed of at least one or more selected therefrom, and k is 1 to 3.]. It is preferably a monomer represented by the formula.

[0054] ​​​​​​It is preferable that the element is a hydrogen atom, a methyl group, or a chlorine atom. ａ It is particularly preferable that it be a hydrogen atom.

[0055] Y ａ It is a divalent to tetravalent group. ａ It is preferable that the group is divalent. ａ This is a hydrocarbon group having 1 carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ It is preferable that the group is composed of at least one selected from - or -NH-. ａ It is preferable that it is not a hydrocarbon group. An example of a hydrocarbon group having 1 carbon atom is -CH ２ -, -CH(-) ２ or -C(-) ３ Examples include: A hydrocarbon group with one carbon atom is repeated, -(CH ２ ) ｍ A hydrocarbon group with 2 or more carbon atoms may be formed, as shown below (where m is an integer from 1 to 5). ａ It may have an NH group.

[0056] Y ａ -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'- , -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- [In the formula, Y' is a direct bond, -O-, -NH- or -S(=O) ２ - and R' is - (CH ２ ) ｍ - (m is an integer between 1 and 5) or -C ６ H ４ - (phenylene group). ] This may be the case.

[0057] Y ａ Specific examples are -O-, -NH-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C ６ H ４-、-O-(CH ２ ) ｍ -O-、-NH-(CH ２ ) ｍ -NHH-、-O-(CH ２ ) ｍ -NH-, -NH-(CH) ２ ) ｍ -O-、-O-(CH ２ ) ｍ -O-C(=O)-、-O-(CH ２ ) ｍ -C(=O)-O-、-NHH-(CH ２ ) ｍ -O-C(=O)-、-NH-(CH ２ ) ｍ -C(=O)-O-、-O-(CH ２ ) ｍ -O-C(=O)-NH-、-O-(CH ２ ) ｍ -NHH-C(=O)-O-、-O-(CH ２ ) ｍ -C(=O)-NH-、-O-(CH ２ ) ｍ -NHH-C(=O)-、-O-(CH ２ ) ｍ -NHH-C(=O)-NH-、-O-(CH ２ ) ｍ -O-C ６ H ４ -、-O-(CH ２ ) ｍ -NH-S(=0) ２ -、-O-(CH ２ ) ｍ -S(=0) ２ -NH-, -NH-(CH) ２ ) ｍ -O-C(=O)-NH-、-NH-(CH ２ ) ｍ -NH-C(=0)-O-、-NH--(CH ２ ) ｍ -C(=O)-NH-、-NHH-(CH ２ ) ｍ -NH-C(=0)-、-NH-(CH ２ ) ｍ -NH-C(=0)-NH-, -NH-(CH ２ ) ｍ-O-C ６ H ４ -, -NH-(CH ２ ) ｍ -NH-C ６ H ４ -, -NH-(CH ２ ) ｍ -NH-S (=O) ２ -, or -NH- (CH ２ ) ｍ -S (=O) ２ -NH- [wherein m is 1 to 5, especially 2 or 4].

[0058] Y ａ is -O-, -NH-, -O-(CH ２ ) ｍ -O-C(=O)-, -O-(CH ２ ) ｍ -NH-C(=O)-, -O-(CH ２ ) ｍ -OC(=O)-NH-, -O-(CH ２ ) ｍ -NH-C(=O)-O-, -O-(CH ２ ) ｍ -NH-C(=O)-NH-, -O-(CH ２ ) ｍ -NH-S (=O) ２ -, -O-(CH ２ ) ｍ -S (=O) ２ -NH-, -NH-(CH ２ ) ｍ -NH-S (=O) ２ -, or -NH- (CH ２ ) ｍ -S (=O) ２ -NH- [wherein m is an integer from 1 to 5, particularly 2 or 4.] is preferable. Y ａ is -O- or -O- (CH ２ ) ｍ -NH-C(=O)-, especially -O-(CH ２ ) ｍ It is more preferable that it be -NH-C(=O)-.

[0059] R ａEach of these is independently a hydrocarbon group having 2 to 40 carbon atoms, and, referring to the previously described content of (hydrocarbon groups having 2 to 40 carbon atoms) above, it is preferable that they are linear or branched hydrocarbon groups. The hydrocarbon group may be a linear hydrocarbon group in particular. The hydrocarbon group is preferably an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group, and especially an alkyl group. The number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example, 12 to 18, 16 to 26, or 15 to 26, and particularly preferably 18 to 22 or 17 to 22.

[0060] A specific example of monomer (a) is (a1) equation: CH ２ = C(-X) ａ１ ) - C (= O) - Y ａ１１ -Z(-Y ａ１２ -R ａ１ ) ｎ [In the formula, R ａ１ Each of these is independently a hydrocarbon group having 2 to 40 carbon atoms, and X ａ１ Y is a hydrogen atom, a monovalent organic group, or a halogen atom. ａ１１ is -O- or -NH-, Y ａ１２ These are independent of each other, and can be directly bonded, or -O-, -C(=O)-, -S(=O) ２ -, -NH- or -CH ２ A monomer represented by formula (a2): CH ２ = C(-X) ａ２ ) - C (= O) - Y ａ２ -R ａ２ [In the formula, R ａ２ X is a hydrocarbon group having 2 to 40 carbon atoms. ａ２ Y is a hydrogen atom, a monovalent organic group, or a halogen atom. ａ２ It is a monomer represented by -O- or -NH-.

[0061] (a1) Monomer Monomer (a1) is a different monomer from monomer (a2).

[0062] Monomer (a1) may be a monomer having a hydrocarbon group having 2 to 40 carbon atoms and an NH group-containing group. Monomer (a1) may contain an amide group, a urea group, a urethane group, or a sulfonamide group. The NH group-containing group may be an amide group, a urea group, a urethane group, or a sulfonamide group. The hydrocarbon monomer may be a combination of a hydrocarbon monomer having an amide group, a urea group, a urethane group, or a sulfonamide group and a hydrocarbon monomer not having an amide group, a urea group, a urethane group, or a sulfonamide group. The effects of this disclosure can be well achieved by including such groups in monomer (a1).

[0063] The monomer (a1) is -O-, -C(=O)-, -S(=O) ２ -, -NH- or -CH ２ - A (meth)acrylate or (meth)acrylamide having a group composed of at least one selected from the above.

[0064] The monomer (a1) is given by formula: CH ２ = C(-X) ａ１ ) - C (= O) - Y ａ１１ -Z(-Y ａ１２ -R ａ１ ) ｎ [In the formula, R ａ１ Each of these is independently a hydrocarbon group having 2 to 40 carbon atoms, and X ａ１ Y is a hydrogen atom, a monovalent organic group, or a halogen atom. ａ１１ is -O- or -NH-, Y ａ１２ These are independent of each other, and can be directly bonded, or -O-, -C(=O)-, -S(=O) ２ -, -NH- or -CH ２ A compound represented by ] is a group composed of at least one selected from the following, where Z is a directly bonded, or divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2. ａ１２ And / or Z does not have to be directly joined. Y ａ１２ And Z does not necessarily have to be in a direct bond at the same time.

[0065] R ａ１This is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group. ａ１ In this, the number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example 16 to 26 or 15 to 26, and particularly preferably 18 to 22 or 17 to 22.

[0066] X ａ１ This may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. A hydrogen atom, a methyl group, or a chlorine atom is preferred.

[0067] Y ａ１２ -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'-, -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- [where Y' is independent, directly combined, -O-, -NH-, or -S(=O)] ２ - and R' is - (CH ２ ) ｍ - (where m is an integer from 1 to 5), a linear hydrocarbon group having unsaturated bonds with 1 to 5 carbon atoms, a branched hydrocarbon group having 1 to 5 carbon atoms, or - (CH ２ ) ｌ -C ６ H ４ - (CH ２ ) ｌ - (where l is an independent integer from 0 to 5, and -C) ６ H ４ (- is a phenylene group). ] This may be the case.

[0068] Y ａ１２ Specific examples include direct bond, -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O) ２ -, -S (=O) ２ -NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -OC ６ H ４ -, -NH-C ６ H４ -、-O-(CH ２ ) ｍ -O-、-NH-(CH ２ ) ｍ -NHH-、-O-(CH ２ ) ｍ -NH-, -NH-(CH) ２ ) ｍ -O-、-O-(CH ２ ) ｍ -O-C(=O)-、-O-(CH ２ ) ｍ -C(=O)-O-、-NHH-(CH ２ ) ｍ -O-C(=O)-、-NH-(CH ２ ) ｍ -C(=O)-O-、-O-(CH ２ ) ｍ -O-C(=O)-NH-、-O-(CH ２ ) ｍ -NHH-C(=O)-O-、-O-(CH ２ ) ｍ -C(=O)-NH-、-O-(CH ２ ) ｍ -NHH-C(=O)-、-O-(CH ２ ) ｍ -NHH-C(=O)-NH-、-O-(CH ２ ) ｍ -O-C ６ H ４ -、-NH-(CH ２ ) ｍ -O-C(=O)-NH-、-NH-(CH ２ ) ｍ -NH-C(=0)-O-、-NH--(CH ２ ) ｍ -C(=O)-NH-、-NHH-(CH ２ ) ｍ -NH-C(=0)-、-NH-(CH ２ ) ｍ -NH-C(=0)-NH-, -NH-(CH ２ ) ｍ -O-C ６ H ４ -、-NH-(CH ２ ) ｍ -NH-C ６ H ４- [In the formula, m is an integer between 1 and 5.]

[0069] Especially Y ａ１２ It may have an NH group.

[0070] Y ａ１２ is -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O) ２ -, -S (=O) ２ -NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -OC ６ H ４ - is preferable. Y ａ１２ It is even more preferable that -NH-C(=O)-, -C(=O)-NH-, -O-C(=O)-NH-, -NH-C(=O)-O-, or -NH-C(=O)-NH-. ａ１２ The bond does not have to be direct.

[0071] Z is a directly bonded, or divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and may have a linear or branched structure. The number of carbon atoms in Z is preferably 2 to 4, particularly 2. Specific examples of Z include directly bonded, -CH ２ -ien-CH ２ CH ２ -ien-CH ２ CH ２ CH ２ -ien-CH ２ CH ２ CH ２ CH ２ -ien-CH ２ CH ２ CH ２ CH ２ CH ２ -ien-CH ２ CH(-) ２ ien-CH ２ (CH-)CH ２ -ien-CH ２ CH ２ CH(-) ２ ien-CH ２ CH ２ CH ２ CH ２ CH(-) ２ ien-CH２ CH ２ (CH-)CH ２ -ien-CH ２ CH ２ CH ２ CH(-) ２ Therefore, Z does not have to be a direct bond.

[0072] The monomer (a1) is CH ２ = C(-X) ａ１ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-R ａ１ ,CH ２ = C(-X) ａ１ )-C(=O)-O-(CH ２ ) ｍ -OC(=O)-NH-R ａ１ ,CH ２ = C(-X) ａ１ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-OR ａ１ ,CH ２ = C(-X) ａ１ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-NH-R ａ１ It is preferable that R ａ１ and X ａ１ This is equivalent to the above. ]. The monomer (a1) is CH ２ = C(-X) ａ１ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-R ａ１ It is particularly preferable that this be the case.

[0073] Monomer (a1) can be produced by reacting a hydroxyalkyl (meth)acrylate or hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate. Examples of long-chain alkyl isocyanates include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, and behenyl isocyanate. Alternatively, monomer (a1) can also be produced by reacting a (meth)acrylate having an isocyanate group in its side chain, such as 2-methacryloyloxyethyl methacrylate, with a long-chain alkylamine or long-chain alkyl alcohol. Examples of long-chain alkylamines include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine. Examples of long-chain alkyl alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

[0074] Preferred examples of monomer (a) are as follows: stearyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, behenyl α-chloroacrylate; stearyl (meth)acrylamide, behenyl (meth)acrylamide;

[0075]

[0076]

[0077]

[0078]

[0079]

[0080] [In the above formula, n is a number from 6 to 40, and m is a number from 1 to 5.] The compound in the above chemical formula is an acrylic compound in which the α-position is a hydrogen atom, but specific examples may be a methacrylic compound in which the α-position is a methyl group and an α-chloroacrylic compound in which the α-position is a chlorine atom.

[0081] The monomer (a1) is given by formula: R ａ１２ -C(=O)-NH-R ａ１３ -O-R ａ１１ [In the formula, R ａ１１ R is an organic residue having an ethylenically unsaturated polymerizable group. ａ１２ R is a hydrocarbon group having 2 to 40 carbon atoms. ａ１３ It is preferably an amide group-containing monomer represented by ], which is a hydrocarbon group having 1 to 5 carbon atoms.

[0082] R ａ１１ This is an organic residue having an ethylenically unsaturated polymerizable group, and is not particularly limited as long as it has a polymer carbon carbon double bond. Specifically, -C(=O)CR ａ１１１ =CH ２ ----CHR ａ１１１ =CH ２ ien-CH ２ CHR ａ１１１ =CH ２ Examples include organic residues having ethylenically unsaturated polymerizable groups, such as R ａ１１１ Examples include a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Also, R ａ１１ In addition to ethylenically unsaturated polymerizable groups, it may have various organic groups, such as chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, and polysiloxane groups, and these organic groups may be substituted with various substituents. ａ１１ -C(=O)CR ａ１１１ =CH ２ It is preferable that this be the case.

[0083] R ａ１２ The hydrocarbon group possessed by monomer (a) is as described above, and is a hydrocarbon group having 2 to 40 carbon atoms, preferably an alkyl group, and includes chain hydrocarbon groups, cyclic hydrocarbon groups, etc. Among these, it is preferably a chain hydrocarbon group, and particularly preferably a linear saturated hydrocarbon group. ａ１２ The number of carbon atoms is 6 to 40, preferably 11 to 27, and particularly preferably 15 to 23.

[0084] R ａ１３This is a hydrocarbon group having 1 to 5 carbon atoms, preferably an alkyl group. The hydrocarbon group having 1 to 5 carbon atoms may be linear or branched, and may have unsaturated bonds, but linear is preferred. ａ１３ The number of carbon atoms is preferably 2 to 4, and particularly preferably 2. ａ１３ It is preferable that it is an alkylene group.

[0085] A monomer containing an amide group is R ａ１２ Those that have only one type (for example, R ａ１２ (only compounds with 17 carbon atoms), or R ａ１２ Those that are combinations of multiple things (for example, R ａ１２ A compound with 17 carbon atoms and R ａ１２ It may be a mixture of a compound having 15 carbon atoms.

[0086] An example of an amide group-containing monomer is alkyl (meth)acrylate carboxylic acid amide. Specific examples of amide group-containing monomers include palmitic acid amide ethyl (meth)acrylate, stearic acid amide ethyl (meth)acrylate, behenic acid amide ethyl (meth)acrylate, myristate acid amide ethyl (meth)acrylate, lauric acid amide ethyl (meth)acrylate, isostearate ethyl amide (meth)acrylate, oleic acid ethyl amide (meth)acrylate, tert-butylcyclohexylcaproic acid amide ethyl (meth)acrylate, adamantane carboxylic acid ethyl amide (meth)acrylate, naphthalene carboxylic acid amide ethyl (meth)acrylate, anthracene carboxylic acid amide ethyl (meth)acrylate, palmitic acid amide propyl (meth)acrylate, stearate amide propyl (meth)acrylate, palmitic acid amide ethyl vinyl ether, stearate amide ethyl vinyl ether, palmitic acid amide ethyl allyl ether, stearate amide ethyl allyl ether, or mixtures thereof.

[0087] The amide group-containing monomer is preferably stearic acid amidoethyl (meth)acrylate. The amide group-containing monomer may be a mixture containing stearic acid amidoethyl (meth)acrylate. In a mixture containing stearic acid amidoethyl (meth)acrylate, the amount of stearic acid amidoethyl (meth)acrylate may be, for example, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight, and may be 90% or less by weight, 80% or less by weight, or 70% or less by weight, based on the total weight of the amide group-containing monomer. The remaining monomer may be, for example, palmitic acid amidoethyl (meth)acrylate.

[0088] (a2) Monomer The monomer (a2) is given by formula: CH ２ = C(-X) ａ２ ) - C (= O) - Y ａ２ -R ａ２ [In the formula, R ａ２ X is a hydrocarbon group having 2 to 40 carbon atoms. ａ２ Y is a hydrogen atom, a monovalent organic group, or a halogen atom. ａ２ It is a compound represented by -O- or -NH-.

[0089] The monomer (a2) is Y ａ２ A long-chain acrylate ester monomer in which is -O-, or Y ａ２ It is a long-chain acrylamide monomer with -NH-. ａ２ This is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group. ａ２ In this, the number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example 16 to 26, and particularly preferably 18 to 22. ａ２ This may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. A hydrogen atom, a methyl group, or a chlorine atom is preferred.

[0090] Preferred examples of long-chain acrylate ester monomers are lauryl (meth)acrylate, stearyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, eicosyl α-chloroacrylate, and behenyl α-chloroacrylate. Preferred examples of long-chain acrylamide monomers are stearyl (meth)acrylamide, eicosyl (meth)acrylamide, and behenyl (meth)acrylamide.

[0091] The polymer (A) of the present disclosure may further comprise repeating units derived from the following monomers.

[0092] (b) Hydrophilic group-containing monomers The polymer (A) of the present disclosure may contain repeating units derived from the hydrophilic group-containing monomer (b). Monomer (b) is a monomer other than monomer (a) that has a hydrophilic group.

[0093] Monomer (b) preferably has a (meth)acrylic group as the group having an ethylenically unsaturated double bond, for example, it may have a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond. Monomer (a) may have one or two groups having an ethylenically unsaturated double bond, but it is preferable to have only one.

[0094] The hydrophilic group is preferably an oxyalkylene-containing group (the alkylene group has 2 to 6 carbon atoms), and is particularly preferably an oxyethylene group. In particular, monomer (b) is preferably an oxyalkylene (meth)acrylate, such as polyalkylene (or monoalkylene) glycol mono(meth)acrylate and / or polyalkylene (or monoalkylene) glycol di(meth)acrylate, or polyalkylene (or monoalkylene) glycol mono(meth)acrylamide.

[0095] Monomer (b) is given by formula: CH ２ = CX ｂ C(=O)-Y ｂ - (R ｂ O) ｎ -A ｂ [In the formula, X ｂis a hydrogen atom or a methyl group, Y ｂ is -O- or -NH-, and R ｂ Each of these is an alkylene group having 2 to 6 carbon atoms, and A ｂ This is a hydrogen atom, an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, or CH ２ = CX ｂ It is preferable that the oxyalkylene (meth)acrylate is represented by [C(=O)-, where n is an integer from 1 to 90].

[0096] An example of monomer (b) is given by formula: CH ２ = CX ｂ C(=O)-O-(R ｂ O) ｎ -A ｂｉ (b1) and CH ２ = CX ｂ C(=O)-O-(R ｂ O) ｎ -C(=O)CX ｂ =CH ２ (b2), CH ２ = CX ｂ C(=O)-NH-(R ｂ O) ｎ -A ｂｉ (b3) [In the formula, X ｂ Each is independently a hydrogen atom or a methyl group, A ｂｉ Each is independently a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, R ｂ It is preferable that each of the following is an alkylene group having 2 to 6 carbon atoms, and n is an integer from 1 to 90.

[0097] n may be, for example, 1 to 50, especially 1 to 30, particularly 1 to 15, or 2 to 15. Alternatively, n may be, for example, 1. ｂ This may be a linear or branched alkylene group, for example, formula -(CH ２ ) ｘ - or - (CH ２ ) ｘ１ - (CH(CH ３ )) ｘ２-[In the formula, x1 and x2 are between 0 and 6, for example, 2 and 5, and the sum of x1 and x2 is between 1 and 6. -(CH ２ ) ｘ１ - and - (CH (CH ３ )) ｘ２ The order of the hyphens is not limited to the given formula and may be random. The base may be represented by ]. -(R ｂ O) ｎ -In this case, R may be of two or more types (for example, 2 to 4 types, especially 2 types), -(R ｂ O) ｎ - is, for example, - (R １ O) ｎ１ - and - (R ２ O) ｎ２ - [wherein, R １ and R ２ The combination may be: 1, n1 and n2 are mutually distinct alkylene groups having 2 to 6 carbon atoms, n1 and n2 are numbers of 1 or more, and the sum of n1 and n2 is 2 to 90.

[0098] R in equations (b1), (b2), and (b3) ｂ R in formulas (b1), (b2), and (b3) is particularly preferably an ethylene group, a propylene group, or a butylene group, and especially preferably a butylene group. ｂ R may be a combination of two or more alkylene groups. In that case, it is preferable that at least one of R is an ethylene group, a propylene group, or a butylene group. ｂ Examples of combinations include ethylene group / propylene group combinations, ethylene group / butylene group combinations, and propylene group / butylene group combinations. Monomer (b) may be a mixture of two or more types. In that case, at least one of monomer (b) is R in formula (b1), (b2), or (b3). ｂ It is preferable that the group is an ethylene group, a propylene group, or a butylene group. Furthermore, when using polyalkylene glycol di(meth)acrylate represented by formula (b2), it is not preferable to use it alone as monomer (b), but rather to use it in combination with monomer (b1). In that case as well, it is preferable that the compound represented by formula (b2) be kept to less than 30% by weight of monomer (b) used.

[0099] Specific examples of monomer (b) include, but are not limited to, the following: CH ２ =CHCOO-CH ２ CH ２ O-H CH ２ =CHCOO-CH ２ CH ２ CH ２ O-H CH ２ =CHCOO-CH ２ CH (CH ３ ) O-H CH ２ =CHCOO-CH(CH ３ )CH ２ O-H CH ２ =CHCOO-CH ２ CH ２ CH ２ CH ２ O-H CH ２ =CHCOO-CH ２ CH ２ CH (CH ３ ) O-H CH ２ =CHCOO-CH ２ CH (CH ３ )CH ２ O-H CH ２ =CHCOO-CH(CH ３ )CH ２ CH ２ O-H CH ２ =CHCOO-CH ２ CH (CH ２ CH ３ ) O-H CH ２ =CHCOO-CH ２ C (CH ３ ) ２ O-H CH ２ =CHCOO-CH(CH ２ CH ３ )CH ２ O-H CH ２ =CHCOO-C(CH ３ ) ２ CH ２ O-H CH ２ =CHCOO-CH(CH ３ )CH(CH ３ ) O-H CH ２ =CHCOO-C(CH ３)(CH ２ CH ３ )O-H CH ２ =CHCOO-(CH ２ CH ２ O) ２ -H CH ２ =CHCOO-(CH ２ CH ２ O) ４ -H CH ２ =CHCOO-(CH ２ CH ２ O) ５ -H CH ２ =CHCOO-(CH ２ CH ２ O) ６ -H CH ２ =CHCOO-(CH ２ CH ２ O) ５ -CH ３ CH ２ =CHCOO-(CH ２ CH ２ O) ９ -CH ３ CH ２ =CHCOO-(CH ２ CH ２ O) ２３ -CH ３ CH ２ =CHCOO-(CH ２ CH ２ O) ９０ -CH ３

[0100] CH ２ =CHCOO-(CH ２ CH(CH ３ )O) ９ -H CH ２ =CHCOO-(CH ２ CH(CH ３ )O) ９ -CH ３ CH ２ =CHCOO-(CH ２ CH(CH ３ )O) １２ -CH ３ CH ２ =CHCOO-(CH ２ CH ２ O)５ -(CH) ２ CH(CH ３ )O) ２ -H CH ２ =CHCOO-(CH ２ CH ２ O) ５ -(CH) ２ CH(CH ３ )O) ３ -CH ３ CH ２ =CHCOO-(CH ２ CH ２ O) ８ -(CH) ２ CH(CH ３ )O) ６ -CH ２ CH(C) ２ H ５ )C ４ H ９ CH ２ =CHCOO-(CH ２ CH ２ O) ２３ -OOC(CH) ３ )C=CH ２ CH ２ =CHCOO-(CH ２ CH ２ O) ２０ -(CH) ２ CH(CH ３ )O) ５ -CH ２ -CH=CH ２

[0101] CH ２ =CHCOO-(CH ２ CH ２ O) ９ -H CH ２ =C(CH ３ )COO-CH ２ CH ２ O-H CH ２ =C(CH ３ )COO-CH ２ CH ２ CH ２ O-H CH ２ =C(CH ３ )COO-CH ２ CH(CH ３ )O-H CH​２ =C(CH ３ )COO-CH(CH ３ )CH ２ O-H CH ２ =C(CH ３ )COO-CH ２ CH ２ CH ２ CH ２ O-H CH ２ =C(CH ３ )COO-CH ２ CH ２ CH(CH ３ )O-H CH ２ =C(CH ３ )COO-CH ２ CH(CH ３ )CH ２ O-H CH ２ =C(CH ３ )COO-CH(CH ３ )CH ２ CH ２ O-H CH ２ =C(CH ３ )COO-CH ２ CH(CH ２ CH ３ )O-H CH ２ =C(CH ３ )COO-CH ２ C(CH ３ ) ２ O-H CH ２ =C(CH ３ )COO-CH(CH ２ CH ３ )CH ２ O-H CH ２ =C(CH ３ )COO-C(CH ３ ) ２ CH ２ O-H CH ２ =C(CH ３ )COO-CH(CH ３ )CH(CH ３ )O-H CH ２ =C(CH ３ )COO-C(CH ３ )(CH ２ CH ３ )O-H CH ２ =C(CH３ )COO-(CH ２ CH ２ O) ２ -H CH ２ =C(CH ３ )COO-(CH ２ CH ２ O) ４ -H CH ２ =C(CH ３ )COO-(CH ２ CH ２ O) ５ -H CH ２ =C(CH ３ )COO-(CH ２ CH ２ O) ６ -H CH ２ =C(CH ３ )COO-(CH ２ CH ２ O) ９ -H CH ２ =C(CH ３ )COO-(CH ２ CH ２ O) ５ -CH ３ CH ２ =C(CH ３ )COO-(CH ２ CH ２ O) ９ -CH ３ CH ２ =C(CH ３ )COO-(CH ２ CH ２ O) ２３ -CH ３ CH ２ =C(CH ３ )COO-(CH ２ CH ２ O) ９０ -CH ３ CH ２ =C(CH ３ )COO-(CH ２ CH(CH ３ )O) ９ -H

[0102] CH ２ =C(CH ３ )COO-(CH ２ CH(CH３ )O) ９ -CH ３ CH ２ =C(CH ３ )COO-(CH ２ CH(CH ３ )O) １２ -CH ３ CH ２ =C(CH ３ )COO-(CH ２ CH ２ O) ５ -(CH) ２ CH(CH ３ )O) ２ -H CH ２ =C(CH ３ )COO-(CH ２ CH ２ O) ５ -(CH) ２ CH(CH ３ )O) ３ -CH ３ CH ２ =C(CH ３ )COO-(CH ２ CH ２ O) ８ -(CH) ２ CH(CH ３ )O) ６ -CH ２ CH(C) ２ H ５ )C ４ H ９ CH ２ =C(CH ３ )COO-(CH ２ CH ２ O) ２３ -OOC(CH) ３ )C=CH ２ CH ２ =C(CH ３ )COO-(CH ２ CH ２ O) ２０ -(CH) ２ CH(CH ３ )O) ５ -CH ２ -CH=CH ２

[0103] CH ２ ​=CH-C(=O)-NH-CH ２ CH ２ O-H CH ２ =CH-C(=O)-NH-CH ２ CH ２ CH ２ O-H CH ２ =CH-C(=O)-NH-CH ２ CH(CH ３ )O-H CH ２ =CH-C(=O)-NH-CH(CH ３ )CH ２ O-H CH ２ =CH-C(=O)-NH-CH ２ CH ２ CH ２ CH ２ O-H CH ２ =CH-C(=O)-NH-CH ２ CH ２ CH(CH ３ )O-H CH ２ =CH-C(=O)-NH-CH ２ CH(CH ３ )CH ２ O-H CH ２ =CH-C(=O)-NH-CH(CH ３ )CH ２ CH ２ O-H CH ２ =CH-C(=O)-NH-CH ２ CH(CH ２ CH ３ )O-H CH ２ =CH-C(=O)-NH-CH ２ C(CH) ３ ) ２ O-H CH ２ =CH-C(=O)-NH-CH(CH ２ CH ３ )CH ２ O-H CH ２ =CH-C(=O)-NH-C(CH ３ ) ２ CH ２ O-H CH ２ =CH-C(=O)-NH-CH(CH ３ )CH(CH ３ )O-H CH ２=CH-C(=O)-NH-C(CH ３ (CH) ２ CH ３ )O-H CH ２ =CH-C(=O)-NH-(CH ２ CH ２ O) ２ -H CH ２ =CH-C(=O)-NH-(CH ２ CH ２ O) ４ -H CH ２ =CH-C(=O)-NH-(CH ２ CH ２ O) ５ -H CH ２ =CH-C(=O)-NH-(CH ２ CH ２ O) ６ -H CH ２ =CH-C(=O)-NH-(CH ２ CH ２ O) ９ -H CH ２ =CH-C(=O)-NH-(CH ２ CH ２ O) ５ -CH ３ CH ２ =CH-C(=O)-NH-(CH ２ CH ２ O) ９ -CH ３ CH ２ =CH-C(=O)-NH-(CH ２ CH ２ O) ２３ -CH ３ CH ２ =CH-C(=O)-NH-(CH ２ CH ２ O) ９０ -CH ３

[0104] CH ２ =CH-C(=O)-NH-(CH ２ CH(CH ３ )O) ９ -H CH ２ =CH-C(=O)-NH-(CH ２ CH(CH ３ )O) ９-CH ３ CH ２ =CH-C(=O)-NH-(CH ２ CH(CH ３ )O) １２ -CH ３ CH ２ =CH-C(=O)-NH-(CH ２ CH ２ O) ５ -(CH) ２ CH(CH ３ )O) ２ -H CH ２ =CH-C(=O)-NH-(CH ２ CH ２ O) ５ -(CH) ２ CH(CH ３ )O) ３ -CH ３ CH ２ =CH-C(=O)-NH-(CH ２ CH ２ O) ８ -(CH) ２ CH(CH ３ )O) ６ -CH ２ CH(C) ２ H ５ )C ４ H ９

[0105] CH ２ =C(CH ３ )-C(=O)-NH-CH ２ CH ２ O-H CH ２ =C(CH ３ )-C(=O)-NH-CH ２ CH ２ CH ２ O-H CH ２ =C(CH ３ )-C(=O)-NH-CH ２ CH(CH ３ )O-H CH ２ =C(CH ３ )-C(=O)-NH-CH(CH ３ )CH ２ O-H CH ２ =C(CH ３ )-C(=O)-NH-CH２ CH ２ CH ２ CH ２ O-H CH ２ =C(CH ３ )-C(=O)-NH-CH ２ CH ２ CH(CH ３ )O-H CH ２ =C(CH ３ )-C(=O)-NH-CH ２ CH(CH ３ )CH ２ O-H CH ２ =C(CH ３ )-C(=O)-NH-CH(CH ３ )CH ２ CH ２ O-H CH ２ =C(CH ３ )-C(=O)-NH-CH ２ CH(CH ２ CH ３ )O-H CH ２ =C(CH ３ )-C(=O)-NH-CH ２ C(CH) ３ ) ２ O-H CH ２ =C(CH ３ )-C(=O)-NH-CH(CH ２ CH ３ )CH ２ O-H CH ２ =C(CH ３ )-C(=O)-NHH-C(CH ３ ) ２ CH ２ O-H CH ２ =C(CH ３ )-C(=O)-NH-CH(CH ３ )CH(CH ３ )O-H CH ２ =C(CH ３ )-C(=O)-NHH-C(CH ３ (CH) ２ CH ３ )O-H CH ２ =C(CH ３ )-C(=O)-NH-(CH ２ CH ２ O)２ -H CH ２ =C(CH ３ )-C(=O)-NH-(CH ２ CH ２ O) ４ -H CH ２ =C(CH ３ )-C(=O)-NH-(CH ２ CH ２ O) ５ -H CH ２ =C(CH ３ )-C(=O)-NH-(CH ２ CH ２ O) ６ -H CH ２ =C(CH ３ )-C(=O)-NH-(CH ２ CH ２ O) ９ -H CH ２ =C(CH ３ )-C(=O)-NH-(CH ２ CH ２ O) ５ -CH ３ CH ２ =C(CH ３ )-C(=O)-NH-(CH ２ CH ２ O) ９ -CH ３ CH ２ =C(CH ３ )-C(=O)-NH-(CH ２ CH ２ O) ２３ -CH ３ CH ２ =C(CH ３ )-C(=O)-NH-(CH ２ CH ２ O) ９０ -CH ３

[0106] CH ２ =C(CH ３ )-C(=O)-NH-(CH ２ CH(CH ３ )O) ９ -H CH ２ =C(CH ３ )-C(=O)-NH-(CH ２CH (CH ３ )O) ９ -CH ３ CH ２ = C(CH ３ )-C(=O)-NH-(CH ２ CH (CH ３ )O) １２ -CH ３ CH ２ = C(CH ３ )-C(=O)-NH-(CH ２ CH ２ O) ５ - (CH ２ CH (CH ３ )O) ２ -H CH ２ = C(CH ３ )-C(=O)-NH-(CH ２ CH ２ O) ５ - (CH ２ CH (CH ３ )O) ３ -CH ３ CH ２ = C(CH ３ )-C(=O)-NH-(CH ２ CH ２ O) ８ - (CH ２ CH (CH ３ )O) ６ -CH ２ CH(C ２ H ５ ) C ４ H ９

[0107] The monomer (b) is X ２ It is preferable that the monomer (b) is a hydrogen atom and is an acrylate or acrylamide. Monomer (b) is particularly preferably hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxyethyl acrylamide.

[0108] (c) Ionic group-containing monomers The polymer (A) of the present disclosure may contain repeating units derived from the ionic group-containing monomer (c). The monomer (c) is preferably a monomer (particularly an acrylic monomer) containing one ethylenically unsaturated double bond and an ionic group. The ionic group is an anionic group and / or a cationic group, or a salt thereof.

[0109] The monomer (c) preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, for example, it may have a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0110] Monomers having anionic groups include monomers having a carboxyl group, a sulfonic acid group, or a phosphate group. Specific examples of monomers having anionic groups include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, (meth)acrylate phosphoric acid, vinylbenzenesulfonic acid, acrylamide tert-butylsulfonic acid, or salts thereof.

[0111] Examples of salts of anionic groups include alkali metal salts, alkaline earth metal salts, or ammonium salts, such as methylammonium salt, ethanolammonium salt, and triethanolammonium salt.

[0112] In monomers having cationic groups, examples of cationic groups are amino groups, preferably tertiary amino groups and quaternary amino groups. In tertiary amino groups, the two groups bonded to the nitrogen atom are the same or different, and are an aliphatic group having 1 to 5 carbon atoms (especially alkyl groups), an aromatic group having 6 to 20 carbon atoms (aryl groups), or an aromatic aliphatic group having 7 to 25 carbon atoms (especially aralkyl groups, such as benzyl groups (C)). ６ H ５ -CH ２ It is preferable that the quaternary amino group is a C1-C5 aliphatic group (especially alkyl group), a C6-C20 aromatic group (aryl group), or a C7-C25 aromatic aliphatic group (especially aralkyl group, for example benzyl group (C)).６ H ５ -CH ２ It is preferable that the following conditions are met. In the tertiary and quaternary amino groups, the remaining group bonded to the nitrogen atom may have an ethylenically unsaturated double bond. The cationic group may also be in the form of a salt.

[0113] The cationic group, which is a salt, is a salt with an acid (organic or inorganic acid). Organic acids, such as carboxylic acids having 1 to 20 carbon atoms (especially monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid), are preferred. Dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate and their salts are preferred.

[0114] Specific examples of monomers having cationic groups are as follows: CH ２ =CHCOO-CH ２ CH ２ -N(CH ３ ) ２ and its salts (e.g., acetate) CH ２ =CHCOO-CH ２ CH ２ -N(CH ２ CH ３ ) ２ and its salts (e.g., acetate) CH ２ = C(CH ３ ) COO-CH ２ CH ２ -N(CH ３ ) ２ and its salts (e.g., acetate) CH ２ = C(CH ３ ) COO-CH ２ CH ２ -N(CH ２ CH ３ ) ２ and its salts (e.g., acetate) CH ２ =CHC(O)N(H)-CH ２ CH ２ CH ２ -N(CH ３ ) ２ and its salts (e.g., acetate) CH ２ =CHCOO-CH ２ CH ２ -N(-CH３ ) (-CH ２ -C ６ H ５ ) and its salts (e.g., acetate) CH ２ = C(CH ３ ) COO-CH ２ CH ２ -N(-CH ２ CH ３ ) (-CH ２ -C ６ H ５ ) and its salts (e.g., acetate) CH ２ =CHCOO-CH ２ CH ２ -N ＋ (CH ３ ) ３ Cl － CH ２ =CHCOO-CH ２ CH ２ -N ＋ (-CH ３ ) ２ (-CH ２ -C ６ H ５ ) Cl － CH ２ = C(CH ３ ) COO-CH ２ CH ２ -N ＋ (CH ３ ) ３ Cl － CH ２ =CHCOO-CH ２ CH(OH)CH ２ -N ＋ (CH ３ ) ３ Cl － CH ２ = C(CH ３ ) COO-CH ２ CH(OH)CH ２ -N ＋ (CH ３ ) ３ Cl － CH ２ = C(CH ３ ) COO-CH ２ CH(OH)CH ２ -N ＋ (-CH ２CH ３ ) ２ (-CH ２ -C ６ H ５ ) Cl － CH ２ = C(CH ３ ) COO-CH ２ CH ２ -N ＋ (CH ３ ) ３ Br － CH ２ = C(CH ３ ) COO-CH ２ CH ２ -N ＋ (CH ３ ) ３ I － CH ２ = C(CH ３ ) COO-CH ２ CH ２ -N ＋ (CH ３ ) ３ O － SO ３ CH ３ CH ２ = C(CH ３ ) COO-CH ２ CH ２ -N ＋ (CH ３ ) (-CH ２ -C ６ H ５ ) ２ Br －

[0115] The ionic group-containing monomer (c) is preferably methacrylic acid, acrylic acid, or dimethylaminoethyl methacrylate, and more preferably methacrylic acid or dimethylaminoethyl methacrylate.

[0116] (d) Halide Olefin Monomer The polymer (A) of the present disclosure may have repeating units derived from the halide olefin monomer (d). The halide olefin monomer (d) does not have to have a fluorine atom. The halide olefin monomer (d) is preferably a carbon 2 to 20 olefin substituted with 1 to 10 chlorine atoms, bromine atoms, or iodine atoms. The halide olefin monomer (d) is preferably a carbon 2 to 20 chlorinated olefin, particularly a carbon 2 to 5 olefin having 1 to 5 chlorine atoms. Preferred specific examples of the halide olefin monomer (d) are vinyl halides, such as vinyl chloride, vinyl bromide, vinyl iodide, and vinylidene halides, such as vinylidene chloride, vinylidene bromide, and vinylidene iodide. Vinyl chloride or vinylidene chloride is preferred because it provides high water repellency (especially water repellency durability). The presence of repeating units derived from halogenated olefin monomer (d) can enhance the wash durability of polymer (A).

[0117] (e) Crosslinkable monomers The polymer (A) of the present disclosure may include repeating units derived from the crosslinkable monomer (e). The crosslinkable monomer (e) has a reactive group and / or an ethylenically unsaturated double bond (preferably a (meth)acrylate group). The crosslinkable monomer (e) may be a monomer that does not contain a fluorine atom. The crosslinkable monomer (e) may be a compound having at least two ethylenically unsaturated double bonds (preferably a (meth)acrylate group), or a compound having at least one ethylenically unsaturated double bond and at least one reactive group. Examples of reactive groups include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, a carboxyl group, and the like.

[0118] Examples of crosslinkable monomers may be vinyl monomers having a reactive group, mono(meth)acrylates, di(meth)acrylates, or di(meth)acrylamides having a reactive group.

[0119] Examples of crosslinkable monomers include, but are not limited to, diacetone (meth)acrylamide, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

[0120] (f) Cyclic hydrocarbon group-containing monomers The polymer (A) of the present disclosure may have repeating units derived from the cyclic hydrocarbon group-containing monomer (f). The cyclic hydrocarbon group-containing monomer (f) is a monomer having a cyclic hydrocarbon group, and may be a monomer having one ethylenically unsaturated double bond and a cyclic hydrocarbon group. The polymer (A) of the present disclosure may be a styrene polymer having repeating units derived from styrene or a styrene derivative.

[0121] The cyclic hydrocarbon group-containing monomer (f) preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, for example, it may have a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0122] The cyclic hydrocarbon group may be alicyclic or aromatic. The cyclic hydrocarbon group may be saturated or unsaturated. The cyclic hydrocarbon group may be monocyclic, polycyclic, or bridged ring group, with bridged ring group being preferred. The cyclic hydrocarbon group may have a chain-like group (for example, a halogen atom, a linear or branched hydrocarbon group (particularly a linear or branched hydrocarbon group having 1 to 20 carbon atoms)).

[0123] The number of carbon atoms in the cyclic hydrocarbon group may be 4 or more, 6 or more, or 8 or more, and may be 30 or less, 26 or less, 22 or less, 18 or less, or 14 or less.

[0124] Specific examples of cyclic hydrocarbon groups include cyclohexyl group, t-butylcyclohexyl group, adamantyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, bornyl group, isobornyl group, norbornyl group, dicyclopentanyl group, dicyclopentenyl group, benzyl group, phenyl group, naphthyl group, 2-t-butylphenyl group, residues obtained by removing one or more hydrogen atoms from these groups (e.g., cyclohexylene group, adamantylene group, phenylene group, naphthylene group, etc.), and substituted groups thereof.

[0125] Specific examples of cyclic hydrocarbon group-containing monomers (f) include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and compounds obtained by substituting these acrylates with acrylamide. These may be used alone or in combination of two or more.

[0126] An example of a cyclic hydrocarbon group-containing monomer (f) is a styrene compound. The styrene compound may be modified with a chain-like group (for example, a halogen atom, a linear or branched hydrocarbon group (particularly a linear or branched hydrocarbon group having 1 to 20 carbon atoms)). Specific examples include styrene, 4-t-butylstyrene, 3,5-di-t-butylstyrene, 2,4,6-tri-t-butylstyrene, 4-methylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, etc. The styrene compound may be an α-methylstyrene compound or an α-chlorostyrene compound with a chlorine atom at the α-position, or a styrene compound with a hydrogen atom at the α-position.

[0127] (g) Polysiloxane group-containing monomer The polymer (A) of the present disclosure may have repeating units derived from the polysiloxane group-containing monomer (g). The monomer (g) has one ethylenically unsaturated double bond and a polysiloxane group.

[0128] The monomer (g) preferably has a (meth)acrylic group, and may, for example, have a (meth)acrylate group or a (meth)acrylamide group as an ethylenically unsaturated double bond.

[0129] The polysiloxane group present in monomer (g) is described in the above explanation of (polysiloxane group). Monomer (g) may have a polydimethylsiloxane group in its side chain.

[0130] The ethylenically unsaturated double bond and the polysiloxane group may be linked by any linker group.

[0131] The monomer (g) is given by the formula: CH ２ = C(-X) ｇ ) - C (= O) - Y ｇ (Note) ｇ ｋ [In the formula, R ｇ X is a group having a polydimethylsiloxane group. ｇ Y is a hydrogen atom, a monovalent organic group, or a halogen atom. ｇ This refers to divalent to tetravalent hydrocarbon groups with one carbon atom (especially -CH ２ -, -CH(-) ２ ), -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ It is preferably a monomer represented by ], which is a group consisting of at least one selected from - or -NH-, where k is 1 to 3.

[0132] X ｇ This may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. ｇ Examples include hydrogen atoms, methyl groups, chlorine atoms, bromine atoms, iodine atoms, and cyano groups. ｇ It is preferable that the element is a hydrogen atom, a methyl group, or a chlorine atom.ｇ It is particularly preferable that it be a hydrogen atom.

[0133] Y ｇ It is a divalent to tetravalent group. ｇ It is preferable that the group is divalent. ｇ This is a hydrocarbon group having 1 carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ It is preferable that the group is composed of at least one selected from - or -NH-. ｇ It is preferable that it is not a hydrocarbon group. An example of a hydrocarbon group having 1 carbon atom is -CH ２ -, -CH(-) ２ or -C(-) ３ Examples include: A hydrocarbon group with one carbon atom is repeated, -(CH ２ ) ｍ A hydrocarbon group with 2 or more carbon atoms may be formed, as shown below (where m is an integer from 1 to 5). ｇ It may have an NH group.

[0134] Y ｇ -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'- , -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- [In the formula, Y' is a direct bond, -O-, -NH- or -S(=O) ２ - and R' is - (CH ２ ) ｍ - (m is an integer between 1 and 5) or -C ６ H ４ - (phenylene group). ] This may be the case.

[0135] Y ｇ Specific examples are -O-, -NH-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C ６ H ４ -, -O-(CH ２ )ｍ -O-、-NH-(CH ２ ) ｍ -NHH-、-O-(CH ２ ) ｍ -NH-, -NH-(CH) ２ ) ｍ -O-、-O-(CH ２ ) ｍ -O-C(=O)-、-O-(CH ２ ) ｍ -C(=O)-O-、-NHH-(CH ２ ) ｍ -O-C(=O)-、-NH-(CH ２ ) ｍ -C(=O)-O-、-O-(CH ２ ) ｍ -O-C(=O)-NH-、-O-(CH ２ ) ｍ -NHH-C(=O)-O-、-O-(CH ２ ) ｍ -C(=O)-NH-、-O-(CH ２ ) ｍ -NHH-C(=O)-、-O-(CH ２ ) ｍ -NHH-C(=O)-NH-、-O-(CH ２ ) ｍ -O-C ６ H ４ -、-O-(CH ２ ) ｍ -NH-S(=0) ２ -、-O-(CH ２ ) ｍ -S(=0) ２ -NH-, -NH-(CH) ２ ) ｍ -O-C(=O)-NH-、-NH-(CH ２ ) ｍ -NH-C(=0)-O-、-NH--(CH ２ ) ｍ -C(=O)-NH-、-NHH-(CH ２ ) ｍ -NH-C(=0)-、-NH-(CH ２ ) ｍ -NH-C(=0)-NH-, -NH-(CH ２ ) ｍ -O-C ６ H４ -, -NH-(CH ２ ) ｍ -NH-C ６ H ４ -, -NH-(CH ２ ) ｍ -NH-S (=O) ２ -, or -NH- (CH ２ ) ｍ -S (=O) ２ -NH- [wherein m is 1 to 5, especially 2 or 4].

[0136] Y ｇ is -O-, -NH-, -O-(CH ２ ) ｍ -O-C(=O)-, -O-(CH ２ ) ｍ -NH-C(=O)-, -O-(CH ２ ) ｍ -OC(=O)-NH-, -O-(CH ２ ) ｍ -NH-C(=O)-O-, -O-(CH ２ ) ｍ -NH-C(=O)-NH-, -O-(CH ２ ) ｍ -NH-S (=O) ２ -, -O-(CH ２ ) ｍ -S (=O) ２ -NH-, -NH-(CH ２ ) ｍ -NH-S (=O) ２ -, or -NH- (CH ２ ) ｍ -S (=O) ２ -NH- [wherein m is an integer from 1 to 5, particularly 2 or 4.] is preferable. Y ｇ is -O- or -O- (CH ２ ) ｍ -NH-C(=O)-, especially -O-(CH ２ ) ｍ It is more preferable that it be -NH-C(=O)-.

[0137] R ｇ This refers to a group having a polydimethylsiloxane group, and the explanation of the polydimethylsiloxane group described above (polysiloxane group) is used for further details.

[0138] Examples of the monomer (g) are as follows. CH ２ =C(−X ｇ )−C(=O)−Y ｇ −[−Si(R ｓ ) ２ −O−] ａ ａ −Si(R[[ID=,15]] ｓ ) ３ CH ２ =C(−X ｇ [[ID=,22]])−C(=O)−Y ｇ −L ｓ１ −[−Si(R ｓ ) ２ −O−] ａ ａ −Si(R ｓ ) ３ CH ２ =C(−X ｇ )−C(=O)−Y ｇ / / 这里原内容似乎有误,多了一个 ｇ 标签,按照要求保留−L ｓ１ −O−L ｓ１ −[−Si(R ｓ ) ２ −O−] ａ ａ −R ｓ CH ２ =C(−X ｇ )−C(=O)−Y ｇ −L ｓ１ −[−Si(R ｓ ) ２ −O−] ａ ａ −Si(R ｓ ) / / 这里原内容似乎有误,多了一个 ３ 标签,按照要求保留 ３ CH ２ =C(−X ｇ )−C(=O)−Y [[ID=,77]] ｇ −L ｓ１ [[ID=,80]]−O−L ｓ１ −[−Si(R ｓ ) ２ [[ID=,86]]−O−] ａ ａ −R ｓ CH ２ =C(−X ｇ )−C(=O)−Y ｇ −L ｓ１ −[−Si(R ｓ )<0×001441> / / 这里原内容似乎有误,标签应为 ２ ,按照要求保留 −O−] ａ ａ −Si(R ｓ ) ３、 CH ２ =C(−X ｇ 请注意,原文中部分标签可能存在错误或不规范的情况,已按照要求保留并在翻译中尽量体现原文结构。你可根据实际情况进一步检查和确认。) - C (= O) - Y ｇ -L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -R ｓ [In the formula, each symbol is used with reference to the explanation above.]

[0139] (h) Other monomers are not limited to these examples and include acrylonitrile, short-chain alkyl (meth)acrylates, vinyl acetate, vinyl alkyl ethers, etc. Other monomers (h) may be used alone or in combination of two or more.

[0140] [Composition of Polymer] The combinations of monomers (a) to (h) that constitute the repeating unit of polymer (A) of this disclosure are not particularly limited, but for example they are as follows (parentheses omitted): a a+b a+b+c a+c a+d a+b+c+d a+b+c+d+e a+b+c+d+e+f a+b+c+d+e+f+g In the above combinations, monomer (g) may be used in place of monomer (a) or in addition to monomer (a). Other monomers (h) may be used in combination with the above combinations. For pulp products, it is preferable to use monomers (a), (b), and (c) in combination.

[0141] The amount of repeating units derived from monomer (a) may be 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may also be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 60% by weight or less, 55% by weight or less, 50% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, relative to polymer (A).

[0142] The amount of monomer (a) (especially monomer (a1)) relative to polymer (A) may be more than 90% by weight, 92% or more by weight, 94% or more by weight, 96% or more by weight, 98% or more by weight, 99% or more by weight, 99.5% or more by weight, or 100% by weight, for example, 93% or more by weight, preferably more than 97% by weight, and also 100% or less by weight, 99% or less by weight, 97% or less by weight, 95% or less by weight, or 93% or less by weight, and in one embodiment, more than 90% by weight and 100% or less by weight. The amount of monomer (a1) may also be 100% by weight relative to polymer (A).

[0143] Of the monomer (a), the amount of monomer (a1) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, or 80% by weight or more, preferably 30% by weight or more, and may also be 100% by weight or less, 90% by weight or less, 80% by weight or less, 50% by weight or less, or 30% by weight or less.

[0144] Of monomer (a), the amount of monomer (a2) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, or 80% by weight or more, and may also be 100% by weight or less, 90% by weight or less, 80% by weight or less, 50% by weight or less, or 30% by weight or less.

[0145] The amount of repeating units derived from monomer (b) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may also be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less. The amount of repeating units derived from monomer (b) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of repeating units derived from monomer (a). Alternatively, it may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less.

[0146] The amount of repeating units derived from monomer (c) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may also be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less. The amount of repeating units derived from monomer (c) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of repeating units derived from monomer (a). Alternatively, it may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less.

[0147] The amount of repeating units derived from monomer (d) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, relative to polymer (A), and the amount of repeating units derived from monomer (d) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, relative to polymer (A). The amount of repeating units derived from monomer (d) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of repeating units derived from monomer (a). Alternatively, it may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less.

[0148] The amount of repeating units derived from monomer (e) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, relative to polymer (A), and may also be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less. The amount of repeating units derived from monomer (e) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, with respect to 100 parts by weight of repeating units derived from monomer (a). Alternatively, it may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less.

[0149] The amount of repeating units derived from monomer (f) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, relative to polymer (A), and may also be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less. The amount of repeating units derived from monomer (f) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of repeating units derived from monomer (a). Alternatively, it may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less.

[0150] The amount of repeating units derived from the monomer (g) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may also be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less. The amount of repeating units derived from the monomer (g) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of repeating units derived from the monomer (a). Alternatively, it may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less.

[0151] The amount of repeating units derived from the monomer (h) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may also be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less. The amount of repeating units derived from monomer (h) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of repeating units derived from monomer (a). Alternatively, it may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less.

[0152] When monomer (g) is used instead of monomer (a), the phrase "100 parts by weight of repeating units derived from monomer (a)" in the above-mentioned description of the amount of each monomer may be read as "100 parts by weight of repeating units derived from monomer (g)."

[0153] The amount of polymer (A) may be 0.01% by weight or more, 0.05% by weight or more, 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 1.0% by weight or more, 2.0% by weight or more, 3.0% by weight or more, or 5.0% by weight or more in the water-repellent composition, and may also be 30% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7% by weight or less, 5% by weight or less, or 3% by weight or less.

[0154] [Polymerization Method] Polymer (A) can be produced by known polymerization methods, and the conditions for the polymerization reaction can be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization.

[0155] In solution polymerization, a method is employed in which monomers are dissolved in an organic solvent in the presence of a polymerization initiator, followed by nitrogen purging, and then heating and stirring at a temperature of 30 to 120°C for 1 to 10 hours. Examples of polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, per 100 parts by weight of monomer.

[0156] Organic solvents are inert to monomers and dissolve them, and may include esters (e.g., esters with 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2 to 40 carbon atoms, specifically methyl ethyl ketone, diisobutyl ketone, and methyl isobutyl ketone), and alcohols (e.g., alcohols with 1 to 40 carbon atoms, specifically ethanol, butanol, and isopropyl alcohol). Specific examples of organic solvents include acetone, chloroform, HCFC225, isopropyl alcohol, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane. The organic solvent is used in an amount of 10 to 3000 parts by weight, for example, 50 to 2000 parts by weight, per 100 parts by weight of the total monomers.

[0157] In emulsion polymerization, a method is employed in which monomers are emulsified in water in the presence of a polymerization initiator and an emulsifier, and then polymerized by stirring at a temperature of 50 to 80°C for 1 to 20 hours after nitrogen purging. The polymerization initiators used are water-soluble ones such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, sodium peroxide, potassium persulfate, and ammonium persulfate, or oil-soluble ones such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 10 parts by weight per 100 parts by weight of monomer.

[0158] To obtain a polymer aqueous dispersion with excellent stability during storage, it is desirable to polymerize the monomers by micronizing them in water using an emulsifying device that can impart strong crushing energy, such as a high-pressure homogenizer or an ultrasonic homogenizer. Various emulsifiers, including anionic, cationic, and nonionic types, can be used as emulsifiers, typically in an amount of 0.5 to 20 parts by weight per 100 parts by weight of monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. If the monomers are not completely miscible, it is preferable to add a compatibilizer that allows them to be sufficiently miscible, such as a water-soluble organic solvent or a low molecular weight monomer. Adding a compatibilizer can improve emulsification and copolymerization properties.

[0159] As the water-soluble organic solvent, the organic solvents mentioned above may be used. For example, acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, etc., may be used in a range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of water. In addition, as low molecular weight monomers, methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., may be used in a range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of the total amount of monomers.

[0160] In polymerization, a chain transfer agent may be used. The molecular weight of the polymer can be changed depending on the amount of chain transfer agent used. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (especially alkyl mercaptans (e.g., with 1 to 40 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium bisulfite. The amount of chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, per 100 parts by weight of the total amount of monomer.

[0161] [(B) Silicone Compounds] The silicone compound (B) of this disclosure will now be described. Silicone compound (B) is a polyorganosiloxane compound having siloxane bonds. Silicone compound (B) may contain two or more polyorganosiloxane compounds. Silicone compound (B) consists of resin-based silicones and non-resin-based silicones.

[0162] In the GPC chart of silicone compound (B), a peak top exists in the region of molecular weight 1500 or higher. The presence of a peak top in the region of molecular weight 1500 or higher in the GPC chart obtained by GPC measurement can be confirmed by the following analysis. The presence of a peak top in the region of molecular weight 1500 or higher in the silicone compound was confirmed by gel permeation chromatography (polystyrene equivalent). For gel permeation chromatography, an HLC-8420GPC EcoSEC Elite-WS (manufactured by Tosoh) was used. Two TSKgel SuperMultiporeHZ-M columns were connected together. An RI detector was used as the detector. Standard polystyrene (SRM706a NIST) was used as the standard material. The analytical sample was prepared by dissolving resin-based silicone in tetrahydrofuran to make a 0.1 wt% solution and passing it through a 0.5 μm filter. When measuring the average molecular weight, the column was maintained at 40°C, tetrahydrofuran was used as the eluent, and 10 μL of the analytical sample was injected at a flow rate of 0.35 mL / min. Furthermore, components with a molecular weight of 1500 or more were separated from the silicone compound by preparative GPC. For gel permeation chromatography, an Agilent 1260 Infinity II LC system (manufactured by Agilent) was used. One SHODEX KF-G column and two SHODEX KF-806L columns were used in series. An ELSD detector was used as the detector. Polymethyl methacrylate was used as the standard substance. The analytical sample was prepared by dissolving the silicone compound in tetrahydrofuran to make a 0.1 wt% solution and passing it through a 0.5 μm filter. When measuring the average molecular weight, the column was maintained at 30°C, tetrahydrofuran was used as the eluent, and 100 μL of the analytical sample was injected at a flow rate of 0.50 mL / min. Components with a molecular weight of 1500 or more were concentrated, and the silicone compound component (Mn > 1500) was isolated. For the silicone compound component (Mn > 1500), １ H-NMR, ２９By measuring Si-NMR, we can confirm that the region contains non-resin silicone components.

[0163] Among silicone compounds, components with a molecular weight of 1500 or more include non-resin silicones other than amino-modified silicones. Components with a molecular weight of 1500 or more refer to components with a molecular weight of 1500 or more per molecule (i.e., resin-based silicones and / or non-resin-based silicones). The presence of resin-based silicones and / or non-resin-based silicones with a molecular weight of 1500 or more can be confirmed by GPC, etc.

[0164] Among silicone compounds, non-resin silicones other than amino-modified silicones with a molecular weight of 1500 or more may be non-resin silicones as described below in [Non-resin Silicone].

[0165] The silicon number of the silicone compound (B) may be 3 or more, 5 or more, 6 or more, 10 or more, 30 or more, 50 or more, 1000 or more, 2000 or more, or 3000 or more, preferably 10 or more, and may also be 50000 or less, 25000 or less, 10000 or less, 7500 or less, 5000 or less, 3000 or less, 1500 or less, 1000 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less, for example, 500 or less.

[0166] The number-average molecular weight of silicone compound (B) is 250 or more, preferably 300 or more, and more preferably 500 or more. The number-average molecular weight of the above silicone compound (B) may be 50,000 or less, or 10,000 or less. The number-average molecular weight of silicone compound (B) may be in the range of 250 to 50,000, or in the range of 250 to 10,000, for example, in the range of 1,000 to 7,000 or 2,000 to 6,000. The number-average molecular weight of silicone compound (B) can be measured using GPC. [Unit]

[0167] The silicone compound (B) is composed of a combination of at least one selected from the group consisting of M units, D units, T units, and Q units.

[0168] The M unit is (R Ｍ ) ３ SiO ０．５ Represents a unit. R Ｍ These are, independently, hydrocarbon groups having 1 to 40 carbon atoms or reactive groups in the silicone compound (B).

[0169] The ratio of M units contained in the silicone compound (B) of this disclosure may be 0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more in the silicone compound (B), or it may be 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less.

[0170] The amount of M units may be 0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, relative to the amount of D units, T units, or Q units, and may be 150 mol% or less, 130 mol% or less, 100 mol% or less, 80 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less.

[0171] The D unit is (R Ｄ ) ２ Represents the SiO unit. R Ｄ These are, independently, hydrocarbon groups having 1 to 40 carbon atoms or reactive groups in the silicone compound (B).

[0172] The proportion of D units in the silicone compound (B) of this disclosure may be 0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, or 95 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less. The silicone compound (B) of this disclosure may not contain D units.

[0173] The T unit is R Ｔ SiO１．５ Represents a unit. R Ｔ These are, independently, hydrocarbon groups having 1 to 40 carbon atoms or reactive groups in the silicone compound (B).

[0174] The proportion of T units contained in the silicone compound (B) of this disclosure may be 0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, or 95 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less. The silicone compound (B) of this disclosure may not contain T units.

[0175] The Q unit is SiO ２ It represents a unit.

[0176] The proportion of Q units in the silicone compound (B) of this disclosure may be 0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, or 95 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less. The silicone compound (B) of this disclosure may not contain Q units.

[0177] Examples of hydrocarbon groups having 1 to 40 carbon atoms include hydrocarbon groups having 1 to 5 carbon atoms and hydrocarbon groups having 6 to 40 carbon atoms.

[0178] Examples of hydrocarbon groups having 1 to 5 carbon atoms include methyl, ethyl, propyl, butyl, and pentyl groups (especially aliphatic hydrocarbon groups, especially alkyl groups, such as methyl or ethyl groups, especially methyl groups).

[0179] The hydrocarbon group having 6 to 40 carbon atoms may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, and particularly preferably a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be cyclic, linear, or branched, preferably linear. The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, preferably 10 or more, more preferably 12 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, more preferably 25 or less. Examples of aromatic hydrocarbon groups include phenyl groups.

[0180] Examples of reactive groups are groups having functional groups (e.g., hydroxyl groups, amino groups, mercapto groups, epoxy groups, carboxyl groups, halogen-substituted alkyl groups, vinyl groups, (meth)acrylic groups, (meth)acryloyloxy groups, oxyalkylene groups, isocyanate groups, and (meth)acrylamide groups, hydrogen atoms directly bonded to a silicon atom, etc.). These functional groups may be directly bonded to a silicon atom or to an organic group directly bonded to a silicon atom. The organic group may be a hydrocarbon group, for example, an alkylene group or a divalent aromatic group. The hydrocarbon group may have 2 to 12 carbon atoms, and alkylene groups with 2 to 10 carbon atoms are preferred. Divalent aromatic groups with 6 to 12 carbon atoms are preferred. The reactive group may be a group selected from the group consisting of hydroxyl groups, epoxy rings, carboxyl groups, (meth)acrylic groups, and amino groups, for example, at least one selected from the group consisting of epoxy rings, hydroxyl groups, (meth)acrylic groups, and carboxyl groups.

[0181] The silicone compound (B) may be an unmodified silicone (such as polyalkylsiloxane, polyalkylphenylsiloxane, or polydimethylsiloxane) in which the reactive groups have not been modified, or it may be a modified silicone (such as amino-modified, polyether-modified, epoxy-modified, carboxy-modified, methylhydrogen silicone, carbinol-modified silicone, carboxyl-modified silicone, or mercapto-modified silicone).

[0182] [Amount of Silicone Compound] The amount of silicone compound (B) is 51 to 99% by weight of the total amount of polymer (A) and silicone compound (B), and may be 51% or more by weight, 55% or more by weight, 60% or more by weight, 70% or more by weight, 80% or more by weight, and may be 99% or less by weight, 90% or less by weight, 85% or less by weight, 80% or less by weight, 75% or less by weight, 70% or less by weight, 65% or less by weight, 60% or less by weight, or 55% or less by weight, and may be 55 to 85% by weight.

[0183] The amount of silicone compound (B) in the water-repellent composition may be 0.01% by weight or more, 0.05% by weight or more, 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 1.0% by weight or more, 2.0% by weight or more, 3.0% by weight or more, or 5.0% by weight or more, and may also be 30% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7% by weight or less, 5% by weight or less, or 3% by weight or less.

[0184] [Ratio of resin-based silicone to non-resin-based silicone] The amount of resin-based silicone may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of non-resin-based silicone, and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

[0185] [Resin-based silicones] Resin-based silicones are organopolysiloxanes that have a three-dimensional structure within their molecules. An organopolysiloxane with a three-dimensional structure within its molecule is an organopolysiloxane that has siloxane bonds that branch in a three-dimensional manner.

[0186] The above three-dimensional structure may be a three-dimensional cross-linked structure in which a main chain composed of siloxane bonds is linked within that main chain and / or with other main chains composed of siloxane bonds. Such a three-dimensional structure can be achieved by including three-way branching T units and / or four-way branching Q units in the silicone, as detailed below. Since resin-based silicones contain a three-dimensional structure composed of three-dimensionally branched siloxane bonds, they are also called silicone resins.

[0187] The state of a resin-based silicone at 25°C is not particularly limited, as long as it has a three-dimensional structure within its molecule. For example, a resin-based silicone can exist in a solid, liquid, or gel state. In a preferred embodiment, the resin-based silicone may be a silicone that is solid at 25°C.

[0188] The resin-based silicone is composed of a combination of at least one type selected from the group consisting of M units, D units, T units, and Q units.

[0189] The resin-based silicone may be a resin composed of one or more units consisting of MQ, MT, MDT, MDQ, MTQ, DT, or MDTQ.

[0190] The molar ratio of M unit to D unit, T unit, or Q unit (M unit / D unit, M unit / T unit, or M unit / Q unit) may be 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, or 1.0 or more, and may also be 1.8 or less, 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, or 1.1 or less, and may be 0.6 or more and 1.7 or less, preferably 0.8 or more and 1.5 or less.

[0191] The molar ratio of D unit to M unit, T unit, or Q unit (D unit / M unit, D unit / T unit, or D unit / Q unit) may be 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, or 1.0 or more, and may also be 1.8 or less, 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, or 1.1 or less, and may be 0.6 or more and 1.7 or less, preferably 0.8 or more and 1.5 or less.

[0192] The ratio of M units contained in the resin-based silicone may be 0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, or 50 mol% or more in the resin-based silicone, and may also be 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less.

[0193] The amount of M units may be 0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, relative to the amount of D units, T units, or Q units, and may be 150 mol% or less, 130 mol% or less, 100 mol% or less, 80 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less.

[0194] The ratio of D units contained in the resin-based silicone may be 0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, or 50 mol% or more in the resin-based silicone, and may also be 95 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less.

[0195] The ratio of T units contained in the resin-based silicone may be 0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, or 50 mol% or more in the resin-based silicone, and may also be 95 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less.

[0196] The ratio of Q units contained in the resin-based silicone may be 0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, or 50 mol% or more in the resin-based silicone, and may also be 95 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less.

[0197] The definitions of M units, D units, T units, and Q units in resin-based silicones are as explained in Silicone Compound (B).

[0198] Resin-based silicones may also be obtained as solutions obtained by dissolving resin-based silicones in alkylpolysiloxane or a liquid medium other than alkylpolysiloxane. Examples of solvents other than alkylpolysiloxane include n-hexane, isopropyl alcohol, methylene chloride, 1,1,1-trichloroethane, and mixtures thereof.

[0199] Examples of solutions obtained by dissolving resin-based silicones in alkylpolysiloxane include KF7312J (trimethylsilyl group-containing polysiloxane:decamethylcyclopentasiloxane = 50:50 mixture), KF7312F (trimethylsilyl group-containing polysiloxane:octamethylcyclotetrasiloxane = 50:50 mixture), KF9021L (trimethylsilyl group-containing polysiloxane:low viscosity methylpolysiloxane = 50:50 mixture), and KF7312L (trimethylsilyl group-containing polysiloxane:low viscosity methylpolysiloxane = 50:50 mixture), all commercially available from Shin-Etsu Chemical Co., Ltd.

[0200] Commercially available resin-based silicones may be used. Examples of commercially available products include MQ-1600, MQ-1640 (manufactured by Dow Chemical Japan Ltd.), KR-220L, KR-251, KR-311, X-40-2406M (manufactured by Shin-Etsu Chemical Co., Ltd.), R2701 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), Silmer HQ20 (manufactured by Siltech), and SILDFORM FLEXIBLE RESIN (manufactured by MOMENTIVE).

[0201] The silicon number of the resin-based silicone may be 3 or more, 5 or more, 6 or more, 10 or more, 30 or more, 50 or more, 1000 or more, 1000 or more, 2000 or more, or 3000 or more, preferably 10 or more, and may also be 50000 or less, 25000 or less, 10000 or less, 7500 or less, 5000 or less, 3000 or less, 1500 or less, 1000 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less, for example, 500 or less.

[0202] Resin-based silicones may also be used as emulsions of resin-based silicones. Examples of resin-based silicone emulsions include X-52-8005, X-52-8432, X-52-8407, X-52-8407, X-52-8499DA, X-52-8500DA, KR-4000GE (all manufactured by Shin-Etsu Chemical Co., Ltd.), R2701 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), and Siltech E-2199 (manufactured by Siltech). The above commercially available products may contain MQ, MDQ, MT, MTQ, MDT, or MDTQ.

[0203] (Molecular Weight) The number average molecular weight Mn of resin-based silicones may be 200 or more, 300 or more, 500 or more, 700 or more, 1000 or more, 1500 or more, 2000 or more, 2500 or more, 3000 or more, 4000 or more, 5000 or more, 6000 or more, 8000 or more, or 10000 or more, and may also be 100000 or less, 80000 or less, 60000 or less, 50000 or less, 40000 or less, 30000 or less, 25000 or less, 20000 or less, 15000 or less, or 10000 or less.

[0204] The number-average molecular weight (Mn) of resin-based silicones can be obtained by GPC (gel permeation chromatography) (polystyrene equivalent). For gel permeation chromatography, an HLC-8420GPC EcoSEC Elite-WS (manufactured by Tosoh Corporation) was used. Two TSKgel SuperMultiporeHZ-M columns were connected together. An RI detector was used. Standard polystyrene (SRM706a NIST) was used as the standard material. The analytical sample was prepared by dissolving resin-based silicone in tetrahydrofuran to a 0.1% by weight solution, which was then filtered through a 0.5 μm filter. When measuring the average molecular weight, the column was maintained at 40°C, tetrahydrofuran was used as the eluent, and 10 μL of the analytical sample was injected at a flow rate of 0.35 mL / min.

[0205] Resin-based silicones may be commercially available products. Examples of commercially available products include MQ-1600 solid Resin (manufactured by Toray Dow Corning Co., Ltd.) and MQ-1640 Flake Resin (manufactured by Toray Dow Corning Co., Ltd.). These commercially available products contain a trimethylsilyl group-containing polysiloxane and may contain MQ, MDQ, MT, MTQ, MDT, or MDTQ.

[0206] [Non-resin silicones] Non-resin silicones are silicones other than resin silicones. Non-resin silicones are silicones that are mainly composed of two-dimensional siloxane bonds, for example, silicones that are mainly composed of linear and / or cyclic structures. In addition to linear and / or cyclic siloxane bonds, non-resin silicones may also contain branched chains that do not form a three-dimensional cross-linking structure (for example, branched chains that branch in a Y-shape or X-shape).

[0207] The state of non-resin silicone at 25°C is not particularly limited, and it can be in a solid, liquid, or gel state, for example. In a preferred embodiment, the non-resin silicone is a silicone that is liquid at 25°C.

[0208] Since non-resin silicones are silicones that primarily consist of two-dimensional siloxane bonds, they are also called silicone oils. However, even with silicone oils, depending on the molecular weight and the presence or absence of substituents such as alkyl groups, silicone oils are not necessarily in a liquid state at 25°C, and a solid state may also exist.

[0209] Non-resin silicones may consist mainly of M units and D units, but may also contain T units and / or Q units. Preferably, non-resin silicones do not contain T units and / or Q units. An example of a non-resin silicone is dimethyl silicone oil.

[0210] The ratio of M units contained in non-resin silicone may be 0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, or 50 mol% or more in the non-resin silicone, and may also be 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less.

[0211] The amount of M units may be 0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, relative to the amount of D units, T units, or Q units, and may be 150 mol% or less, 130 mol% or less, 100 mol% or less, 80 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less.

[0212] The ratio of D units contained in non-resin silicone may be 10 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, or 70 mol% or more in the non-resin silicone, and may also be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less.

[0213] The proportion of T units in non-resin silicones may be 0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, or 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less. Non-resin silicones do not need to contain T units.

[0214] The ratio of Q units in non-resin silicones may be 0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, or 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less. Non-resin silicones do not need to contain Q units.

[0215] The definitions of M units, D units, T units, and Q units in non-resin silicones are as explained in Silicone Compound (B).

[0216] The viscosity of non-resin silicone is 0.1 mm ２ / s or more, 1.0mm ２ / s or more, 5.0mm ２ / s or more, 10mm ２ / s or more, 50mm ２ / s or more, 100mm ２ / s or more, 300mm ２ / s or more, 500mm ２ / s or more, 1000mm ２ / s or more, 3000mm ２ / s or more, 5000mm ２ / s or more, 10000mm ２ / s or more, 30000mm ２ / s or more, 50000mm ２ / s or more, 100000mm ２ / s or more, 300000mm ２ / s or more, 500000mm ２ It may be greater than or equal to / s, and also 1,000,000 mm ２ / s or less, 500000mm ２ / s or less, 300000mm ２ / s or less, 100000mm ２ / s or less, 50000mm ２ / s or less, 30000mm ２ / s or less, 10000mm ２ / s or less, 5000mm ２ / s or less, 3000mm ２ / s or less, 1000mm ２ It may be less than or equal to / s.

[0217] The above-mentioned linear non-resin silicone may be a so-called straight silicone oil or a modified silicone oil. Examples of straight silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil. Examples of modified silicone oils include straight silicone oils modified with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, carbinol, mercapto, etc. Examples of cyclic silicone oils include cyclic dimethylsiloxane oil.

[0218] The silicon number of the non-resin silicone may be 3 or more, 5 or more, 6 or more, 10 or more, 30 or more, 50 or more, 1000 or more, 2000 or more, or 3000 or more, preferably 10 or more, and may also be 50000 or less, 25000 or less, 10000 or less, 7500 or less, 5000 or less, 3000 or less, 1500 or less, 1000 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less, for example, 500 or less.

[0219] A linear non-resin silicone (in other words, a linear polyorganosiloxane) may be a compound in which the side chains and terminals are saturated hydrocarbon groups. For example, a non-resin silicone may be a compound represented by the following formula (1).

[0220] [In the formula, R １１ , R １２ , R １３ , R １４ , R １５ , and R １６ Each of these is independently a monovalent saturated hydrocarbon group having 1 to 18 carbon atoms, and a is an integer greater than or equal to 1.

[0221] R １１ , R １２ , R １３ , R １４ , R １５ , and R １６Each of these is independently a monovalent saturated hydrocarbon group having 1 to 18 carbon atoms. The number of carbon atoms in such a monovalent saturated hydrocarbon group may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and may also be 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 2 or less.

[0222] R １１ , R １２ , R １３ , R １４ , R １５ , and R １６ The monovalent saturated hydrocarbon groups in this compound may be linear or branched, but linear is preferred, and linear alkyl groups are more preferred.

[0223] In one embodiment, R １１ , R １２ , R １３ , R １４ , R １５ , and R １６ The monovalent saturated hydrocarbon group in this compound is preferably a methyl group or an ethyl group, and more preferably a methyl group.

[0224] a is an integer greater than or equal to 1. The value of a may be selected such that the kinematic viscosity of the non-resin silicone represented by formula (1) falls within the range of the following non-resin silicones.

[0225] In one embodiment, a may be 3 or more, 5 or more, 6 or more, 10 or more, 30 or more, 50 or more, 100 or more, 500 or more, 1000 or more, 2000 or more, or 3000 or more, preferably 10 or more, and may also be 10000 or less, 7500 or less, 5000 or less, 3000 or less, 1500 or less, 1000 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less, preferably 1000 or less.

[0226] Examples of non-resin silicones represented by formula (1) include dimethylpolysiloxane and diethylpolysiloxane.

[0227] A cyclic non-resin silicone (in other words, a cyclic organopolysiloxane) may be a compound in which the side chain is a saturated hydrocarbon group. For example, a non-resin silicone may be a compound represented by the following formula (2).

[0228] [In the formula, R １７ and R １８ Each of these is independently a monovalent saturated hydrocarbon group having 1 to 18 carbon atoms, and w is an integer between 2 and 20.

[0229] R １７ and R １８ Each of these is independently a monovalent saturated hydrocarbon group having 1 to 18 carbon atoms. The number of carbon atoms in such saturated hydrocarbon groups is 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and may also be 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 2 or less, and preferably 1 to 10.

[0230] R １７ and R １８ The saturated hydrocarbon groups in this compound may be linear or branched, but linear is preferred, and linear alkyl groups are more preferred.

[0231] In one embodiment, R １７ and R １８ The saturated hydrocarbon group in this compound is preferably a methyl group or an ethyl group, and more preferably a methyl group.

[0232] b is an integer between 2 and 20. Preferably, b is between 3 and 10, and more preferably 4 or 5.

[0233] Examples of compounds represented by formula (2) include decamethylcyclopentasiloxane and octamethylcyclotetrasiloxane.

[0234] Non-resin silicones may be used individually or in combination of two or more types.

[0235] (Molecular Weight) Non-resin silicones may have a peak top in the region of molecular weight 1500 or more in the GPC chart obtained by GPC measurement. They may also contain at least one non-resin silicone other than amino-modified silicone. Non-resin silicones having a peak top in the region of molecular weight 1500 or more may be non-resin silicones other than amino-modified silicones, for example, the straight silicone oil or modified silicone oil (excluding amino-modified) exemplified above.

[0236] The non-resin silicone in silicone compound (B) may be a non-resin silicone with a molecular weight of 1500 or more, other than amino-modified silicones. A non-resin silicone with a molecular weight of 1500 or more means a non-resin silicone with a molecular weight of 1500 or more per molecule. The presence of a non-resin silicone with a molecular weight of 1500 or more can be confirmed by GPC or the like.

[0237] The number average molecular weight Mn of non-resin silicones may be 200 or more, 300 or more, 500 or more, 700 or more, 1000 or more, 1500 or more, 2000 or more, 2500 or more, 3000 or more, 4000 or more, 5000 or more, 6000 or more, 8000 or more, or 10000 or more, and may also be 100000 or less, 80000 or less, 60000 or less, 50000 or less, 40000 or less, 30000 or less, 25000 or less, 20000 or less, 15000 or less, or 10000 or less.

[0238] The number-average molecular weight (Mn) of non-resin silicones can be obtained by GPC (gel permeation chromatography) (polystyrene equivalent). For gel permeation chromatography, an HLC-8420GPC EcoSEC Elite-WS (manufactured by Tosoh Corporation) was used. Two TSKgel SuperMultiporeHZ-M columns were connected together. An RI detector was used. Standard polystyrene (SRM706a NIST) was used as the standard material. The analytical sample was prepared by dissolving non-resin silicone in tetrahydrofuran to a 0.1% by weight solution, which was then filtered through a 0.5 μm filter. When measuring the average molecular weight, the column was maintained at 40°C, tetrahydrofuran was used as the eluent, and 10 μL of the analytical sample was injected at a flow rate of 0.35 mL / min.

[0239] Non-resin silicones may be commercially available. Examples of commercially available products include KF-96-30CS (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-96-50CS (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-96-300CS (manufactured by Shin-Etsu Chemical Co., Ltd.), and KF-96-1000CS (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0240] [Silicone Emulsion] Silicone compound (B) may be a silicone emulsion emulsified with a dispersant, surfactant, etc. In other words, silicone compound (B) may be included in the water-repellent composition in an emulsified state combined with a dispersant, surfactant, etc.

[0241] The dispersant and surfactant may be those specified in this disclosure. The emulsification of the silicone compound (B) may be carried out by known methods. When the silicone compound (B) is emulsified, it becomes easier to uniformly disperse the silicone compound (B) in the water-repellent composition, and it becomes easier to suitably impart liquid repellency.

[0242] The silicone emulsion may be either an oil-in-water (O / W) emulsion or a water-in-oil (W / O) emulsion. The liquid medium used in the silicone emulsion may be one of the liquid media described in the section on [Liquid Media] of this disclosure.

[0243] The silicone emulsion contained in the water-repellent composition in this disclosure may be anionic, cationic, or nonionic, with nonionic surfactants being preferred.

[0244] The water-repellent compositions of this disclosure may further include the resin-based silicones and / or non-resin-based silicones exemplified above.

[0245] The water-repellent compositions of this disclosure may not contain amino-modified silicones.

[0246] The water-repellent composition or aqueous dispersion described herein may be an aqueous dispersion.

[0247] The pH of the water-repellent composition of this disclosure is not particularly limited, but may be between 3.0 and 11.0.

[0248] [Wax] The water-repellent compositions of this disclosure may include wax, particularly hydrocarbon wax. The wax may be an organic substance that is solid at room temperature and becomes liquid when heated. For example, the wax may be a hydrocarbon compound or a compound having a hydrocarbon group (e.g., alkyl group) with 6 to 40 carbon atoms.

[0249] The wax in this disclosure adheres to a substrate (particularly a pulp substrate) and can impart to the substrate liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance.

[0250] [Wax Properties, etc.] The properties of the wax are as follows.

[0251] The wax may be in particulate form (powder). The average particle size of the wax may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, and may also be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less. The above particle sizes are primary particle sizes. Being within the above range can result in excellent particle stability and good liquid repellency. The average particle size can be measured with a microscope (scanning electron microscope). Specifically, a sample of wax particles is observed with a microscope at any magnification. Next, if the particle shape is spherical, its diameter will be considered as the particle size; if it is non-spherical, the average of the longest and shortest diameters will be considered as the particle size. The particle size of all particles present in the field of view will be measured, and the field of view will be moved and the particle size measured again. By repeating this process, the particle size will be measured at more than 100 points, and the average value of these measurements will be taken as the average particle size.

[0252] The HD (n-hexadecane) contact angle of the wax may be 10° or more, 20° or more, 25° or more, 30° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 60° or more, or 65° or more, preferably 25° or more, more preferably 30° or more, and may also be 100° or less, 90° or less, or 75° or less. By having an HD contact angle of the wax above the lower limit, good liquid repellency (especially oil repellency) can be imparted to the substrate. The HD contact angle is the static contact angle of the wax with respect to the spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle 1 second after dropping.

[0253] The water contact angle of the wax may be 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more, and may also be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. By having a water contact angle of the wax above the lower limit, good liquid repellency (especially water repellency) can be imparted to the substrate. The water contact angle is the static contact angle of the wax with respect to the spin-coated film, and is obtained by dropping 2 μL of water onto the spin-coated film and measuring the contact angle 1 second after the drop.

[0254] The wax may be low molecular weight (for example, molecular weight of 1000 or less, or 500 or less) or high molecular weight. If the wax is high molecular weight, its weight-average molecular weight may be 1000 or more, 3000 or more, 5000 or more, 7500 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may also be 10000000 or less, 7500000 or less, 5000000 or less, 3000000 or less, 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 100000 or less, 7500 or less, 5000 or less, or 3000 or less.

[0255] The melting point of the wax may be 30°C or higher, 40°C or higher, 50°C or higher, 60°C or higher, 80°C or higher, 100°C or higher, or 120°C or higher, preferably 40°C or higher, particularly preferably 55°C or higher, and may also be 250°C or lower, 225°C or lower, 200°C or lower, 150°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, 80°C or lower, or 50°C or lower, preferably 120°C or lower. The melting point of the wax may be measured in accordance with JIS K 2235-1991. The melting point usually corresponds to the peak top temperature of the endothermic peak of the maximum temperature before melting, as observed by DSC (Differential Scanning Calorimetry).

[0256] [Types of Wax, etc.] Examples of waxes include mineral waxes (petroleum waxes) such as paraffin wax, microcrystalline wax, montane wax, ozokerite wax, ceresin wax, and petrolatum wax; and synthetic waxes such as Fischer-Tropsch wax, polyethylene wax, and polypropylene wax, with paraffin wax or microcrystalline wax being preferred. The wax in this disclosure may be a hydrocarbon wax, preferably a linear aliphatic hydrocarbon, for example, a linear or branched hydrocarbon, and particularly a linear hydrocarbon.

[0257] [Isocyanate Derivatives] The water-repellent compositions of this disclosure may contain isocyanate derivatives. The isocyanate derivatives have hydrocarbon groups having 2 to 40 carbon atoms, particularly monovalent hydrocarbon groups having 2 to 40 carbon atoms.

[0258] Isocyanate derivatives are compounds obtained by the reaction of an active hydrogen compound with a starting isocyanate, and have a portion derived from the active hydrogen-containing compound and a portion derived from the starting isocyanate. Unlike isocyanate-based curing agents, isocyanate derivatives do not usually have an isocyanate group.

[0259] Isocyanate derivatives have an NHCO- group formed by the reaction of an active hydrogen compound with a starting isocyanate (where NHCO- may be part of a urethane group or urea group). The NHCO- group is formed by the reaction of an active hydrogen-containing group (typically a hydroxyl group) of the active hydrogen compound with an active hydrogen-reactive group (typically an isocyanate group) of the starting isocyanate. Isocyanate derivatives are typically urethanes (especially polyurethanes).

[0260] The hydrocarbon group having 2 to 40 carbon atoms in the isocyanate derivative is preferably a monovalent hydrocarbon group. The hydrocarbon group having 2 to 40 carbon atoms is described above in the section on (hydrocarbon group having 2 to 40 carbon atoms).

[0261] The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched, cyclic, or linear, and is more preferably linear, particularly linear. The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 10 or more, 12 or more, or 16 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, 25 or less, or 20 or less.

[0262] The weight-average molecular weight of the isocyanate derivative may be 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more, and may also be 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, or 5,000 or less.

[0263] [Active Hydrogen Compounds] Active hydrogen compounds contain active hydrogen groups that react with isocyanate groups.

[0264] Examples of active hydrogen groups include hydroxyl groups, amino groups, and carboxyl groups, but typically it is the hydroxyl group.

[0265] The (α1) hydrocarbon alcohol active hydrogen compound may be an active hydrogen compound (α1) composed of a hydrocarbon group and a hydroxyl group.

[0266] The hydrocarbon group in the active hydrogen compound (α1) is a hydrocarbon group having 2 to 40 carbon atoms as described above, and the above explanation applies.

[0267] Furthermore, the active hydrogen compound (α1) preferably has one hydroxyl group per molecule.

[0268] Examples of active hydrogen compounds (α1) include linear saturated hydrocarbon group-containing alcohols such as n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol (stearyl alcohol), n-nonadecanol, and eicosanol; branched saturated hydrocarbon group-containing alcohols such as isomiristyl alcohol, isocetyl alcohol, isostearyl alcohol, and isoicosyl alcohol; linear unsaturated hydrocarbon group-containing alcohols such as tetradecenyl alcohol, hexadecenyl alcohol, oleyl alcohol, icocenyl alcohol, dococenyl alcohol, tetracocenyl alcohol, hexacocenyl alcohol, and octacocenyl alcohol; and branched unsaturated hydrocarbon group-containing active hydrogen compounds such as phytol.

[0269] Here, a linear saturated hydrocarbon group-containing alcohol and a linear unsaturated hydrocarbon group-containing alcohol may be used in combination. When a linear saturated hydrocarbon group-containing alcohol and a linear unsaturated hydrocarbon group-containing alcohol are used in combination, the blending ratio of the linear saturated hydrocarbon group-containing alcohol is, for example, 40 parts by mass or more, preferably 55 parts by mass or more, more preferably 70 parts by mass or more, and also, for example, 90 parts by mass or less, preferably 80 parts by mass or less, based on 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol. The blending ratio of the linear unsaturated hydrocarbon group-containing alcohol is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, and also, for example, 60 parts by mass or less, preferably 45 parts by mass or less, and more preferably 30 parts by mass or less, based on 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol. If the proportion of linear saturated hydrocarbon group-containing alcohol is above the lower limit mentioned above, the crystallinity of the hydrocarbon group will improve, and as a result, the liquid repellency of the treated object can be improved.

[0270] The (α2) sugar alcohol / hydroxy acid modified active hydrogen compound may be a sugar alcohol / hydroxy acid modified compound (α2) which is a sugar alcohol / hydroxy acid (sugar alcohol and / or hydroxy acid) modified with a hydrocarbon group having 2 to 40 carbon atoms. The type of sugar alcohol / hydroxy acid is not limited and may be cyclic or acyclic. Examples of sugar alcohols include monosaccharides, reducing sugars, amino sugars, aldonic acids, and aldonic acid lactones, and examples of hydroxy acids include hydroxypolycarboxylic acids, etc. The sugar alcohol / hydroxy acid may be a substance that exists in living organisms. Examples of sugar alcohols / hydroxy acids include compounds derived from aldoses and ketoses, such as tetrose, pentose, hexose, and heptose, but are not limited to these. Specific examples include glucose, glyceraldehyde, erythrose, arabinose, ribose, arabinose, allose, altrose, mannose, xylose, lyxose, glycerol, galactose, talose, fructose, ribulose, mannoheptulose, sedoheptulose, threose, erythritol, threitol, glucopyranose, and mannopyranose. Examples include sugar alcohols, taropyranose, allopyranose, altropyranose, idopyranose, globyranose, glucitol, mannitol, erythritol, sorbitol, arabitol, xylitol, ribitol, galactitol, fusitol, iditol, inositol, pentaerythritol, dipentaerythritol, boremitol, gluconic acid, glyceric acid, xylonic acid, galactaric acid, ascorbic acid, citric acid, gluconate lactone, glyceric acid lactone, xylonate lactone, glucosamine, galactosamine, or mixtures thereof. The number of carbon atoms in the sugar alcohol / hydroxy acid may be 2 or more, 4 or more, or 6 or more, and may be 30 or less, 20 or less, or 10 or less. The average OH value of the compound (α2) may be in the range of greater than 0 to about 230, preferably about 10 to about 175, most preferably about 25 to about 140.

[0271] The number of hydrocarbon groups having 2 to 40 carbon atoms in the sugar alcohol / hydroxy acid modified product (α2) may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more, and may also be 12 or less, 9 or less, 6 or less, or 3 or less.

[0272] In the sugar alcohol / hydroxy acid modified product (α2), at least one active hydrogen (e.g., hydrogen in the OH group, carboxyl group) of the sugar alcohol and / or hydroxy acid is -R α２ , -C(O)R α２ ,-(CH ２ CH ２ O) ｎ (CH(CH ３ )CH ２ O) ｍ R α２ ,-(CH ２ CH ２ O) ｎ (CH(CH ３ )CH ２ O) ｍ C(O)R α２ R may be substituted with an active hydrogen substituent selected from a mixture thereof. α２ n is a hydrogen atom or a hydrocarbon group having 2 to 40 carbon atoms, each n is independently 0 to 20, each m is independently 0 to 20, and m+n may be greater than 0. Compound (α2) has at least one active hydrogen, and for example, in a sugar alcohol / hydroxy acid modified product, at least one (1 or more) of the active hydrogens of the sugar alcohol / hydroxy acid may be unmodified, and this active hydrogen (e.g., an -OH group) may react with the active hydrogen reactant group (especially an isocyanate group) of compound (b) to form -NHCO-.

[0273] (α21) Sorbitan-modified sugar alcohol / hydroxy acid modified product (α2) may be a sorbitan-modified product (α21) obtained by modifying sorbitan with a hydrocarbon group having 2 to 40 carbon atoms, and may particularly be an alkylsorbitan, with sorbitan being -R α２ , -C(O)R α２ ,-(CH ２ CH ２ O) ｎ (CH(CH ３ )CH２ O) ｍ R α２ ,-(CH ２ CH ２ O) ｎ (CH(CH ３ )CH ２ O) ｍ C(O)R α２ , or compounds substituted with a mixture thereof (where R α２ (A hydrocarbon group has 2 to 40 carbon atoms). For example, sorbitan is -C(O)R α２ The compound may be monosubstituted, disubstituted, or trisubstituted. Here, sorbitan may contain amounts of sorbitol, isosorbide, or other intermediates or by-products. Commercially available sorbitan such as SPAN can be used as the alkylsorbitan.

[0274] In one embodiment, at least one active hydrogen substituent is -C(O)R α２ It is fine if R α２ The C1 is a linear or branched alkyl group having 6 to 40 carbon atoms, more preferably 7 to 21, and most preferably 11 to 21 carbon atoms. Preferred compounds include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, and monosubstituted, disubstituted, and trisubstituted sorbitans derived from mixtures thereof. Particularly preferred compounds include monosubstituted, disubstituted, and trisubstituted sorbitan stearates, or sorbitan behenin.

[0275] In one embodiment, R α２ It may contain at least one unsaturated bond. An example of such a compound (at least one active hydrogen substituent is -C(O)R α２ Selected from, R α２ As an example of a compound containing at least one unsaturated bond, sorbitan trioleate (i.e., in the formula R α２ Ha-C ７ H １４ CH = CHC ８ H １７Examples include, but are not limited to, palmitoleic acid, linoleic acid, arachidonic acid, and erucic acid, which are monosubstituted, disubstituted, and trisubstituted sorbitans.

[0276] In one embodiment, the sorbitan modified product (α21) has at least one active hydrogen substituent, and the active hydrogen substituent is independently -(CH ２ CH ２ O) ｎ (CH(CH ３ )CH ２ O) ｍ R α２ or - (CH ２ CH ２ O) ｎ (CH(CH ３ )CH ２ O) ｍ C(O)R α２ It is acceptable that each m is independently between 0 and 20, each n is independently between 0 and 20, and m + n is greater than 0. Such compounds are known as polysorbates and are marketed under the trademark name TWEEN. These sorbitans are R α２ Therefore, monosubstituted, disubstituted, or trisubstituted compounds can be used. Commercially available polysorbates have each R ２ From various polysorbates in which H (unsubstituted), each R α２ It is known to contain a wide range of mixtures, from polysorbates in which α21 is a linear or branched alkyl group having 6 to 40 carbon atoms (fully substituted), and mixtures of various substitutions thereof. Examples of such sorbitan modified products (α21) include polysorbates such as polysorbate tristearate and polysorbate monostearate. m+n is greater than 0, and R α２ Examples of sorbitan modifications (α21) containing at least one unsaturated bond include, but are not limited to, polysorbate trioleates (where R α２ C ７ H １４ CH = CHC ８ H １７Examples include (which are commercially available under the name polysorbate 80). The sorbitan modified product (α21) may contain a mixture of compounds having various active hydrogen substituents, and R α２ A compound containing at least one unsaturated bond, and R α２ It may also contain a mixture with a completely saturated compound.

[0277] (α22) The citrate-modified sugar alcohol / hydroxy acid-modified (α2) may be a citrate-modified (α22) obtained by modifying citrate with a hydrocarbon group having 6 to 40 carbon atoms, and may particularly be an alkyl citrate. For example, the citrate-modified (α22) may exist as a monosubstituted, disubstituted, or trisubstituted product having an alkyl group. A mixture of citrates having active hydrogen substituents of various values ​​may be used, and R α２ A compound having a hydrocarbon group having at least one unsaturated bond, and R α２ It may also contain a mixture with a compound that is a completely saturated hydrocarbon. The citric acid modified compound (α22) is -(CH ２ CH ２ O) ｎ (CH(CH ３ )CH ２ O) ｍ R α２ Or, -(CH ２ CH ２ O) ｎ (CH(CH ３ )CH ２ O) ｍ C(O)R α２ It may have an active hydrogen substituent selected from (where R α２ (This refers to a hydrocarbon group having 6 to 40 carbon atoms.) Examples of citrate-modified (α22) compounds include, but are not limited to, trialkyl citrates.

[0278] (α23) Pentaerythritol-modified sugar alcohol / hydroxy acid-modified (α21) may be a pentaerythritol-modified (α23) obtained by modifying pentaerythritol with a hydrocarbon group having 6 to 40 carbon atoms, and may be a monosubstituted, disubstituted, or trisubstituted product having a hydrocarbon group (especially an alkyl group) having 6 to 40 carbon atoms, for example, a dipentaerythriol ester. The active hydrogen substituent is -CH ２ C[CH ２ OR α２ ] ３ It may include (where R α２ ( is a hydrocarbon group having 6 to 40 carbon atoms). Also, the pentaerythritol modified compound (α23) is a compound having a mixture of hydrocarbon groups with different chain lengths, or R α２ A compound containing at least one unsaturated bond, and R α２ It may also contain a mixture with a completely saturated compound.

[0279] (α3) Cationic active hydrogen compound The active hydrogen compound may be a cationic active hydrogen compound (α3) having an active hydrogen group and a cationic group.

[0280] Furthermore, the cationic active hydrogen compound (α3) preferably has two or more hydroxyl groups per molecule.

[0281] Examples of cationic groups include tertiary amino groups.

[0282] In other words, the cationic active hydrogen compound (α3) preferably has two or more hydroxyl groups per molecule as active hydrogen groups and a tertiary amino group as a cationic group.

[0283] Such cationic active hydrogen compounds can impart good dispersibility to liquid media (e.g., water), and can also introduce cationic groups that have affinity for textile products (described later) into the resin, thereby improving wash durability.

[0284] More preferably, the cationic active hydrogen compound has two hydroxyl groups per molecule as active hydrogen groups and a tertiary amino group as a cationic group.

[0285] Examples of such cationic active hydrogen compounds include alkyldialkanolamines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, N-methyldipropanolamine, and propanolamine, as well as trialkanolamines such as N-triethanolamine and N-triisopropanolamine, with N-methyldiethanolamine being preferred.

[0286] The cationic active hydrogen compound (or the portion of the hydrophobic compound derived from the cationic active hydrogen compound) may form a salt with the acid compound.

[0287] Examples of acid compounds include organic acids and inorganic acids. Examples of organic acids include acetic acid, lactic acid, tartaric acid, and malic acid, with acetic acid and lactic acid being preferred, and acetic acid being more preferred. Examples of inorganic acids include hydrochloric acid, sulfuric acid, and phosphoric acid, with hydrochloric acid being preferred. Examples of acid compounds include organic acids. If the acid compound contains an organic acid, the acid will volatilize upon heat treatment, thereby improving the liquid repellency of the treated product treated with this water-repellent composition. Furthermore, the volatilization of the acid upon heat treatment can improve the wash durability of textile products from the viewpoint of making it easier for cationic groups to adsorb onto textile products. (α4) Other active hydrogen-containing compounds The active hydrogen compound (α) may contain other active hydrogen compounds (α4).

[0288] (α41) Compound Active Hydrogen Compound (α4) is of formula R α４１ -X α４１ [In the formula, R α４１ C may contain at least one unsaturated group. １ ~C ３０ Linear or branched alkyl, hydroxy-functional C １ ~C ３０ Linear or branched alkyl, hydroxy-functionalized linear or branched C １ ~C ３０ Polyethers, hydroxy-functional linear or branched polyesters, hydroxy-functional linear or branched organosiloxanes, thiol-functional C １ ~C３０ Linear or branched alkyl, amine-functionalized C １ ~C ３０ Linear or branched alkyl groups, Y － R α４１１ R α４１２ R α４１３ N ＋ -R α４１４ - (Here, Y is a halide ion, for example, Cl － It is. ), HOS (=O) ２ -R α４１４ -, or R α４１１ R α４１２ C = N - (where R α４１１ , R α４１２ , R α４１３ These are independently -H and C １ ~C ６ It is alkyl, R α４１４ X is a divalent alkyl group having 1 to 20 carbon atoms. α４１ is -OH, -C(O)OH, -SH, -NH(R'), -O-(CH ２ CH ２ O) ｓ (CH(CH ３ )CH ２ O) ｔ -H or -C(O)-O-(CH ２ CH ２ O) ｓ (CH(CH ３ )CH ２ O) ｔ -H is an isocyanate-reactive functional group (where R ’ is a -H or monovalent organic group, s is an integer from 0 to 50, t is an integer from 0 to 50, and s + t is greater than 0. ) The compound may be represented by (α41) as ].

[0289] Compound (α41) may be a hydrophilic water-soluble material containing at least one hydroxy-terminated polyether, where X α４１ is -O-(CH ２ CH ２ O) ｓ (CH(CH ３ )CH ２ O) ｔ -H or -C(O)-O-(CH ２ CH２ O)s(CH(CH ３ )CH ２ O) ｔ -H. -(CH ２ CH ２ O)- represents the oxyethylene group (EO), and -(CH(CH ３ )CH ２ O)- represents an oxypropylene group (PO). These polyethers may contain only EO groups, only PO groups, or mixtures thereof. These polyethers may also exist as the specified PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol) triblock copolymer.

[0290] In one embodiment, X α４１ -OH, -C(O)OH, -SH, -NH(R) ’ ) and R α４１ C, which optionally contains at least one unsaturated group. １ ~C ３０ Linear or branched alkyl, hydroxy-functional C １ ~C ３０ Linear or branched alkyl, hydroxy-functionalized linear or branched C １ ~C ３０ Polyethers, hydroxy-functional linear or branched polyesters, hydroxy or amine-functional linear or branched organosiloxanes, thiol-functional C １ ~C ３０ Linear or branched alkyl, amine-functionalized C １ ~C ３０ Selected from linear or branched alkyl groups.

[0291] X α４１ is a -OH group, and examples of such compounds (α41) include alkyl alcohols such as propanol and butanol, or aliphatic alcohols including stearyl alcohol (R α４１ C optionally contains at least one unsaturated group. １ ~C ３０ Alkyl diols or polyols such as ethanediol, propanediol, butanediol, or hexanediol (R) are linear or branched alkyl groups.α４１ is hydroxy-functional C １ ~C ３０ Alkylene glycol ethers such as triethylene glycol, tetraethylene glycol, poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), poly(tetrahydrofuran), or glycol ethers having a mixture of PEG, PPG, or THF units (R α４１ This refers to hydroxy-functional linear or branched C2 molecules. １ ~C ３０ Polyether), polyester polyol (R α４１ (R) is a hydroxy-functional linear or branched polyester, a silicone prepolymer polyol. α４１ (R is a hydroxy-functional linear or branched organosiloxane) α４１ C is an amine-functionalized C １ ~C ３０ (R) choline chloride or betaine HCl (R) α４１ Y － R α４１１ R α４１２ R α４１３ N ＋ -R α４１４ - is), butanone oxime (R α４１ R α４１１ R α４１２ Examples include, but are not limited to, polyether polyols (where C=N-). Polyether polyols may contain only EO groups, only PO groups, only THF groups, or mixtures thereof. These polyethers may also exist as block copolymers, such as those specified by PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol). Polyether glycols preferably have an average molecular weight of about 200 or more, most preferably 350 to 2000.

[0292] X α４１is -C(O)OH, and examples of such compounds (α41) include fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, palmitoleic acid, linoleic acid, arachidonic acid, oleic acid, or erucic acid (R α４１ C, which optionally contains at least one unsaturated group. １ ~C ３０ Hydroxy-containing acids (R) such as hydroxycaprylic acid, hydroxycapric acid, hydroxylauric acid, hydroxymyristic acid, hydroxypalmitic acid, hydroxystearic acid, hydroxyarachidic acid, hydroxybehenic acid, hydroxylignoceric acid, hydroxypalmitoleic acid, hydroxylinoleic acid, hydroxyarachidonic acid, hydroxyoleic acid, or hydroxyerucic acid (R) α４１ is hydroxy-functional C １ ~C ３０ (R) mercaptoalkanoic acid (R) such as mercaptopropionic acid (which is linear or branched alkyl) α４１ This is thiol functional C １ ~C ３０ Examples include, but are not limited to, linear or branched alkyl groups.

[0293] X α４１ This may be -SH, and examples of such compounds (α41) include alkylthiols such as lauryl mercaptan or dodecyl mercaptan (R α４１ C, which optionally contains at least one unsaturated group. １ ~C ３０ Examples include, but are not limited to, linear or branched alkyl groups.

[0294] X α４１ This may be -NH(R'), and examples of such compounds (α41) include alkylamines such as diisopropylamine, propylamine, hexylamine, or laurylamine (R α４１ C, which optionally contains at least one unsaturated group. １ ~C ３０Alkanolamines such as ethanolamine or propanolamine (R) are linear or branched alkyl groups. α４１ is hydroxy-functional C １ ~C ３０ (R) Silicone prepolymer polyamine (R) α４１ (R) is an amine-functional linear or branched organosiloxane, alkyldiamine ( α４１ C is an amine-functionalized C １ ~C ３０ (R) (linear or branched alkyl), and aminoalkanesulfonic acids such as 2-aminoethanesulfonic acid α４１ HO-S(O) ２ R α４１４ Examples include, but are not limited to, these.

[0295] (α42) Compound Compound (α42) is of formula R α４２１ - (OCH ２ CH(OR α４２２ )CH ２ ) ｚ -OR α４２３ [In the formula, R α４２１ , R α４２２ and R α４２３ is at least one R α４２１ , R α４２２ or R α４２３ -H, and independently of each other, -H and -R α４２４ , -C(O)R α４２４ And R α４２４ This is a linear or branched alkyl group having 5 to 29 carbon atoms, which may independently contain at least one unsaturated bond, and z is 1 to 15.

[0296] Compound (α42) may be a compound generally known as polyglycerol. Other specific examples include, but are not limited to, triglycerol monostearate, triglycerol distearate, hexaglycerol monostearate, hexaglycerol distearate, decaglyceryl mono(caprylate / caprate), decaglyceryl di(caprylate / caprate), decaglycerol, polyglycerol-3, and C18 diglycerides.

[0297] The (α43) chain extender compound (α4) may also be the chain extender (α43). The chain extender (α43) is a compound having two or more (for example, two) functional groups containing active hydrogen within its molecule. Known chain extenders can be used as chain extenders, and examples include aliphatic or aromatic diols or polyols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripylene glycol, 1,4-butanediol, 1,6-hexanediol, and cyclohexanedimethanol; aliphatic or aromatic diamines or polyamines such as ethylenediamine, piperazine, aminoethylpiperazine, phenylenediamine, and diethyltoluenediamine; phenol hydroxyl group-containing compounds such as resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxylphenyl)-1-phenylethane), bisphenol F, bisphenol K, bisphenol M, tetramethylbiphenol, and o,o'-diallyl-bisphenol A; and alcohol amines such as aminoethylethanolamine, aminopropylethanolamine, aminohexylethanolamine, aminoethylpropanolamine, aminopropylpropanolamine, and aminohexylpropanolamine.

[0298] [Raw material isocyanate] Isocyanate derivatives have a portion derived from the raw material isocyanate.

[0299] The raw material isocyanate may be an aromatic polyisocyanate, an acyclic aliphatic polyisocyanate, a cyclic alicyclic polyisocyanate, or a bridged cyclic alicyclic polyisocyanate.

[0300] Aromatic polyisocyanates are compounds having aromatic rings and isocyanate groups. The aromatic rings in an aromatic polyisocyanate may be one or more, two or more, or three or more, and may be five or fewer, four or fewer, or three or fewer.

[0301] Acyclic aliphatic polyisocyanates are aliphatic polyisocyanates that do not have a cyclic structure. Acyclic aliphatic polyisocyanates may have aliphatic hydrocarbon groups having 2 to 20 carbon atoms. The aliphatic hydrocarbon groups having 2 to 20 carbon atoms may be divalent aliphatic hydrocarbon groups. The number of carbon atoms in the aliphatic hydrocarbon group may be 2 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, or 14 or more, preferably 4 or more, 6 or more, or 8 or more. The number of carbon atoms in the aliphatic hydrocarbon group may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, or 10 or less, preferably 14 or less, 12 or less, or 10 or less. In one embodiment, the acyclic aliphatic polyisocyanate may be a polyisocyanate compound having an isocyanate group at the terminus of an alkylene group.

[0302] Cyclic alicyclic polyisocyanates are aliphatic polyisocyanates having a cyclic structure. Cyclic alicyclic polyisocyanates have a carbon ring that is not an aromatic ring. Cyclic alicyclic polyisocyanates may have an aliphatic hydrocarbon group having 2 to 20 carbon atoms. The aliphatic hydrocarbon group having 2 to 20 carbon atoms is described in the same way as described for acyclic aliphatic polyisocyanates above.

[0303] Bridged alicyclic polyisocyanates are polycyclic compounds having a crosslinking structure in their ring structure, such as a methylene group. Bridged alicyclic polyisocyanates may also have aliphatic hydrocarbon groups having 2 to 20 carbon atoms. The aliphatic hydrocarbon groups having 2 to 20 carbon atoms are described in the same way as described for acyclic aliphatic polyisocyanates above.

[0304] The raw material isocyanate may be a derivative of the raw material isocyanate. Here, examples of derivatives include isocyanurate derivatives, allophanate derivatives, polyol derivatives, biuret derivatives, urea derivatives, oxadiazinetrione derivatives, carbodiimide derivatives, uretodione derivatives, uretonimine derivatives, and the like.

[0305] The raw material isocyanate may be a derivative of a polyisocyanate selected from the group consisting of aromatic polyisocyanates, acyclic aliphatic polyisocyanates, cyclic alicyclic polyisocyanates, and bridged cyclic alicyclic polyisocyanates.

[0306] In one embodiment, the raw material isocyanate may be an isocyanurate derivative or a biuret derivative.

[0307] In one embodiment, the raw material isocyanate may be an acyclic aliphatic polyisocyanate.

[0308] Examples of raw material isocyanates include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or mixture thereof) (TDI), phenylene diisocyanate (m-,p-phenylene diisocyanate or mixture thereof), 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4' or 2,2'-diphenylmethane diisocyanate or mixture thereof) (MDI), 4,4'-toluidine isocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or Aromatic polyisocyanates selected from 1,4-tetramethylxylylene diisocyanate or a mixture thereof (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4- or 1,8-naphthalene diisocyanate or a mixture thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatephenyl)thiophosphate, polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate;Acyclic aliphatic polyisocyanates selected from trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl caprate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, and decamethylene diisocyanate; 1,3-Cyclopentane diisocyanate, 1,3-Cyclopentene diisocyanate, Cyclohexane diisocyanate (1,4-Cyclohexane diisocyanate, 1,3-Cyclohexane diisocyanate), 3-Isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), Methylenebis(cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylenebis(cyclohexyl isocyanate) or mixtures thereof) (Hydrogenated MDI), Methylcyclohex Cyclic alicyclic polyisocyanates selected from diisocyanates (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanate methyl)cyclohexane (1,3- or 1,4-bis(isocyanate methyl)cyclohexane or a mixture thereof) (hydrogenated XDI), dimer acid diisocyanate, transcyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), hydrogenated tetramethylxylylene diisocyanate (hydrated TMXDI); bridged cyclic alicyclic polyisocyanates selected from norbornene diisocyanate, norbornane diisocyanate methyl, bicycloheptane triisocyanate, diisocyanate methylbicycloheptane, di(diisocyanate methyl)tricyclodecane; Compounds selected from the above; and biuret-modified isocyanates, polyisocyanate polymers (e.g., dimers, trimers (e.g., isocyanurate derivatives, iminooxadiazinedione derivatives), pentamers, heptamers, etc.), allophanate derivatives (e.g., allophanate derivatives produced by the reaction of the above polyisocyanate with a monohydric or dihydric alcohol), polyol derivatives (e.g., polyol derivatives produced by the reaction of the above polyisocyanate with a trihydric alcohol (e.g., trimethylolpropane, etc.) (alcohol adducts, preferably trimethylolpropane) Examples include: (adducts, etc.), biuret derivatives (for example, biuret derivatives produced by the reaction of the above-mentioned polyisocyanate with water or amines), urea derivatives (for example, urea derivatives produced by the reaction of the above-mentioned polyisocyanate with diamines), oxadiazinetrione derivatives (for example, oxadiazinetrione produced by the reaction of the above-mentioned polyisocyanate with carbon dioxide), carbodiimide derivatives (for example, carbodiimide derivatives produced by the decarboxylation condensation reaction of the above-mentioned polyisocyanate), uretdione derivatives, uretonimine derivatives, etc.

[0309] The average number of isocyanate groups in the raw material isocyanate is 2 or more, preferably 2.5, more preferably 2.9, and also, for example, 3.8 or less. The raw material isocyanate may be a polyisocyanate having multiple isocyanate groups.

[0310] [Method for synthesizing isocyanate derivatives]

[0311] To obtain an isocyanate derivative, the active hydrogen compound and the starting isocyanate are reacted. The reaction may be carried out in one step or in multiple steps in a sequential manner. For example, if the product contains unreacted active hydrogen groups or active hydrogen reactive groups, the synthesis may be carried out sequentially. Sequential reactions are particularly useful when using substituted sugar alcohols with a high number of OH groups. The reaction conditions, such as reaction concentration and reaction temperature, are not particularly limited and can be determined by those skilled in the art. Specifically, the active hydrogen compound and the starting isocyanate may be blended such that the equivalent ratio of active hydrogen reactive groups (isocyanate groups) to active hydrogen groups (active hydrogen reactive groups / active hydrogen groups) is, for example, 1.2 or more, preferably 1.5 or more, and for example, 2.0 or less.

[0312] [Composition of the isocyanate derivative] The amount of the portion derived from the active hydrogen compound may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more relative to the isocyanate derivative, and may also be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less.

[0313] The amount of the portion derived from the hydrocarbon alcohol (α1) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, relative to the portion derived from the active hydrogen compound, and may also be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less.

[0314] The amount of the portion derived from the sugar alcohol / hydroxy acid modified product (α2) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, relative to the portion derived from the active hydrogen compound, and may also be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less.

[0315] The amount of the portion derived from the cationic active hydrogen compound (α3) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, relative to the portion derived from the active hydrogen compound, and may also be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less.

[0316] The amount of the portion derived from the other active hydrogen-containing compound (α4) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more relative to the portion derived from the active hydrogen compound, and may also be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less.

[0317] The amount of the portion derived from the raw material isocyanate may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more relative to the isocyanate derivative, and may also be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less.

[0318] [Amount of isocyanate derivative] The amount of isocyanate derivative may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more per 100 parts by weight of polymer (A). The amount of isocyanate derivative may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less per 100 parts by weight of polymer (A).

[0319] [Dispersant] The water-repellent composition in this disclosure may contain a dispersant. The dispersant may be at least one selected from organic dispersants and inorganic dispersants. The dispersant may be at least one selected from anionic dispersants, nonionic dispersants, cationic dispersants, amphoteric dispersants, and inorganic dispersants. In particular, the water-repellent composition in this disclosure may contain a nonionic dispersant, or a combination of a nonionic dispersant and a cationic dispersant. By including a dispersant, good water repellency, slip resistance, and storage stability can be achieved.

[0320] The dispersant may be either an organic dispersant or an inorganic dispersant, or a combination of both.

[0321] Organic dispersants may be used as dispersants. Organic dispersants can be classified into nonionic dispersants, anionic dispersants, cationic dispersants, and amphoteric dispersants, and the term "organic dispersant" may refer to surfactants.

[0322] The dispersant does not need to contain fluorine atoms.

[0323] [Nonionic Dispersant] The dispersant may contain a nonionic dispersant. The nonionic dispersant may be a nonionic surfactant.

[0324] The nonionic dispersant may be of low molecular weight (for example, molecular weight of 2000 or less, particularly 1000 or less) or high molecular weight (for example, molecular weight of 2000 or more). The molecular weight of the nonionic dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 750 or less, or 250 or less.

[0325] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides.

[0326] Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0327] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are alcohols with 1 to 50 carbon atoms (especially 10 to 30 carbon atoms) with 1 to 30 valencies (especially 2 to 10 valencies) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0328] Examples of ester ethers are compounds obtained by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are alcohols with 1 to 50 carbon atoms (especially 3 to 30 carbon atoms) with a novalence of 1 to 30 (especially 2 to 10) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0329] Examples of alkanolamides are formed from fatty acids and alkanolamines. Alkanolamides may be monoalkanolamides or dialkanolamides. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. Alkanolamines may be alkanols having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0330] The polyol may be a divalent to pentavalent alcohol having 10 to 30 carbon atoms. The amine oxide may be an oxide of an amine (secondary amine or preferably tertiary amine) (for example, having 5 to 50 carbon atoms).

[0331] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group of the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic dispersant is generally preferably 2 to 100.

[0332] The nonionic dispersant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides, and is preferably a nonionic dispersant having an oxyalkylene group.

[0333] The nonionic dispersant may be an alkylene oxide adduct of linear and / or branched aliphatic (saturated and / or unsaturated) groups, a polyalkylene glycol ester of linear and / or branched fatty acids (saturated and / or unsaturated), a sorbitan ester of linear and / or branched fatty acids (saturated and / or unsaturated), a glycerol ester of linear and / or branched fatty acids (saturated and / or unsaturated), a polyglycerol ester of linear and / or branched fatty acids (saturated and / or unsaturated), a sucrose ester of linear and / or branched fatty acids (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, and the like. Among these, those in which the alkylene oxide addition portion and the polyalkylene glycol portion are structured as polyoxyethylene (POE), polyoxypropylene (POP), or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Furthermore, the nonionic dispersant does not need to contain aromatic groups.

[0334] Nonionic dispersants are given by formula: R １ O-(CH ２ CH ２ O) ｐ - (R ２ O) ｑ -R ３ [In the formula, R １ R is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or acyl group having 2 to 22 carbon atoms. ２ Each of them is independently identical or distinct, an alkylene group having 3 or more carbon atoms (for example, 3 to 10), R ３ The compound may be represented by [where p is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, and q is a number of 0 or 1 or more].

[0335] R １ The carbon atoms have 8 to 20 carbon atoms, and are more preferably 10 to 18 carbon atoms. １Preferred specific examples include the octyl group, nonyl group, trimethylnonyl group, lauryl group, tridecyl group, oleyl group, and stearyl group. ２ Examples include propylene groups and butylene groups. In nonionic dispersants, p may be a number of 3 or more (e.g., 5 to 200). q may be a number of 2 or more (e.g., 5 to 200). That is, -(R ２ O) ｑ - may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) in the center. Examples of hydrophobic oxyalkylene chains include oxypropylene chains, oxybutylene chains, and styrene chains, but oxypropylene chains are preferred among them.

[0336] Specific examples of nonionic dispersants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, and alkanes (C). １２ -C １６ ) Thiol, sorbitan monofatty acid (C ７ -C １９ ) or alkyl (C １２ -C １８ This includes condensation products with amines, sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lecithin derivatives, etc. Examples of nonionic dispersants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycol, polyethyleneimine ethoxylate, etc.

[0337] The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example 30 to 75% by weight, and particularly 40 to 70% by weight, relative to the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of the nonionic dispersant is generally 300 to 5,000, for example 500 to 3,000. The nonionic dispersant may be a single type or a mixture of two or more types. The nonionic dispersant may contain compounds with an HLB (hydrophilic-hydrophobic balance) of 10 or less, and may be a mixture of compounds with an HLB of less than 15 (particularly 5 or less) and compounds with an HLB of 15 or more. Specifically, it is preferable to select from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, polyoxypropylene with an HLB of 1 to 18, or from sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, and polyoxyethylene sorbitan fatty acid esters with an HLB of less than 7.

[0338] [Cationic Dispersant] The dispersant may contain a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a compound that does not have an amide group.

[0339] The cationic dispersant may be of low molecular weight (for example, molecular weight of 2000 or less, particularly 1000 or less) or high molecular weight (for example, molecular weight of 2000 or more). The molecular weight of the cationic dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 750 or less, or 250 or less.

[0340] Cationic dispersants may be aliphatic or aromatic, such as ammonium salts (e.g., quaternary ammonium salts). Cationic dispersants may also be oxyethylene-additive ammonium salts. Specifically, examples include amine salt type dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazoline; quaternary ammonium salt type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, and benzethonium chloride; and polymeric cationic dispersants such as polyquaternium-1 to 47. Examples of cationic dispersants include alkylamine salts and quaternary ammonium salts.

[0341] Low molecular weight cationic dispersants are R ２１ -N ＋ (-R ２２ ) (-R ２３ ) (-R ２４ ) X － [In the formula, R ２１ , R ２２ , R ２３ and R ２４ R is a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms, and X is an anionic group. The compound may be represented by [ ]. ２１ , R ２２ , R ２３ and R ２４ Specific examples of X include alkyl groups (e.g., methyl group, butyl group, stearyl group, palmityl group) and aromatic groups (e.g., benzyl group, phenyl group). Specific examples of X include halogens (e.g., chlorine) and acids (e.g., hydrochloric acid, acetic acid). Examples of cationic dispersants include monoalkyltrimethylammonium salts (alkyl group with 4 to 40 carbon atoms) and benzalkonium chloride.

[0342] Specifically, low molecular weight cationic dispersants are defined by formula: R １ ｐ -N ＋ R ２ ｑ X － [In the formula, R １ is C12 or higher (for example, C１２ ~C ５０ ) is a linear and / or branched aliphatic (saturated and / or unsaturated) group, R ２ (CH) is an H or C1-C4 alkyl group, a benzyl group, a polyoxyethylene group (number of oxyethylene groups e.g., 1 (especially 2, particularly 3) to 50) ３ , C ２ H ５ (particularly preferred) where X is a halogen atom (e.g., chlorine), or C １ ~C ４ fatty acid salts of, or C １ ~C ４ It is a sulfonate of , where p is 1 or 2, q is 2 or 3, and p + q = 4. It may be an ammonium salt represented by ]. １ The number of carbon atoms may be 12 to 50, for example, 12 to 30.

[0343] Low molecular weight cationic dispersants may include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride, etc.

[0344] The polymeric cationic dispersant may be various polymers (e.g., polyquaternium-1 to 47) having cationic groups (e.g., ammonium groups, quaternary ammonium groups). Examples of polymeric cationic dispersants include cationized starch, cationized cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propylhydroxyethylcellulose chloride), cationized guar gum, cationized xanthan gum, chitosan, and other cationized natural products (especially cationized sugars); polymers of cationic group-containing monomers such as aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternized dimethylammonium ethyl methacrylic acid, diallyldimethylammonium chloride, dimethylaminopropylamine, and quaternized vinylimidazole.

[0345] [Anionic Dispersant] The dispersant may contain an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant does not have to contain an anionic dispersant.

[0346] The anionic dispersant may be of low molecular weight (for example, molecular weight of 2000 or less, particularly 1000 or less) or of high molecular weight (for example, molecular weight of 2000 or more). The molecular weight of the anionic dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 750 or less, or 250 or less.

[0347] Examples of anionic dispersants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfone fatty acid salts, N-acyl amino acid type dispersants, phosphate mono or diester type dispersants, and sulfosuccinate esters. An example of anionic dispersants is a carboxylate salt (e.g., a fatty acid salt).

[0348] [Amphoteric Dispersant] The dispersant may contain an amphoteric dispersant. The amphoteric dispersant may be an amphoteric surfactant.

[0349] The amphoteric dispersant may be of low molecular weight (for example, molecular weight of 2000 or less, particularly 1000 or less) or high molecular weight (for example, molecular weight of 2000 or more). The molecular weight of the amphoteric dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 750 or less, or 250 or less.

[0350] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amide betaines, and betaine acetate. Specifically, these include lauryl betaine, stearyl betaine, laurylcarboxymethylhydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, and fatty acid amidopropyldimethylaminoacetic acid betaine.

[0351] [Inorganic Dispersant] The dispersant may contain an inorganic dispersant.

[0352] The average primary particle size of the inorganic dispersant may be 5 nm or larger, 30 nm or larger, 100 nm or larger, 1 μm or larger, 10 μm or larger, or 25 μm or larger, and may also be 100 μm or smaller, 50 μm or smaller, 10 μm or smaller, 1 μm or smaller, 500 nm or smaller, or 300 nm or smaller. The average primary particle size can be measured, for example, by observation with a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant may also be hydrophilic particles.

[0353] Examples of inorganic dispersants include polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and hydroxyapatite; carbonates such as calcium carbonate and magnesium carbonate; silicates such as calcium metasilicate; sulfates such as calcium sulfate and barium sulfate; and hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

[0354] [Amount of dispersant] The amount of dispersant may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of polymer (A), and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

[0355] [Liquid Medium] The water-repellent composition in this disclosure may include a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The water-repellent composition may be a dispersion or a solution. The water-repellent composition in this disclosure is preferably an aqueous dispersion or aqueous dispersion.

[0356] Examples of organic solvents include esters (e.g., esters with 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2 to 40 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols with 1 to 40 carbon atoms, specifically isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes with 5 to 10 carbon atoms, specifically naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain compounds having at least one hydroxyl group (e.g., polyols such as alcohols and glycol-based solvents, ethers of polyols (e.g., monoethers)). These may be used individually or in combination of two or more.

[0357] [Amount of liquid medium] The amount of liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, per 1 part by weight of polymer (A). Alternatively, it may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less.

[0358] The amount of water may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, per 1 part by weight of polymer (A).

[0359] The amount of organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, per 1 part by weight of polymer (A), and may also be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less.

[0360] [Organic Acids] The water-repellent compositions of this disclosure may contain organic acids. Known organic acids can be used. Preferred organic acids include carboxylic acids, sulfonic acids, sulfinic acids, etc., with carboxylic acids being particularly preferred. Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., with formic acid or acetic acid being particularly preferred. In this disclosure, one organic acid may be used, or two or more may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0361] [Amount of Organic Acid] The amount of organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more per 100 parts by weight of polymer (A), or 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of organic acid may be adjusted so that the pH of the water-repellent composition is 3 to 10, for example 5 to 9, particularly 6 to 8. The water-repellent composition may be acidic (pH 7 or less, for example 6 or less).

[0362] [Inorganic Acids] The water-repellent compositions of this disclosure may contain inorganic acids. Known inorganic acids can be used. Examples of inorganic acids include hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, boric acid, sulfuric acid, and phosphoric acid. In this disclosure, one inorganic acid may be used, or two or more may be used in combination. Adding inorganic acids can improve the stability of the aqueous dispersion.

[0363] [Amount of inorganic acid] The amount of inorganic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more per 100 parts by weight of polymer (A), and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of inorganic acid may be adjusted so that the pH of the water-repellent composition is 3 to 10, for example 5 to 9, particularly 6 to 8. The water-repellent composition may be acidic (pH 7 or less, for example 6 or less).

[0364] [Curing agent] The water-repellent compositions of this disclosure may contain a curing agent (an active hydrogen-reactive compound or an active hydrogen-containing compound). If the water-repellent composition is for paper (for example, an oil-resistant agent for paper), it may not contain a curing agent.

[0365] The curing agent (crosslinking agent) in a water-repellent composition can effectively cure the water-repellent composition. The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with active hydrogen or an active hydrogen-reactive group. Examples of active hydrogen-reactive compounds are isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of active hydrogen-containing compounds are hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, melamine compounds, and urea-based compounds.

[0366] The curing agent may contain an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. A polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound acts as a crosslinking agent. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (for example, a blocked polyisocyanate compound). A blocked isocyanate compound is a compound in which the isocyanate groups of an isocyanate compound are masked with a blocking agent to suppress the reaction.

[0367] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diiso These include aliphatic diisocyanates such as cyanatomethyl caproate, lysine ester triisocyanates, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane. These may be used alone or in combination of two or more.

[0368] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,3,5-triisocyanatocyclohexane, 4,4'methylenebis(cyclohexyl isocyanate), and 1,3-bis(isocyanatomethyl)cyclohexane. These may be used individually or in combination of two or more.

[0369] Examples of aromatic aliphatic polyisocyanates include aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of aromatic aliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or mixtures thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used individually or in combination of two or more.

[0370] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylenediisocyanate, p-phenylenediisocyanate, 4,4'-diphenyldiisocyanate, 1,5-naphthalenediisocyanate, 2,4'- or 4,4'-diphenylmethanediisocyanate or mixtures thereof, 2,4- or 2,6-tolylenediisocyanate or mixtures thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate, etc. These may be used individually or in combination of two or more.

[0371] Examples of polyisocyanate derivatives include various derivatives of the polyisocyanate compounds described above, such as dimers, trimers, biuretes, allophanates, carbodiimides, uretodiones, uretoimines, isocyanurates, and iminooxadiazinediones. These may be used individually or in combination of two or more.

[0372] These polyisocyanates can be used individually or in combination of two or more. It is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of a polyisocyanate compound is blocked with a blocking agent. The use of a blocked polyisocyanate compound is preferable because it is relatively stable in solution and can be used in the same solution as the water-repellent composition.

[0373] Blocking agents sequester free isocyanate groups. Blocked polyisocyanate compounds can be easily reacted with hydroxyl groups by heating them to, for example, 100°C or higher, for example, 130°C or higher, which regenerates the isocyanate groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, oxime compounds, and pyrazole compounds. Polyisocyanate compounds can be used alone or in combination of two or more.

[0374] Epoxy compounds are compounds that contain an epoxy group. Examples of epoxy compounds include epoxy compounds containing a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. Chloromethyl group-containing compounds are compounds that contain a chloromethyl group. Examples of chloromethyl group-containing compounds include chloromethyl polystyrene. Carboxyl group-containing compounds are compounds that contain a carboxyl group. Examples of carboxyl group-containing compounds include (poly)acrylic acid and (poly)methacrylic acid.

[0375] Specific examples of ketone group-containing compounds include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of hydrazide compounds include hydrazine, carbohydrazide, and adipic acid hydrazide. Specific examples of melamine compounds include melamine resin and methyl etherified melamine resin. Specific examples of urea-based compounds include dimethylol dihydroxyethylene urea (DMDHEU) and dimethyl dihydroxyethylene urea.

[0376] [Amount of curing agent] The amount of curing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of polymer (A), and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0377] [Other Components] The water-repellent composition may contain other components besides those listed above. Other components may be added after the hydrocarbon-based water-repellent resin has been manufactured. Examples of other components include water-repellent and / or oil-repellent agents, anti-slip agents, antistatic agents, preservatives, antibacterial agents, deodorants, penetrating agents, etc. These may be used alone or in combination of two or more. In addition to the above components, other components may include texture adjusters, softeners, antibacterial agents, flame retardants, wrinkle inhibitors, crosslinking agents, film-forming aids, compatibilizers, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, defoaming agents, shrinkage inhibitors, wrinkle inhibitors, shape-retaining agents, drape-retaining agents, ironing-improving agents, polymer dispersants, scum dispersants, fluorescent whitening agents, dye fixatives, and antifoaming agents. These may be used alone or in combination of two or more.

[0378] (Antistatic agents) Examples of antistatic agents include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate esters, phosphonates, and phosphate esters; amphoteric antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, alanine and its derivatives; and nonionic antistatic agents such as amino alcohols and their derivatives, glycerin and its derivatives, polyethylene glycol and its derivatives. These may also be ion-conductive polymers obtained by polymerizing or copolymerizing monomers having cationic, anionic, or amphoteric ion-conductive groups. These may be used alone or in combination of two or more.

[0379] (Preservatives) Preservatives can be used mainly to enhance preservative and bactericidal properties and maintain preservation during long-term storage. Examples of preservatives include isothiazolone-type organosulfur compounds, benzisothiazolone-type organosulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol. The preservative content is preferably 0.0001 to 1% by weight of the total weight of the water-repellent composition. If the preservative content is above the lower limit of the above range, the effect of adding the preservative is sufficiently obtained, and if it is below the upper limit, the storage stability of the water-repellent composition is good.

[0380] (Antibacterial agents) Antibacterial agents are components that suppress the growth of bacteria on fibers and also suppress the generation of unpleasant odors derived from microbial decomposition products. Examples of antibacterial agents include cationic disinfectants such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide)zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, and polylysine.

[0381] (Deodorizers) Examples of deodorizers include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, and aminocarboxylic acid metal complexes (such as the zinc complex of trisodium methylglycinidacetate described in International Publication No. 2012 / 090580).

[0382] (Anti-slip agent) This is an ingredient that has the effect of suppressing slippage of fibers and shifting of seams during sewing and wearing. Examples of anti-slip agents include polysiloxane compounds, colloidal silicas, silicone resin derivatives, colloidal organosilicones, and amino-modified silicones.

[0383] (Fabric softener) Fabric softener is an ingredient that gives fabrics a soft and smooth texture. Examples of fabric softener ingredients include cationic surfactants such as quaternary ammonium salts and amine salts, anionic surfactants such as soap, sulfated oils, higher alcohol sulfate salts and sulfonates, nonionic surfactants such as polyhydric alcohols and polyethylene glycols, amphoteric surfactants such as betaine and amino acid types, and siloxane resins.

[0384] [Amount of other components] The amount of each or total amount of other components may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of polymer (A), and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0385] <Uses of Water-Repellent Compositions> Examples of uses for the water-repellent compositions in this disclosure include external treatment agents (surface treatment agents) or internal treatment agents, water repellents (water repellents, oil repellents, or water- and oil-repellent agents, especially water repellents), antifouling agents, dirt removal agents, release agents, mold release agents (external mold release agents or internal mold release agents), etc.

[0386] <Method for manufacturing the treated product> The method for manufacturing the treated product in this disclosure includes the step of treating a substrate with a water-repellent composition.

[0387] [Processed Products] Examples of substrates treated with the water-repellent composition of this disclosure include fibrous substrates, stone materials, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster. Various examples of fibrous substrates can be given. For example, natural animal and plant fibers such as cotton, hemp, wool, and silk; synthetic fibers such as polyamide, polyester, 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; or mixed fibers thereof. An example of a substrate treated with the water-repellent composition will be described in detail regarding woven and knitted fabrics.

[0388] (Woven and Knitted Fabrics) ・Method of manufacturing woven and knitted fabrics Woven and knitted fabrics can be obtained by weaving and knitting long fibers and short fibers made of the above fibers to obtain raw fabric, and then by post-processing and water-repellent treatment. Weaving and knitting can be carried out using known looms and knitting machines, and the preparation process preceding weaving and knitting can also be carried out using known equipment.

[0389] Woven or knitted fabrics can be post-processed using known scouring and dyeing methods and equipment suitable for the fiber material of the woven or knitted fabric.

[0390] After post-processing, the woven or knitted fabric may be treated to be water-repellent. For water-repellent treatment, first, an aqueous solution containing a water-repellent agent (which may be a water-repellent agent composition as described herein) is prepared. Next, the aqueous solution is applied to the woven or knitted fabric after the post-processing using a padding method, spray method, slit coater method, etc., and after drying, it is subjected to dry heat treatment. The aqueous solution may also contain a crosslinking agent, softener, antistatic agent, etc., as needed. After water-repellent treatment, the woven or knitted fabric may be calendered.

[0391] Woven and knitted fabrics are ideally suited for clothing applications where water repellency is required, particularly for sportswear such as outdoor wear, skiing, snowboarding, and golf, as well as uniform wear.

[0392] - Laminated Fabric The laminated fabric may be provided as a woven or knitted fabric with a breathable waterproof layer on one side. The breathable waterproof layer may be directly laminated to the woven or knitted fabric, or it may be laminated to the woven or knitted fabric via an adhesive layer. When the laminated fabric of this disclosure is used for clothing or the like, the woven or knitted fabric side is positioned to repel rainwater, etc.

[0393] • Breathable waterproof layer: A breathable waterproof layer is a layer that covers one side of a woven or knitted fabric, and is formed of a resin or structured film that has waterproof and breathable properties.

[0394] The breathable waterproof layer may be formed by directly applying resin (the resin constituting the breathable waterproof layer) to the woven or knitted fabric, or it may be laminated to one side of the woven or knitted fabric via an adhesive layer as described later.

[0395] The resins used to make up the breathable waterproof layer are not particularly limited, but non-porous and porous resins are used. For non-porous resins, polyurethane resins and polyester elastomer resins that have hydrophilic components are used to provide breathability. For porous resins, polyurethane resins that form wet porous membranes and polyurethane resins that become porous by electrospinning are used, as well as porous membranes of PTFE, PE, and PP.

[0396] As the polyurethane resin, conventionally known resins obtained by reacting a polyisocyanate component with a polyol component can be used.

[0397] A breathable waterproof membrane having a microporous structure can be obtained by a wet solidification method using a DMF solution of polyurethane resin containing inorganic fine powder. Examples of inorganic fine powder include silicon dioxide, aluminum dioxide, or titanium dioxide. The average primary particle size of the inorganic fine powder is preferably about 7 to 40 nm. The inorganic fine powder content is preferably 3 to 50% by weight, and more preferably 5 to 50% by weight, relative to the total amount of the breathable waterproof layer.

[0398] The thickness of the breathable waterproof layer is preferably 5 μm or more, and more preferably 10 to 30 μm. A thickness within this range provides an excellent balance of waterproofing and breathability, and also offers advantages in terms of texture.

[0399] - Adhesive layer laminated fabric preferably includes an adhesive layer. In other words, it is preferable that the woven or knitted fabric and the breathable waterproof layer are laminated with an adhesive layer in between. Furthermore, it is preferable for the adhesive layer to be a discontinuous layer such as a dot or grid pattern in terms of breathability.

[0400] The type of adhesive that makes up the adhesive layer is not particularly limited, but it is preferable that it has excellent adhesion to the breathable waterproof layer. For example, if a resin mainly composed of polyurethane resin is selected as the resin that makes up the breathable waterproof layer, it is preferable to use an adhesive layer made of polyurethane adhesive. The polyurethane adhesive may be of any structure, such as ether-based, ester-based, or polycarbonate-based.

[0401] The adhesive layer may be formed over the entire surface of one side of the woven or knitted fabric, or it may be formed in a pattern from the viewpoint of breathability or texture. The pattern is not particularly limited, but examples include dots, lines, grids, checkerboard patterns, tortoiseshell patterns, etc., and it is preferable that they are uniformly arranged throughout.

[0402] The thickness of the adhesive layer is preferably about 10 to 100 μm, and more preferably 20 to 80 μm.

[0403] - Lining Fiber Fabric In the laminated fabric disclosed herein, the lining fiber fabric may be laminated on the breathable waterproof layer (on the side of the breathable waterproof layer opposite to the side on which the woven or knitted fabric disclosed herein is laminated). The lining fiber fabric can protect the breathable waterproof layer, and the waterproofness (water pressure resistance) and strength can be further improved.

[0404] Examples of lining fabrics include various woven and knitted fabrics. Among these, knitted fabrics are preferable because, compared to woven fabrics, the constituent threads tend to protrude more easily from the surface, resulting in a less flat surface. This allows for a greater anchoring effect, making it less likely to separate from the breathable waterproof layer.

[0405] Furthermore, tricot knit fabric is preferable because it allows for the production of long lengths of raw material during the knitting process, resulting in fewer seams and enabling uniform lamination on a breathable waterproof layer.

[0406] The material of the fibers constituting the lining fabric is not particularly limited and can be selected as appropriate, but nylon fibers are preferred. This is because, since acid dyes are generally used for nylon fibers, the migration and sublimation of disperse dyes to the breathable waterproof layer, which is a problem with polyester fibers and the like that use disperse dyes, is less likely to occur. The form (long fibers, short fibers, or spun yarn) or fineness of the constituent fibers of the lining fabric is not particularly limited and can be selected as appropriate within a range that does not impair the effects of this disclosure.

[0407] Characteristics of Laminated Fabrics Laminated fabrics have excellent waterproofing properties. A preferred example of the waterproofing properties of the laminated fabrics of this disclosure is a water level measured according to the water resistance test specified in JIS L 1092:2009 Method A (low water pressure method), which is, for example, 10,000 mm or more, preferably 15,000 mm or more, more preferably 16,000 mm or more, and particularly preferably 20,000 mm or more.

[0408] Laminated fabrics have excellent moisture permeability. A preferred example of the moisture permeability of the laminated fabrics of this disclosure is a moisture permeability of, for example, 10,000 g / m², as measured according to JIS L 1099:2021 B-1 method (potassium acetate method). ２ ・24 hours or more, preferably 15,000 g / m² ２ ・24 hours or more, more preferably 20,000 g / m² ２ - 24 hours or more is an example. There are no particular restrictions on the upper limit of this moisture permeability, but for example, 40,000 g / m ２ ・24h or 35,000 g / m ２ One example is 24 h·mm. Additionally, the water vapor permeability measured according to JIS L 1099:2021 A-1 method (calcium chloride method) is, for example, 4000 g / m³. ２ ・24 hours or more, preferably 8000 g / m² ２ ・24 hours or more, more preferably 10,000 g / m² ２- 24 hours or more is mentioned. The upper limit of this moisture permeability is 13,000 to 15,000 g / m², as this is the limit of the measurement method. ２ It will take approximately 24 hours.

[0409] In the laminated fabric of this disclosure, the peel strength between the woven or knitted fabric and the breathable waterproof layer, measured according to the method of JIS K 6404-2, is preferably 2.55 N / 2.54 cm or more for clothing applications, and may be preferably 5 N / 2.54 cm or more for use applications.

[0410] ・Method for manufacturing laminated fabric The method for manufacturing laminated fabric is not particularly limited, but examples include the first and second manufacturing methods shown below. First manufacturing method: Includes the step of forming the moisture-permeable waterproof layer by applying the resin constituting the moisture-permeable waterproof layer to the surface of the woven or knitted fabric. Second manufacturing method: Includes the step of forming an adhesive layer on the woven or knitted fabric or the moisture-permeable waterproof layer, and the step of bonding the woven or knitted fabric and the moisture-permeable waterproof layer via the adhesive layer.

[0411] In the first manufacturing method, a coating method can be used to apply the resin constituting the moisture-permeable waterproof layer to the surface of the woven or knitted fabric. In the coating method, a knife coater or a comma coater can be used. Furthermore, from the viewpoint of providing excellent moisture permeability, it is preferable to obtain the moisture-permeable waterproof layer by a wet method.

[0412] In the second manufacturing method, a lamination method is used as a method for forming an adhesive layer on a woven or knitted fabric or a breathable waterproof layer. In the lamination method, a resin solution or a hot melt method can be used to form the adhesive layer. First, a resin composition for forming a breathable waterproof layer (for example, a resin composition containing resin and an organic solvent) is applied to the surface of a release agent (release paper, release cloth, or release film, etc.) with a clearance, and the breathable waterproof layer is formed while adjusting the thickness. The film is then dried and heat-treated to obtain the film. The release agent can be removed as appropriate after lamination or maturation. When laminating by the hot melt method, the release agent can be peeled off and the film can be laminated on its own. Furthermore, the breathable waterproof membrane can be made by laminating a membrane produced by extrusion methods such as the T-die method or inflation without solvents, a porous membrane produced by the electrospinning method, or a porous membrane such as PTFE, PE, or PP.

[0413] Then, an adhesive layer is formed on the woven or knitted fabric or the breathable waterproof layer. For example, if a resin solution is used, a two-component curing polyurethane resin solution, adjusted to a viscosity in the range of 500 to 5000 mPa·s, may be applied to the entire surface or in a pattern. After drying, an adhesive layer is formed, and the woven or knitted fabric and the breathable waterproof layer are bonded together via the adhesive layer, and the two are then pressed together or heat-pressed to carry out the second manufacturing method.

[0414] On the other hand, in the case of hot melt, it is preferable to use a moisture-curing resin that reacts with moisture in the air, and in practical terms, it is more preferable to use one that melts in a temperature range of about 80 to 150°C. In this case, first, the hot melt resin is melted while considering the melting point of the resin and the viscosity when melted. Then, the molten resin is applied to the woven or knitted fabric or the breathable waterproof layer to form an adhesive layer, and the woven or knitted fabric and the breathable waterproof layer are bonded together and pressed to carry out the second manufacturing method. Alternatively, if texture is important, the resin can be applied to the breathable waterproof membrane in a pattern and bonded to the woven or knitted fabric.

[0415] Subsequently, a lining fabric can be laminated onto the breathable waterproof layer using a known and appropriate method.

[0416] • Applications of laminated fabrics: Laminated fabrics offer excellent water repellency and breathable waterproofing, and the breathable waterproof layer does not peel off even in harsh environments. Therefore, they are ideally suited for use in fields such as uniforms, sportswear, and outdoor products used outdoors.

[0417] [Processing Method] The water-repellent composition of this disclosure can be applied to a substrate (especially a fibrous substrate) by conventionally known methods as a treatment agent (especially a surface treatment agent). The water-repellent composition of this disclosure may be diluted by dispersing it in an organic solvent or water as necessary, and then applied to the surface of the substrate by known methods such as immersion coating, spray coating, foam coating, etc., and dried. After drying, a fibrous product with the solid components of the water-repellent composition attached is obtained. If necessary, it may also be applied together with a suitable crosslinking agent and cured. Furthermore, the water-repellent composition of this disclosure can be used in combination with various additives such as water-repellent and / or oil-repellent agents, anti-slip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, anti-wrinkle agents, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, ultraviolet absorbers, antioxidants, pH adjusters, insecticides, and defoaming agents. Examples of various additives may be the same as those described in the "other components" section of the water-repellent composition described above. The concentration of the hydrocarbon-based water-repellent resin in the treatment agent that comes into contact with the substrate may be appropriately changed depending on the application, but may be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0418] [Textile Products] Various examples can be given of textile base materials, such as cloth products and paper products.

[0419] Examples of textile products include natural animal and plant fibers such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, 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; or blends thereof. Textile products include woven fabrics, knitted fabrics, and nonwoven fabrics, as well as fabrics and carpets. However, treatment may also be applied to fibers, yarns, and intermediate fiber products (e.g., slivers or rovings) before they are made into fabric.

[0420] Examples of paper products include paper made from bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulps such as crushed wood pulp, mechanical pulp or thermomechanical pulp, recycled paper pulp such as recycled newspaper, recycled magazine, recycled corrugated cardboard or deinked paper, paper containers, and molded products made from paper. Specific examples of paper products include food packaging paper, gypsum board base paper, coated base paper, medium-grade paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-preventive liners and metal interlining paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, and molded paper (molded containers).

[0421] The water-repellent composition can be applied to a textile substrate (e.g., cloth) by any known method for treating the textile substrate with a liquid. The textile substrate may be immersed in the water-repellent composition, or the solution may be applied to or sprayed onto the textile substrate. The treated textile substrate is preferably dried and cured by heating to exhibit water-repellent and oil-repellent properties. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. Good performance can also be obtained with low-temperature heating (e.g., 100°C to 140°C) in this disclosure. The heating time may be 5 seconds to 60 minutes in this disclosure, for example, 30 seconds to 3 minutes.

[0422] Alternatively, the polymer may be applied to the fibrous substrate by a cleaning method, for example, by washing or dry cleaning.

[0423] The fibrous substrate to be treated may be a cloth, including woven fabrics, knitted fabrics and nonwoven fabrics, cloth in the form of clothing and carpets, but may also be a fiber or yarn or intermediate fibrous product (e.g., sliver or roving). The water-repellent compositions of this disclosure are particularly effective in making fibrous products (e.g., synthetic fibers) water-repellent.

[0424] The fibers constituting the fibrous base material may be natural fibers, synthetic fibers, semi-synthetic fibers, regenerated fibers, or inorganic fibers. The fibers may be used individually or in combination of two or more types.

[0425] Examples of natural fibers include cellulose fibers such as cotton, flax, and pulp, as well as chitin, chitosan, wool, and silk. Specific examples of wood pulp include mechanical pulps such as groundwood pulp (GP), pressed groundwood pulp (PGW), and thermomechanical pulp (TMP); chemical pulps such as high-yield unbleached softwood kraft pulp (HNKP; N material), bleached softwood kraft pulp (NBKP; N material, NB material), unbleached hardwood kraft pulp (LUKP; L material), and bleached hardwood kraft pulp (LBKP, L material); recycled paper pulps such as deinking pulp (DIP) and waste pulp (WP), and semi-chemical pulps (CP).

[0426] Examples of synthetic fibers include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and copolymerized polyester; polyolefins such as linear low-density polyethylene, low-density polyethylene, high-density polyethylene, and polypropylene; polyamides such as nylon 6, nylon 66, nylon 610, and nylon 46; acrylic fibers such as polyacrylonitrile; polyvinyl alcohol, polyurethane, and polyvinyl chloride. Examples of semi-synthetic fibers include acetate and triacetate. Examples of regenerated fibers include rayon, cupro, polynosic rayon, lyocell, and Tencel. Examples of inorganic fibers include glass fiber and carbon fiber.

[0427] Alternatively, the fibrous base material may be leather. The manufactured polymer may be applied to the leather in the form of an aqueous solution or aqueous emulsion at various stages of leather processing, for example, during the wetting process or during the finishing process, in order to make the leather hydrophobic and oleophobic. Alternatively, the fibrous base material may be paper. The manufactured polymer may be applied to pre-formed paper, or at various stages of papermaking, for example, during the drying period of the paper.

[0428] "Treatment" means applying the water-repellent composition to a substrate by immersion, spraying, coating, etc. Through treatment, the polymer (A) and silicone compound (B), which are the active ingredients of the water-repellent composition, penetrate into the interior of the substrate and / or adhere to the surface of the substrate. In other words, through treatment, a substrate (e.g., a textile product) to which the polymer (A) and silicone compound (B) of the water-repellent composition of this disclosure are attached is obtained.

[0429] [Pretreatment of Fiber Substrate] The fiber substrate may be pretreated before being treated with the water-repellent composition of this disclosure. Pretreatment of the fiber substrate can impart excellent fastness to the fiber substrate after treatment with the water-repellent composition.

[0430] Examples of pretreatments for fiber substrates include cationization by reaction with reactive quaternary ammonium salts, anionization by sulfonation, carboxylation, phosphorylation, etc., acetylation, benzoylation, carboxymethylation, grafting, tannic acid treatment, and polymer coating after anionization.

[0431] The method for pre-treating the fiber substrate is not limited, but it can be pre-treated by conventionally known methods. The pre-treatment solution may be diluted by dispersing it in an organic solvent or water as needed, and then applied to the surface of the fiber substrate by known methods such as immersion coating, spray coating, or foam coating, followed by drying. The pH and temperature of the pre-treatment solution may be adjusted according to the desired degree of treatment. As an example of a method for pre-treating a fiber substrate, a method of pre-treating the fiber substrate with a hydrocarbon-based water repellent will be described in detail.

[0432] The pretreatment method for the fiber substrate involves applying -SO to the fibers. ３ M １ (In the formula, M １ (represents a monovalent cation) a monovalent group represented by -COOM ２ (In the formula, M ２ A monovalent group represented by (where represents a monovalent cation), and -O-P(O)(OX １ ) (OX ２ ) (wherein, X １ and X ２The process may include a step of conferring at least one functional group (hereinafter sometimes referred to as a "specific functional group") selected from the group consisting of monovalent groups (each representing a hydrogen atom or an alkyl group having 1 to 22 carbon atoms).

[0433] M １ Examples include H, K, Na, or ammonium ions which may have substituents. ２ Examples include H, K, Na, or ammonium ions which may have substituents. １ or X ２ If it is an alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms, and more preferably an alkyl group having 4 to 12 carbon atoms.

[0434] Fibers containing the above-mentioned specific functional groups (hereinafter sometimes referred to as "functional group-containing fibers") can be prepared, for example, by the following methods: (i) A compound having the above-mentioned specific functional group is attached to a fiber material. Note that the attachment of the compound may be such that a portion of the compound and a portion of the fiber are chemically bonded, to the extent that a sufficient amount of the above-mentioned specific functional group remains. (ii) Fibers are prepared in which the above-mentioned specific functional group is directly introduced into the material constituting the fiber.

[0435] (i) For example, a functional group-containing fiber can be obtained by a functional group introduction step in which the fiber material is treated with a pretreatment solution containing one or more compounds having the above-mentioned specific functional group.

[0436] There are no particular restrictions on the material of the fiber material, and examples include natural fibers such as cotton, linen, silk, and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene; and composite fibers and blended fibers thereof. The fiber material may take any form, such as fibers (tow, sliver, etc.), yarn, knitted fabrics (including interwoven fabrics), woven fabrics (including interwoven fabrics), nonwoven fabrics, and paper.

[0437] In this embodiment, from the viewpoint of obtaining good water repellency in the resulting textile product, it is preferable to use a fiber material containing polyamide and polyester as a base material. In particular, it is preferable to use nylon such as nylon 6 and nylon 6,6, polyester such as polyethylene terephthalate (PET), polytrimethyl terephthalate, and polylactic acid, and mixed fibers containing these.

[0438] Above - SO ３ M １ As a compound having this property, phenolic polymers can be used. Examples of such phenolic polymers include those containing at least one compound represented by the following general formula.

[0439] [In formula (2), X ２ Ha-SO ３ M ３ (In the formula, M ３ (where represents a monovalent cation) or a group represented by the following general formula, where n is an integer between 20 and 3000.

[0440] [In the formula, M ４ This represents a monovalent cation.

[0441] The above M ３ Examples include H, K, Na, or ammonium ions which may have substituents.

[0442] The above M ４ Examples include H, K, Na, or ammonium ions which may have substituents.

[0443] The compound represented by the above general formula may, for example, be a formalin condensate of phenolsulfonic acid or a formalin condensate of sulfonated bisphenol S.

[0444] Above - COOM ２ Examples of compounds having this property include polycarboxylic acid polymers.

[0445] As polycarboxylic acid polymers, for example, polymers synthesized by conventionally known radical polymerization methods using acrylic acid, methacrylic acid, maleic acid, etc. as monomers, or commercially available polymers can be used.

[0446] One method for producing polycarboxylic acid polymers is to add a radical polymerization initiator to an aqueous solution of the monomer and / or its salt, and heat the reaction at 30 to 150°C for 2 to 5 hours. At this time, alcohols such as methanol, ethanol, isopropyl alcohol, or aqueous solvents such as acetone may be added to the aqueous solution of the monomer and / or its salt. Examples of radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, redox polymerization initiators formed by combinations of persulfates and sodium bisulfite, hydrogen peroxide, and water-soluble azo polymerization initiators. These radical polymerization initiators may be used alone or in combination of two or more. Furthermore, during radical polymerization, a chain transfer agent (e.g., octyl thioglycolate) may be added to adjust the degree of polymerization.

[0447] In radical polymerization, copolymerizable monomers can be used in addition to the monomers mentioned above. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, as well as acrylamide, acrylates, and methacrylates. Acrylates and methacrylates are preferably those having a hydrocarbon group with 1 to 3 carbon atoms, which may have substituents such as hydroxyl groups. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, and propyl methacrylate. These copolymerizable monomers may be used individually or in combination of two or more.

[0448] The carboxyl groups in the polycarboxylic acid polymer may be free or neutralized by alkali metals or amine compounds. Examples of alkali metals include sodium, potassium, and lithium, while examples of amine compounds include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0449] The weight-average molecular weight of the polycarboxylic acid polymer is preferably 1,000 to 20,000, and more preferably 3,000 to 15,000, from the viewpoint of obtaining good water repellency in the resulting textile product.

[0450] For polycarboxylic acid polymers, commercially available products such as "NeoCrystal 770" (manufactured by Nikka Chemical Co., Ltd., product name) and "Cellopol PC-300" (manufactured by Sanyo Chemical Industries, Ltd., product name) can be used.

[0451] The above -O-P(O)(OX １ ) (OX ２ Examples of compounds having the following are phosphate ester compounds represented by the following general formula. [In the formula, X １ or X ２ This is synonymous with the above, X ３ This represents an alkyl group having 1 to 22 carbon atoms.

[0452] As the phosphate ester compound mentioned above, phosphate monoesters, diesters, and triesters in which the alkyl ester portion has an alkyl group having 1 to 22 carbon atoms, as well as mixtures thereof, can be used.

[0453] From the viewpoint of obtaining good water repellency in the resulting textile product, it is preferable to use lauryl phosphate esters and decyl phosphate esters.

[0454] For the phosphate ester compound, commercially available products such as "Phosphanol ML-200" (manufactured by Toho Chemical Industry Co., Ltd., trade name) can be used.

[0455] The pretreatment solution containing one or more compounds having the above-mentioned specific functional groups can, for example, be an aqueous solution of the compounds described above. The pretreatment solution may also contain acids, alkalis, surfactants, chelating agents, etc.

[0456] Methods for treating fibrous materials with the above-mentioned pretreatment solution include, for example, padding, immersion, spraying, and coating. For padding, for example, methods using padding equipment described on pages 396-397 of the Dictionary of Textile Dyeing and Processing (published in 1963 by Nikkan Kogyo Shimbun) and pages 256-260 of Color Dyeing Chemistry III (published in 1975 by Jikkyo Shuppan Co., Ltd.) can be used. For coating, for example, methods using coating machines described on pages 473-477 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senshi-sha) can be used. For immersion, for example, methods using batch-type dyeing machines described on pages 196-247 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senshi-sha) can be used, and liquid flow dyeing machines, air flow dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, cheese dyeing machines, etc. can be used. Examples of spray treatments include air sprays that atomize the treatment solution using compressed air, and air sprays that use a hydraulic atomization system. The concentration of the treatment solution and the treatment conditions such as heat treatment after application can be adjusted as appropriate, taking into consideration the purpose, performance, and other conditions. If the pretreatment solution contains water, it is preferable to dry it to remove the water after it has been applied to the fiber material. There are no particular restrictions on the drying method, and either a dry heat method or a wet heat method may be used. There are no particular restrictions on the drying temperature, but for example, drying at room temperature to 200°C for 10 seconds to several days is sufficient. If necessary, after drying, heat treatment may be performed at a temperature of 100 to 180°C for about 10 seconds to 5 minutes.

[0457] Furthermore, if the fiber material is to be dyed, the pretreatment with the pretreatment solution may be performed before dyeing or in the same bath as the dyeing. However, if reducing soaping is performed, there is a risk that the compounds having the specific functional groups adsorbed during the process (for example, phenolic polymer compounds, etc.) may be removed. Therefore, it is preferable to perform the pretreatment after reducing soaping following dyeing.

[0458] The treatment temperature during the immersion process can be 60 to 130°C. The treatment time can be 5 to 60 minutes.

[0459] In the functional group introduction step using the pretreatment solution, it is preferable to treat the material in such an amount that the amount of compound having the specified functional group attached is 1.0 to 7.0 parts by weight per 100 parts by weight of the fiber material. Within this range, a high level of both durable water repellency and texture can be achieved.

[0460] The pretreatment solution is preferably adjusted to a pH of 3 to 5. pH adjustment can be done using pH adjusting agents such as acetic acid or malic acid.

[0461] In the pretreatment solution, salt can also be used in combination to effectively adsorb the compound having the above-mentioned specific functional group onto the fiber material through a salting-out effect. Examples of salts that can be used include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate.

[0462] In the functional group introduction step using a pretreatment solution, it is preferable to remove any compounds having the specified functional groups that have been excessively treated. One method of removal is washing with water. By ensuring sufficient removal, it is possible to suppress the inhibition of water repellency development in the subsequent water-repellent treatment, and in addition, the texture of the resulting textile product will be improved. Furthermore, it is preferable to thoroughly dry the resulting functional group-containing fibers before contacting them with a hydrocarbon-based water repellent.

[0463] (ii) Examples of fibers in which the above-mentioned specific functional groups are directly introduced into the material constituting the fiber include cationic dyeable polyester (CD-PET).

[0464] From the viewpoint of obtaining good water repellency in the resulting textile product, the functional group-containing fibers preferably have a surface zeta potential of -100 to -0.1 mV, and more preferably -50 to -1 mV. The surface zeta potential of the fibers can be measured, for example, using the zeta potential and particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0465] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0466] <Testing Method> The testing procedure is as follows:

[0467] [Water Repellency Test] The water repellency of the test fabric was evaluated according to the spray method of JIS-L-1092 (AATCC-22). The water repellency was evaluated according to the following criteria. A higher score indicates better water repellency, and intermediate values ​​(95, 85, 75, 65, 55) were assigned depending on the condition.

[0468] 100 No wetting or water droplets were observed on the surface. 90 The surface was not wet, but small water droplets were observed. 80 Wetting was observed on the surface in the form of small individual water droplets. 70 Wetting was observed on half of the surface, and small individual wettings were observed penetrating the fabric. 50 Wetting was observed on the entire surface. 0 Wetting was observed on both the front and back surfaces.

[0469] [Durable Water Repellency] The water repellency of the test fabric was evaluated after washing it 20 times in accordance with JIS L 1930 Annex F C4M and then drying it in a tumble dryer (60°C for 30 minutes).

[0470] [Texture] The test fabric was evaluated by handling on a five-point scale as shown below. Depending on the condition, an intermediate value (3-4, 4-5) was assigned. 1: Stiff ~ 5: Soft

[0471] [Chalk Mark Resistance] The test cloth was placed on a flat surface, and the surface of the test cloth was lightly scratched with a fingernail. The trace left behind, resembling chalk marks, was visually evaluated. ◎○: No trace visible ○: Almost no trace visible 〇△: Faint trace visible △: Trace visible △×: Slightly dark trace visible

[0472] [Peel Strength] A hot-melt adhesive tape (MELCO Tape, manufactured by Sun Chemical Co., Ltd.) was heat-bonded to the test fabric using a heat-sealing device at 160°C for 15 seconds. The peel strength between the test fabric and the seam tape was measured using an Autograph (AGS-J, manufactured by Shimadzu Corporation). The gripper was moved at a speed of 200 mm / min and the average stress was defined as the peel strength [N / inch].

[0473] [Seam Slippage] The test fabric was tested according to ISO 13936-2, except that the load was set to 160 N, and the seam slippage (mm) was measured. A smaller seam slippage value indicates better resistance to seam slippage.

[0474] [Color Change] The color difference (color difference ΔE*ab in the L*a*b color space) between the test fabric and the unprocessed fabric was measured using a colorimeter (CR-410, manufactured by Konica Minolta, Inc.). A smaller color change value indicates less color difference and a superior result.

[0475] [Preparation of raw materials] (Example of production of aqueous dispersion containing acrylic polymer) Production example 1 In a 500 ml poly container, 30 g of water-soluble glycol solvent as an organic solvent, 120 g of pure water as a liquid medium, 48 g of stearyl acrylate as a long-chain aliphatic hydrocarbon group-containing (meth)acrylate, 2.0 g of cationic emulsifier, 2.0 g of sorbitan fatty acid ester, 6.0 g of polyoxyethylene alkyl ether and 0.1 g of acetic acid were charged, heated to 60°C, stirred with a homomixer at 2000 rpm for 1 minute, and then emulsified and dispersed with ultrasound for 15 minutes. Next, this emulsified dispersion was transferred to a 500 ml autoclave, and after nitrogen purging, 0.2 g of lauryl mercaptan and 12 g of vinyl chloride were charged as chain transfer agents. Furthermore, 1.0 g of azo group-containing water-soluble initiator was added, the temperature was raised to 60°C, and the mixture was reacted for 4 hours to obtain an aqueous dispersion of the polymer. This dispersion was further diluted with pure water to prepare an aqueous dispersion with a non-volatile concentration of 30%.

[0476] In Production Examples 2 and 3, an aqueous dispersion containing an acrylic polymer, a surfactant, and a liquid medium was prepared in the same manner as in Production Example 1, except that the formulation was changed according to Table 1.

[0477] Manufacturing Example 4: In a 500 ml poly container, 30 g of a water-soluble glycol solvent was added as an organic solvent, 120 g of pure water and 60 g of stearyl acrylate were added as liquid media, and 2.0 g of a cationic emulsifier, 2.0 g of sorbitan fatty acid ester, and 6.0 g of polyoxyethylene alkyl ether were added as surfactants. The mixture was heated to 80°C and stirred with a homomixer at 2000 rpm for 1 minute, followed by emulsification and dispersion using ultrasound for 15 minutes. The emulsion dispersion was transferred to a 500 cc four-necked flask equipped with a nitrogen inlet tube, thermometer, stirring rod, and reflux tube. After purging with nitrogen, 0.2 g of lauryl mercaptan was added and stirred. Then, 1.0 g of an azo group-containing water-soluble initiator was added, and the mixture was heated to 60°C and reacted for 4 hours to obtain an aqueous dispersion of the polymer. Subsequently, pure water was added to prepare an aqueous dispersion with a non-volatile content of 30%.

[0478] Manufacturing Example 5 1. Synthesis of Aliphatic Polyisocyanate Derivatives In a reactor equipped with a thermometer, stirrer, nitrogen inlet tube, and condenser, under a nitrogen atmosphere, 500 parts by mass of 1,6-hexamethylene diisocyanate (HDI, manufactured by Mitsui Chemicals, trade name: Takenate 700), 0.25 parts by mass of 2,6-di(tert-butyl)-4-methylphenol (also known as dibutylhydroxytoluene, BHT, hindered phenol antioxidant), and 0.25 parts by mass of tetraphenyl dipropylene glycol diphosphite (organic phosphite ester, co-catalyst) were mixed. Then, 10.7 parts by mass of 1,3-butanediol was added to this mixture, and nitrogen was introduced into the liquid phase for 1 hour. After that, the mixture was heated to 80°C and reacted for 3 hours, then cooled to 60°C. Subsequently, 0.2 parts by mass of trimethyl-N-2-hydroxypropylammonium 2-ethylhexanoate was added as an isocyanurate catalyst, and the reaction was allowed to proceed for 1.5 hours. Then, 0.04 parts by mass of o-toluenesulfonamide was added per 100 parts by mass of HDI. After that, this reaction mixture was passed through a thin-film distillation apparatus (temperature 150°C, vacuum 93.3 Pa) and distilled until the amount of remaining HDI monomer was 0.5% or less, to obtain an aliphatic polyisocyanate derivative (isocyanurate derivative of hexamethylene diisocyanate). The obtained aliphatic polyisocyanate derivative had an isocyanate group content of 20.9% and an average number of isocyanate functional groups of 3.0.

[0479] 2. In a reactor equipped with a stirrer, thermometer, cooler, and nitrogen gas inlet tube for the production of hydrocarbon polyurethanes, 100.20 g of the aliphatic polyisocyanate derivative, 67.60 g of Calcol 8098 (stearyl alcohol, manufactured by Kao Corporation) and 22.30 g of oleic alcohol were mixed and reacted at 110°C under a nitrogen atmosphere for 4 hours until the concentration of isocyanate groups reached 3.67%. Next, the reaction solution was cooled to 80°C, and 9.90 g of N-methyldiethanolamine was added as a cationic active hydrogen compound, and the mixture was reacted at 80°C for 1 hour. Next, 50.00 g of methyl ethyl ketone was added as a solvent, and the mixture was reacted at 80°C until the disappearance of isocyanate groups could be confirmed by infrared absorption spectroscopy. Next, 57.69 g of methyl ethyl ketone was added to the reaction solution, the temperature was raised to 80°C, and the mixture was stirred until the reaction solution was completely dissolved, and then it was cooled to 75°C. Subsequently, 18.96 g of acetic acid was added as an acid compound to neutralize the mixture. Next, while maintaining the reaction solution at 75°C, 800.0 g of deionized water heated to 70°C was gradually added to emulsify (internal emulsification). Then, the solvent was removed using an evaporator under reduced pressure at a water bath temperature of 60°C until the solid content concentration reached 20% by weight or more. Finally, an aqueous dispersion containing polyurethane was obtained by adjusting the solid content concentration, excluding the acid compound (acetic acid), with deionized water to 20% by weight.

[0480] Preparation Example 1: 9.0 g of MQ-1600 (manufactured by Dow Toray Industries, Inc.) as a resin-based silicone, 9.0 g of KF-96-6CS (polydimethylsiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.) as a non-resin-based silicone, and 22 g of KF-96-50CS (polydimethylsiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.) as a non-resin-based silicone with a number average molecular weight of 1500 or more were mixed and mixed until the MQ-1600 was dissolved. 4.0 g of polyoxyethylene alkyl ether was added and mixed. Then, 89 g of pure water was added to the mixture in small amounts as an aqueous medium to obtain a dispersion containing a total of 30.0% by mass of resin-based silicone and non-resin-based silicone.

[0481] Preparation Examples 2-7: Dispersions containing a total of 30.0% by mass of resin-based silicone and non-resin-based silicone were obtained in the same manner as in Preparation Example 1, except that the formulation was changed according to Table 1.

[0482] Comparative Preparation Example 1: 9.0 g of MQ-1600 (manufactured by Dow-Toray Industries, Inc.) as a resin-based silicone, 9.0 g of KF-96-6CS (polydimethylsiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.) as a non-resin-based silicone with a number average molecular weight of less than 1500, and 22 g of FZ-3710 (manufactured by Dow-Toray Industries, Inc.) as an amino-modified non-resin-based silicone were mixed and mixed until the MQ-1600 was dissolved. 4.0 g of polyoxyethylene alkyl ether was added and mixed. Then, 89 g of pure water was added to the mixture in small amounts as an aqueous medium to obtain a dispersion containing a total of 30.0% by mass of resin-based silicone and non-resin-based silicone.

[0483] Example 1 A fluorine-free acrylic polymer dispersion, a silicone compound dispersion, and tap water were mixed to obtain treatment solutions for the water-repellent compositions shown in Table 3 (the values ​​in the table indicate (weight %)). Polyester cloth, nylon cloth, polyester / polyurethane (PU) cloth, and cotton cloth were immersed in these treatment solutions and then squeezed with a mangle. These treated cloths were passed through a pin tenter at 170°C for 1 minute, then dried and cured. For the cotton cloth, it was passed through a pin tenter at 170°C for 3 minutes, then dried and cured. The test cloths treated in this way were tested for water repellency, durable water repellency, texture, chalk mark resistance, and peel strength. The results are shown in Table 3.

[0484] Examples 2-19 and Comparative Examples 1-4: Except for changing the formulation according to Table 3, the fabric was treated in the same manner as in Example 1, and tests were conducted for water repellency, durable water repellency, texture, chalk mark resistance, peel strength, seam slippage, and color change. The results are shown in Table 3.

[0485]

[0486]

[0487]

Claims

The present invention comprises a polymer (A) containing repeating units derived from a hydrocarbon group-containing monomer (a) having hydrocarbon groups with 2 to 40 carbon atoms, and a silicone compound (B) consisting of a resin-based silicone and a non-resin-based silicone. In the GPC chart of the aforementioned silicone compound (B), a peak top exists in the region of molecular weight 1500 or more. Among the aforementioned silicone compounds, the component with a molecular weight of 1500 or more includes non-resin silicones other than amino-modified silicones. A water-repellent composition in which the amount of the silicone compound (B) is 51 to 99% by weight of the sum of the amount of the polymer (A) and the amount of the silicone compound (B). The water-repellent composition according to claim 1, wherein the hydrocarbon group in the hydrocarbon group-containing monomer (a) is a linear alkyl group having 10 or more carbon atoms. The hydrocarbon group-containing monomer (a) is formula: CH2=C(-X ａ )-C(=O)-Y ａ (R ａ ) ｋ [In the formula, R ａ Each of these is independently a hydrocarbon group having 2 to 40 carbon atoms. X ａ is a hydrogen atom, a monovalent organic group, or a halogen atom. Y ａ is a group composed of at least one selected from divalent to tetravalent hydrocarbon groups having 1 carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ - or -NH- k is between 1 and 3. The water-repellent composition according to claim 1, wherein the monomer is represented by . The water-repellent composition according to any one of claims 1 to 3, wherein the amount of the silicone compound (B) is 55 to 85% by weight of the sum of the amount of the polymer (A) and the amount of the silicone compound (B). A water-repellent composition according to any one of claims 1 to 4, comprising a surfactant. The water-repellent composition according to claim 5, wherein the surfactant includes a nonionic surfactant. 　 A water-repellent composition according to any one of claims 1 to 6, further comprising an isocyanate derivative. The hydrocarbon group-containing monomer (a) is formula: CH2=C(-X ａ )-C(=O)-Y ａ (R ａ ) ｋ [In the formula, R ａ Each of these is independently a hydrocarbon group having 12 to 22 carbon atoms. X ａ is a hydrogen atom or a methyl group, Y ａ is -O- or -O-(CH ２ ) m -NH-C(=O)- (m is 2 or 4), k is 1. It is a monomer represented by The water-repellent composition according to any one of claims 1 to 7, wherein the amount of resin-based silicone is 10 parts by weight or more and 30 parts by weight or less per 100 parts by weight of non-resin-based silicone. The water-repellent composition according to any one of claims 1 to 8, which is an aqueous dispersion. A method for producing a textile product, comprising applying a water-repellent composition according to any one of claims 1 to 9 to a textile substrate. Before applying the water-repellent composition to the fiber substrate, the fibers -SO ３ M １ (In the formula, M １ A monovalent group represented by (where indicates a monovalent cation), - COOM ２ (In the formula, M ２ (represents a monovalent cation) and a monovalent group represented by, -O-P(O)(OX １ ) (OX ２ ) (wherein, X １ and X ２ A method for producing a textile product according to claim 10, comprising the step of imparting one or more functional groups selected from the group consisting of monovalent groups (each representing a hydrogen atom or an alkyl group having 1 to 22 carbon atoms). A textile product having the polymer (A) and the silicone compound (B) of the water-repellent composition according to any one of claims 1 to 9 attached to a fibrous base material. -SO ３ M １ (In the formula, M １ A monovalent group represented by (where indicates a monovalent cation), - COOM ２ (In the formula, M ２ (represents a monovalent cation) and a monovalent group represented by, -O-P(O)(OX １ ) (OX ２ ) (wherein, X １ and X ２ The textile product according to claim 12, wherein a compound having one or more functional groups selected from the group consisting of monovalent groups (each independently representing a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) is attached to it.

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