Water repellent composition and method for producing same

Abstract

Provided is a water repellent composition capable of imparting good water repellency and good chalk mark resistance to a base (particularly a fibrous product). The water repellent composition contains a polymer (A) and an organosilicon compound (B) containing a silicone oil and a silicone resin, the polymer (A) containing a repeating unit derived from a hydrocarbon group-containing monomer (a) having a C2-40 hydrocarbon group, and the organosilicon compound (B) having a peak top in a region having a molecular weight of 1500 or more in a GPC diagram of the organosilicon compound (B). A component having a molecular weight of 1500 or more in the organosilicon compound contains a silicone oil other than an amino-modified silicone, and the amount of the organosilicon compound (B) is 1-49 wt% with respect to the total amount of the polymer (A) and the amount of the organosilicon compound (B).

Description

Technical Field

[0001] This invention relates to a water-repellent composition and its manufacturing method. Background Technology

[0002] Non-fluorinated water-repellent agents have been developed as water-repellent agents used to impart water-repellent properties to base materials (especially fiber products).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: International Publication No. 2020 / 130002

[0006] Patent Document 2: International Publication No. 2019 / 131456

[0007] Patent Document 3: Japanese Patent Application Publication No. 2017 / 226946 Summary of the Invention

[0008] The technical problem that the invention aims to solve

[0009] When water-repellent agents are used in fiber products, not only water repellency but also resistance to chalk marks is required. Existing water-repellent agents neither address chalk mark resistance nor offer any inspiration.

[0010] The purpose of this invention is to provide a water-repellent composition that imparts good water-repellent properties and good chalk stain resistance to a base agent (especially a fiber product).

[0011] Technical solutions for solving technical problems

[0012] This invention includes the following methods:

[0013] [Item 1] A water-repellent composition comprising a polymer (A) and an organosilicon compound (B) comprising silicone oil and silicone resin, wherein the polymer (A) comprises repeating units derived from a hydrocarbon-containing monomer (a) having a hydrocarbon group having 2 to 40 carbon atoms.

[0014] In the GPC plot of the above organosilicon compound (B), a peak exists in the region with a molecular weight above 1500.

[0015] The components with a molecular weight of 1500 or higher in the aforementioned organosilicon compounds contain silicone oils other than amino-modified silicones.

[0016] The amount of the organosilicon compound (B) is 1 to 49 by weight, relative to the total amount of the polymer (A) and the organosilicon compound (B).

[0017] [Item 2] The water-repellent composition according to Item 1, wherein,

[0018] The hydrocarbon group in the above-mentioned hydrocarbon-containing monomer (a) is a straight-chain alkyl group with 10 or more carbon atoms.

[0019] [Item 3] The water-repellent composition according to item 1 or 2, wherein,

[0020] The aforementioned hydrocarbon-containing monomer (a) is the monomer shown in the following formula.

[0021] CH2=C(-X a )-C(=O)-Y a (R a ) k

[0022] [In the formula, R] a Each is independently a hydrocarbon group with 2 to 40 carbon atoms.

[0023] X a It can be a hydrogen atom, a monovalent organic group, or a halogen atom.

[0024] Y a It is a group consisting of at least one selected from a hydrocarbon group with one carbon atom in the divalent to tetravalent state, -C6H4-, -O-, -C(=O)-, -S(=O)2-, or -NH-, where k is 1 to 3.

[0025] [Item 4] The water-repellent composition according to any one of items 1 to 3, wherein,

[0026] The amount of the organosilicon compound (B) is 1 to 25 by weight, relative to the total amount of the polymer (A) and the organosilicon compound (B).

[0027] [Item 5] The water-repellent composition according to any one of items 1 to 4, wherein it contains a surfactant.

[0028] [Item 6] The water-repellent composition according to claim 5, wherein...

[0029] The surfactants mentioned above include nonionic surfactants.

[0030] [Item 7] The water-repellent composition according to any one of items 1 to 6 is an aqueous dispersion.

[0031] [Item 8] A method for manufacturing a fiber product, comprising:

[0032] The step of applying the water-repellent composition of any one of items 1 to 7 to a fiber substrate.

[0033] [Item 9] The method for manufacturing the fiber article according to Item 8 includes:

[0034] The process of imparting the fiber with one or more functional groups selected from monovalent groups shown in the following formula before applying the above-mentioned water-repellent composition to the above-mentioned fiber substrate:

[0035] -SO3M 1 (where M is in the formula) 1 The monovalent group (representing a monovalent cation) is shown in the diagram.

[0036] -COOM 2 (where M is in the formula) 2 The monovalent group (representing a monovalent cation) is shown in the diagram.

[0037] -OP(O)(OX 1 (OX) 2 (where X) 1 and X 2 The monovalent group (representing either a hydrogen atom or an alkyl group with 1 to 22 carbon atoms, respectively) is independently represented.

[0038] [Item 10] A fiber article having the polymer (A) and the organosilicon compound (B) of any one of the water-repellent compositions described in items 1 to 7 attached to a fiber substrate.

[0039] [Item 11] The fiber article according to item 10 is attached with a compound having one or more functional groups selected from the monovalent groups shown in the following formula:

[0040] -SO3M 1 (where M is in the formula) 1 The monovalent group (representing a monovalent cation) is shown in the diagram.

[0041] -COOM 2 (where M is in the formula) 2 The monovalent group (representing a monovalent cation) is shown in the diagram.

[0042] -OP(O)(OX 1 (OX) 2 (where X) 1 and X 2 The monovalent group (representing either a hydrogen atom or an alkyl group with 1 to 22 carbon atoms, respectively) is independently represented.

[0043] Invention Effects

[0044] The water-repellent composition of the present invention can impart good water repellency and good chalk mark resistance to the base material (especially fiber products). Detailed Implementation

[0045] <Definition of Terms>

[0046] In this specification, the term "n-valent group" refers to a group having n bonds, i.e., a group forming n bonds. Furthermore, the term "n-valent organic group" refers to an n-valent group containing carbon. There is no particular limitation on the aforementioned organic group; it can be a hydrocarbon group or its derivative. A hydrocarbon derivative refers to a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, or halogen groups at the end of the hydrocarbon group or in the molecular chain.

[0047] In the context of this specification, "hydrocarbon group" refers to a group containing carbon and hydrogen, after the hydrogen atom has been removed from a hydrocarbon. Without particular limitation, examples of hydrocarbon groups include: C 1-20 Hydrocarbon groups, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The aforementioned "aliphatic hydrocarbon group" can be straight-chain, branched, or cyclic, and can be saturated or unsaturated. Furthermore, the hydrocarbon group can contain one or more ring structures. Where explicitly stated, the hydrocarbon group can be substituted by one or more substituents.

[0048] In this specification, regardless of whether it is explicitly stated as "independently in each occurrence," "independently in each other," "independently in each other," or the same expression, except where it is stated as an exception, when multiple terms (symbols) may appear in a chemical structure and are defined, the definition applies independently each time it appears.

[0049] The chemical structures described in this specification should be understood to exclude chemical structures that are considered chemically impossible or extremely unstable by those skilled in the art.

[0050] <Water-repellent composition>

[0051] The water-repellent composition of this invention comprises a polymer (A) and an organosilicon compound (B) comprising silicone oil and silicone resin. The polymer (A) comprises repeating units derived from a hydrocarbon-containing monomer (a) having 2 to 40 carbon atoms. The organosilicon compound (B) comprises silicone resin and silicone oil. In the GPC plot of the organosilicon compound (B), peaks exist in the region with a molecular weight of 1500 or higher, and the components in the organosilicon compound with a molecular weight of 1500 or higher contain silicone oil other than amino-modified silicone. The amount of organosilicon compound (B) is 1 to 49% by weight, relative to the total amount of the polymer (A) and the organosilicon compound (B). The water-repellent composition of this invention adheres to a substrate (particularly a fibrous product) and imparts both good water repellency and good chalk residue resistance to the substrate.

[0052] [(A) Polymer]

[0053] The polymer (A) of the present invention will be described. Polymer (A) comprises repeating units derived from hydrocarbon-containing monomers (a) having 2 to 40 carbon atoms. Polymer (A) is a polymer formed by polymerizing monomers and exhibits water-repellent properties. Here, the monomer can be any compound having a polymerizable carbon-carbon double bond (olefinic unsaturated double bond) (>C=C<), and can be a monomer containing vinyl, vinylidene, vinylidene, acryloyl, methacryloyl, or derivatives thereof.

[0054] The polymer (A) of the present invention is attached to a substrate (particularly a fibrous substrate) and imparts liquid-repellent properties, such as water resistance, oil resistance, water repellency, oil repellency and / or stain resistance, particularly oil resistance.

[0055] [Characteristics, etc.]

[0056] The following describes the properties that the polymer (A) of the present invention may have.

[0057] The HD (n-hexadecane) contact angle of polymer (A) can 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 can also be 100° or less, 90° or less, or 75° or less. By having an HD contact angle of polymer (A) at or above the lower limit mentioned above, good liquid repellency (particularly water repellency) can be imparted to the substrate. The HD contact angle refers to the static contact angle of the spin-coated film of polymer (A), and is a value obtained by adding 2 μL of HD to the spin-coated film at room temperature (25°C) and measuring the contact angle after 1 second of dripping.

[0058] 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. Alternatively, it can 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 polymer (A) above or below the aforementioned lower limit, good liquid repellency (especially water repellency) can be imparted to the substrate. The water contact angle refers to the static contact angle of the spin-coated film of polymer (A), and is obtained by adding 2 μL of water to the spin-coated film at room temperature (25°C) and measuring the contact angle after 1 second of dripping.

[0059] Polymer (A) is preferably a carbon compound of bio-based origin. Biomass content is determined according to ASTM D6866. The biomass content of polymer (A) can be 20% or more, preferably 30% or more, more preferably 50% or more, further preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example, 100%. High biomass content means that the amount of fossil resources such as petroleum used is low; therefore, from the above perspective, it can be said that the higher the biomass content of polymer (A), the more preferred it is.

[0060] The biodegradability of polymer (A) at 180 days is preferably 5% or more. From the perspective of minimizing environmental impact, the higher the biodegradability, the more preferred. The biodegradability of polymer (A) at 180 days can 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, further preferably 70% or more, and most preferably 80% or more. The biodegradability of polymer (A) at 60 days is preferably 5% or more. From the perspective of minimizing environmental impact, the higher the biodegradability, the more preferred. The biodegradability of polymer (A) at 60 days can 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, more preferably 30% or more. The biodegradability mentioned above can be the biodegradability specified in JISK 6953-1 or ASTM D6400.

[0061] The melting point of polymer (A) can be above 30°C, above 40°C, above 60°C, above 80°C, above 100°C, or above 120°C, preferably above 40°C. Alternatively, it can be below 250°C, below 225°C, below 200°C, below 150°C, below 130°C, below 120°C, below 110°C, below 100°C, below 80°C, or below 50°C.

[0062] [Structure, etc.]

[0063] The polymer (A) in this invention may not have any of the following: fluoroalkyl groups with 8 or more carbon atoms, perfluoroalkyl groups with 8 or more carbon atoms, fluoroalkyl groups with 4 or more carbon atoms, perfluoroalkyl groups with 4 or more carbon atoms, perfluoroalkyl groups, fluoroalkyl groups, and fluorine atoms. Even if the polymer (A) does not contain these fluorine-containing groups, it can impart liquid-repellent properties to the substrate.

[0064] The polymer (A) in this invention may not be a fatty acid ester with a glycosidic bond. A fatty acid ester with a glycosidic bond is typically a compound in which a fatty acid is added to the hydroxyl group of a compound with a glycosidic bond structure (typically a sugar (monosaccharide or polysaccharide)) via an ester bond.

[0065] The polymer (A) in this invention can be a compound having at least one group selected from hydrocarbon groups having 2 to 40 carbon atoms and polysiloxane groups. In particular, polymer (A) can be a compound having at least one group selected from hydrocarbon groups having 2 to 40 monovalent carbon atoms and polysiloxane groups.

[0066] (Polysiloxane)

[0067] Polymer (A) may have a polysiloxane group. Similar to hydrocarbon groups that may have substituents with two or more carbon atoms, the polysiloxane group can impart liquid-repellent properties to the substrate.

[0068] Polysiloxane is a group having a polysiloxane structure. In this specification, when referred to as polysiloxane, unless otherwise specified, it refers to an organopolysiloxane modified with an organic group.

[0069] The polysiloxane has 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. Alternatively, it can 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.

[0070] The polysiloxane alkyl group can be monovalent, located at the end of the molecule, or divalent or polyvalent, located inside the molecule, but is preferably monovalent.

[0071] Polysiloxane can be represented by the following formula:

[0072] -[-Si(R s )2-O-] a -

[0073] [In the formula,

[0074] R s Each occurrence is independently a hydrocarbon group or reactive group with 1 to 40 carbon atoms, where 'a' is an integer from 5 to 10,000.

[0075] R s It is a hydrocarbon group or a reactive group with 1 to 40 carbon atoms.

[0076] Examples of hydrocarbon groups with 1 to 40 carbon atoms include hydrocarbon groups with 1 to 5 carbon atoms and hydrocarbon groups with 6 to 40 carbon atoms.

[0077] Examples of hydrocarbon groups with 1 to 5 carbon atoms include: methyl, ethyl, propyl, butyl, pentyl, etc. (especially aliphatic hydrocarbon groups, especially alkyl groups, such as methyl or ethyl, especially methyl).

[0078] The hydrocarbon group having 2 to 40 carbon atoms can be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, and particularly preferably a saturated aliphatic hydrocarbon group (alkyl). The hydrocarbon group can be cyclic, linear, or branched, preferably linear. The number of carbon atoms in the hydrocarbon group can 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. Alternatively, it can 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.

[0079] Examples of reactive groups are groups having functional groups (e.g., hydroxyl, amino, mercapto, epoxy, carboxyl, haloalkyl, vinyl, (meth)propenyl, (meth)acryloyloxy, and (meth)acrylamido, hydrogen atoms directly bonded to silicon atoms, etc.). These functional groups can be directly bonded to silicon atoms or bonded to organic groups directly bonded to silicon atoms. The organic group can be a hydrocarbon group, for example, an alkylene group or a divalent aromatic group. The hydrocarbon group can have 2 to 12 carbon atoms, and as an alkylene group, it is preferred to have 2 to 10 carbon atoms. As a divalent aromatic group, it is preferred to have 6 to 12 carbon atoms. The reactive group can be a group selected from hydroxyl, epoxy, carboxyl, (meth)propenyl, and amino, for example, it can be at least one selected from epoxy, hydroxyl, (meth)propenyl, and carboxyl.

[0080] a can 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. Alternatively, it can be less than 10000, less than 7500, less than 5000, less than 3000, less than 1500, less than 1000, less than 500, less than 300, less than 200, less than 100, or less than 50, preferably less than 500.

[0081] In polysiloxane, relative to R s The total, as R of hydrocarbon groups with 1 to 5 carbon atoms sThe amount can be 20 mol% or more, 40 mol% or more, 60 mol% or more, or 80 mol% or more, preferably 50 mol% or more, and can also be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less. For example, relative to R s The total amount of the radicals, more than 50 mol%, can be methyl or ethyl (especially methyl).

[0082] In polysiloxane, relative to R s The total, as R of hydrocarbon groups with 2 to 40 carbon atoms s The amount can be 3 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more. Alternatively, it can be less than 100 mol%, less than 90 mol%, less than 80 mol%, or less than 70 mol%.

[0083] In polysiloxane, relative to R s The total of R as a reactive group s The amount can be 5 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more; alternatively, it can be less than 50 mol%, less than 40 mol%, less than 30 mol%, or less than 20 mol%. The polysiloxane may also be free of R, which is a reactive group. s .

[0084] R s Bases can be imported in random or block form, but random is preferred.

[0085] The terminal structure of the aforementioned polysiloxane alkyl group is not limited and can be -R. s -OR s 、-Si(R s )3, etc. R of the end structure s It may have more than one reactive group, or it may not have more than one reactive group. Examples of reactive groups are as described above, for example, it may be at least one selected from epoxy ring, hydroxyl, (meth)propenyl and carboxyl groups.

[0086] The polysiloxane may have a linking group, and the parent structure and the polysiloxane may be bonded via the linking group. There is no limitation on such a linking group, which may be a hydrocarbon group with 1 to 40 (e.g., 1 to 20) carbon atoms that can be interrupted by an oxygen atom, or a (poly)oxyalkylene group with 1 to 40 (e.g., 1 to 20) carbon atoms.

[0087] Examples of polysiloxanes include:

[0088] -[-Si(R s )2-O-] a -Si(R s3.

[0089] -L s1 -[-Si(R s )2-O-] a -Si(R s 3.

[0090] -L s1 -OL s1 -[-Si(R s )2-O-] a -R s ,

[0091] -L s1 -[-Si(R s )2-O-] a -Si(R s 3.

[0092] -L s1 -OL s1 -[-Si(R s )2-O-] a -R s ,

[0093] -L s1 -[-Si(R s )2-O-] a -Si(R s 3.

[0094] -L s1 -[-Si(R s )2-O-] a -R s

[0095] [In the formula,

[0096] R s Each occurrence is independently a hydrocarbon group or reactive group with 1 to 40 carbon atoms, relative to R. s Of the total amount of groups, 50 mol% or more are methyl groups.

[0097] L s1 Each occurrence is independently a hydrocarbon group with 1 to 20 carbon atoms.

[0098] a is between 5 and 10000.

[0099]

[0100] [In the formula, a represents an integer from 0 to 150, b represents an integer from 1 to 150, (a+b) is from 5 to 200, and n is an integer from 0 to 36.] etc.

[0101] Polysiloxane groups can form branched structures (silicone resin structures) by having silsesquioxane and / or silica structures, for example, they can be formed from...

[0102] -O-Si(R s (-O-)2、

[0103] -O-Si(-O-)3

[0104] Such branched structures form branched structures.

[0105] The weight-average molecular weight of polymer (A) can be 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more. Alternatively, it can be less than 5000000, less than 3000000, less than 1000000, less than 750000, less than 500000, less than 300000, less than 100000, less than 75000, less than 50000, less than 30000, less than 10000, or less than 5000. The weight-average molecular weight can be the converted molecular weight of polystyrene determined by GPC.

[0106] (a) Hydrocarbon-containing monomers

[0107] The polymer (A) of the present invention comprises repeating units derived from hydrocarbon monomers (a) having 2 to 40 carbon atoms.

[0108] Monomer (a) preferably has a (meth)propene group as a group having an olefinic unsaturated double bond, for example, it may have a (meth)acrylate group or a (meth)acrylamide group as an olefinic unsaturated double bond.

[0109] The monomer (a) has a hydrocarbon group having 2 to 40 carbon atoms. This hydrocarbon group may have substituents, but is preferably unsubstituents. Here, the hydrocarbon group is a monovalent group.

[0110] The monomer (a) may contain an aromatic or aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, and particularly preferably a saturated aliphatic hydrocarbon group (alkyl). The hydrocarbon group may be branched or linear, more preferably linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl).

[0111] The hydrocarbon group can typically be monovalent and located at the end of the molecule, or it can have one or more methyl groups at the end of the hydrocarbon group. For clarity, in this specification, a hydrocarbon compound (e.g., a hydrocarbon wax) is understood as a substance consisting only of a monovalent hydrocarbon group and one hydrogen atom; for example, a 20-carbon n-alkane (eicosane) is understood as a substance consisting only of a 20-carbon alkyl group and one hydrogen atom.

[0112] The number of carbon atoms in the hydrocarbon group can 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. Alternatively, it can 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 2 or more and 40 or less, but for example, when the polymer (A) is a hydrocarbon compound (hydrocarbon wax), it can exceed 40.

[0113] The hydrocarbon group may have substituents, but is preferably unsubstituented. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms, etc. (where R' is independently a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms in each occurrence). 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 with substituents, 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, as a substituent, can have 1 to 3 (e.g., 1) -OR' (especially -OH) (e.g., outside the terminal).

[0114] The hydrocarbon-containing monomer (a) is preferably a monomer represented by the following formula.

[0115] CH2=C(-X a )-C(=O)-Y a (R a ) k

[0116] [In the formula, R] a Each is independently a hydrocarbon group with 2 to 40 carbon atoms.

[0117] X a It can be a hydrogen atom, a monovalent organic group, or a halogen atom.

[0118] Y a It is a group composed of at least one hydrocarbon group selected from divalent to tetravalent carbon atoms (especially -CH2-, -CH(-)2), -C6H4-, -O-, -C(=O)-, -S(=O)2- or -NH-.

[0119] k is 1 to 3.

[0120] X a It can 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. X a Examples include hydrogen atoms, methyl groups, chlorine atoms, bromine atoms, iodine atoms, and cyano groups. X a Preferably, it contains hydrogen atoms, methyl groups, or chlorine atoms. Particularly preferred is X. a It is a hydrogen atom.

[0121] Y a It consists of divalent to tetravalent groups. Y a Preferably, it has a divalent group.

[0122] Y a Preferably, it consists of at least one group selected from a hydrocarbon group having one carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2-, or -NH-. Y is preferred. a It is not a hydrocarbon group. Examples of hydrocarbon groups with one carbon atom include -CH2-, -CH(-)2, or -C(-)3. Hydrocarbon groups with one carbon atom are arranged in a repeating sequence, such as -(CH2). m -(m is an integer from 1 to 5) in this way, hydrocarbon groups with more than 2 carbon atoms can be formed. Y a It can have an NH group.

[0123] Y a Can be -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'-

[0124] [In the formula, Y' represents a valence bond, -O-, -NH-, or -S(=O)2-,

[0125] R' is -(CH2) m -(m is an integer from 1 to 5) or -C6H4-(phenylene).

[0126] Y a Specific examples are -O-, -NH-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m-NH-, -NH-(CH2) m -O-, -O-(CH2) m -O-C(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -O-C(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -O-C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, -NH-(CH2) m -NH-C6H4-, -NH-(CH2) m -NH-S(=O)2-, or -NH-(CH2) m -S(=O)2-NH-[where m is 1 to 5, especially 2 or 4.]

[0127] Y a Preferably -O-, -NH-, -O-(CH2) m -O-C(=O)-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2)m -S(=O)2-NH-、-NH-(CH2) m -NH-S(=O)2- or -NH-(CH2) m -S(=O)2-NH- [where m is an integer from 1 to 5, especially 2 or 4. ] Y a More preferably, it is -O- or -O-(CH2). m -NH-C(=O)-, particularly preferred is -O-(CH2). m -NH-C(=O)-.

[0128] R a Each hydrocarbon group is independently composed of 2 to 40 carbon atoms. Referring to the description already provided above (hydrocarbon groups with 2 to 40 carbon atoms), it is preferably a straight-chain or branched hydrocarbon group. The hydrocarbon group is particularly preferably a straight-chain hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly preferably a saturated aliphatic hydrocarbon group, and particularly preferably 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.

[0129] Specific examples of monomer (a) are the monomer represented by formula (a1) and the monomer represented by formula (a2).

[0130] (a1) formula:

[0131] CH2=C(-X a1 )-C(=O)-Y a11 -Z(-Y a12 -R a1 ) n

[0132] [In the formula, R] a1 Each is independently a hydrocarbon group with 2 to 40 carbon atoms.

[0133] X a1 It can be a hydrogen atom, a monovalent organic group, or a halogen atom.

[0134] Y a11 It is -O- or -NH-.

[0135] Y a12 Each of the following groups is independently a valence bond, or is composed of at least one group selected from -O-, -C(=O)-, -S(=O)2-, -NH-, or -CH2-.

[0136] Z is a valence bond, or a hydrocarbon group with 1 to 5 carbon atoms in a divalent or trivalent state.

[0137] n is 1 or 2.

[0138] Equation (a2):

[0139] CH2=C(-X a2 )-C(=O)-Y a2 -R a2

[0140] [In the formula, R] a2 Hydrocarbon groups with 2 to 40 carbon atoms

[0141] X a2 It can be a hydrogen atom, a monovalent organic group, or a halogen atom.

[0142] Y a2 It is either -O- or -NH-.

[0143] (a1) monomer

[0144] Monomer (a1) is a different monomer from monomer (a2).

[0145] The monomer (a1) can be a monomer having a hydrocarbon group having 2 to 40 carbon atoms and a group containing an NH group. The monomer (a1) can contain an amide group, a urea group, a carbamate group, or a sulfonamide group. The group containing an NH group can be an amide group, a urea group, a carbamate group, or a sulfonamide group. The hydrocarbon monomer can be a combination of a hydrocarbon monomer having an amide group, a urea group, a carbamate group, or a sulfonamide group and a hydrocarbon monomer not having an amide group, a urea group, a carbamate group, or a sulfonamide group. By containing the above-mentioned groups in the monomer (a1), the effects of the present invention can be effectively achieved.

[0146] The monomer (a1) is a (meth)acrylate or (meth)acrylamide having a group consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH- or -CH2-.

[0147] The monomer (a1) can be a compound represented by the following formula:

[0148] CH2=C(-X a1 )-C(=O)-Y a11 -Z(-Y a12 -R a1 ) n

[0149] [In the formula, R] a1 Each is independently a hydrocarbon group with 2 to 40 carbon atoms.

[0150] X a1 It can be a hydrogen atom, a monovalent organic group, or a halogen atom.

[0151] Y a11 It is -O- or -NH-.

[0152] Y a12 Each of the following groups is independently a valence bond, or is composed of at least one group selected from -O-, -C(=O)-, -S(=O)2-, -NH-, or -CH2-.

[0153] Z is a valence bond, or a hydrocarbon group with 1 to 5 carbon atoms in a divalent or trivalent state.

[0154] n is 1 or 2.

[0155] Y a12 And / or Z may not be a valence bond. Y a12 Z and Z can not both be valence bonds.

[0156] R a1 Preferably, it is an aliphatic hydrocarbon group, particularly preferably a saturated aliphatic hydrocarbon group, and especially preferably an alkyl group. In R a1 In the hydrocarbon group, the number of carbon atoms is preferably 12 to 30, for example 16 to 26 or 15 to 26, and particularly preferably 18 to 22 or 17 to 22.

[0157] X a1 It can 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. Preferably, it is a hydrogen atom, a methyl group, or a chlorine atom.

[0158] Y a12 It can be -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 independently a valence bond, -O-, -NH-, or -S(=O)2-, and R' is -(CH2]. m -(m is an integer from 1 to 5), a straight-chain hydrocarbon group with 1 to 5 carbon atoms and unsaturated bonds, a hydrocarbon group with 1 to 5 carbon atoms and a branched structure, or -(CH2). l -C6H4-(CH2) l -(l are independent integers from 0 to 5, -C6H4- is phenylene).

[0159] Y a12Specific examples include valence bonds, -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-, -O-C6H4-, -NH-C6H4-, and -O-(CH2). m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -C(=O)-O-、-NH-(CH2) m -OC(=O)-, -NH-(CH2) m -C(=O)-O-、-O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-、-O-(CH2) m -O-C6H4-、-NH-(CH2) m -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-、-NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-、-NH-(CH2) m -NH-C6H4- [where m is an integer from 1 to 5.]

[0160] Special Y a12 It can have an NH group.

[0161] Y a12Preferred are -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-, -O-C6H4-. Y a12 Further preferred are -NH-C(=O)-, -C(=O)-NH-, -OC(=O)-NH-, -NH-C(=O)-O-, or -NH-C(=O)-NH-. a12 It doesn't have to be a price key.

[0162] Z is a valence bond, or a divalent or trivalent hydrocarbon group with 1 to 5 carbon atoms. It can have a straight-chain structure or a branched structure. The number of carbon atoms in Z is preferably 2 to 4, and particularly preferably 2. Specific examples of Z are valence bonds, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH(-)2, -CH2(CH-)CH2-, -CH2CH2CH(-)2, -CH2CH2CH2CH2CH(-)2, -CH2CH2(CH-)CH2-, and -CH2CH2CH2CH(-)2. Z may not be a valence bond.

[0163] The monomer (a1) is preferably CH2=C(-X) a1 )-C(=O)-O-(CH2) m -NH-C(=O)-R a1 CH2=C(-X) a1 )-C(=O)-O-(CH2) m -OC(=O)-NH-R a1 CH2=C(-X) a1 )-C(=O)-O-(CH2) m -NH-C(=O)-OR a1 CH2=C(-X) a1 )-C(=O)-O-(CH2) m -NH-C(=O)-NH-R a1 [wherein, R] a1 and X a1 Same meaning as above.

[0164] The monomer (a1) is particularly preferred to be CH2=C(-X) a1 )-C(=O)-O-(CH2) m -NH-C(=O)-R a1 .

[0165] The monomer (a1) can be produced by reacting a hydroxyalkyl (meth)acrylate or a hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate. Examples of long-chain alkyl isocyanates include lauryl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate, oleyl isocyanate, and dodecyl isocyanate.

[0166] Alternatively, the monomer (a1) can also be produced by reacting a (meth)acrylate with an isocyanate group on its side chain, such as 2-methacryloyloxyethyl methacrylate, with a long-chain alkylamine or a long-chain alkyl alcohol. Examples of long-chain alkylamines include laurylamine, tetradecylamine, hexadecylamine, octadecylamine, oleylamine, and behenylamine. Examples of long-chain alkyl alcohols include lauryl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, oleyl alcohol, and behenyl alcohol.

[0167] Preferred examples of monomer (a) are described below:

[0168] Octadecyl (meth)acrylate, docosyl (meth)acrylate, octadecyl α-chloroacrylate, docosyl α-chloroacrylate;

[0169] Octadecyl (methyl)acrylamide, docosyl (methyl)acrylamide;

[0170]

[0171]

[0172] [In the above formula, n is a number from 6 to 40, and m is a number from 1 to 5.]

[0173] The compounds with the above chemical formulas are acrylic acid compounds with a hydrogen atom at the α-position. Specific examples include methacrylic acid compounds with a methyl atom at the α-position and α-chloroacrylic acid compounds with a chlorine atom at the α-position.

[0174] The monomer (a1) is preferably an amide-containing monomer represented by the following formula.

[0175] R a12 -C(=O)-NH-R a13 -OR a11

[0176] [In the formula, R] a11 It consists of organic residues with olefinically unsaturated polymerizable groups.

[0177] R a12 Hydrocarbon groups with 2 to 40 carbon atoms

[0178] R a13 It consists of a hydrocarbon group with 1 to 5 carbon atoms.

[0179] R a11 This refers to organic residues containing olefinically unsaturated polymerizable groups; there are no particular limitations as long as they contain a polymeric carbon-carbon double bond. Specifically, examples include: -C(=O)CR a111 ]=CH2、-CHR a111 =CH2、-CH2CHR a111 =CH2 and other organic residues with olefinically unsaturated polymerizable groups, R a111 Examples include alkyl groups having 1 to 4 hydrogen atoms or carbon atoms. Additionally, R... a11 In addition to olefinic unsaturated polymerizable groups, it can also have various organic groups, such as chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, and polysiloxane groups. These organic groups can be replaced by various substituents. a11 Preferably -C(=O)CR a111 =CH2.

[0180] R a12 The hydrocarbon group present in monomer (a) is, as described above, a hydrocarbon group with 2 to 40 carbon atoms, preferably an alkyl group, and examples include chain hydrocarbon groups and cyclic hydrocarbon groups. Among these, chain hydrocarbon groups are preferred, and linear saturated hydrocarbon groups are particularly preferred. R a12 The number of carbon atoms is 6 to 40, preferably 11 to 27, and particularly preferably 15 to 23.

[0181] R a13 It is a hydrocarbon group having 1 to 5 carbon atoms, preferably an alkyl group. The hydrocarbon group having 1 to 5 carbon atoms can be either straight-chain or branched, and can also have unsaturated bonds, preferably straight-chain. R a13 The number of carbon atoms is preferably 2 to 4, and particularly preferably 2. R a13 Preferably, it is an alkylene group.

[0182] Amide monomers can be R a12 A substance of one kind (e.g., R) a12 Compounds with only 17 carbon atoms), or R a12 For substances that are multiple combinations (e.g., R) a12 The compound with 17 carbon atoms and R a12 (A mixture of compounds having 15 carbon atoms).

[0183] Examples of monomers containing amide groups are carboxylic amide alkyl (meth)acrylates.

[0184] Specific examples of amide-containing monomers include: palmitamide ethyl (meth) acrylate, stearamide ethyl (meth) acrylate, behenamide ethyl (meth) acrylate, myristamide ethyl (meth) acrylate, lauramide ethyl (meth) acrylate, isostearate acetamide (meth) acrylate, oleate acetamide (meth) acrylate, tert-butylcyclohexylhexamide ethyl (meth) acrylate, adamantane carboxylic acid acetamide (meth) acrylate, naphtholic carboxylic acid acetamide ethyl (meth) acrylate, anthracene carboxylic acid acetamide ethyl (meth) acrylate, palmitamide propyl (meth) acrylate, stearamide propyl (meth) acrylate, palmitamide ethyl vinyl ether, stearamide ethyl vinyl ether, palmitamide ethyl allyl ether, stearamide ethyl allyl ether, or mixtures thereof.

[0185] The amide-containing monomer is preferably stearamide ethyl (meth)acrylate. The amide-containing monomer can be a mixture containing stearamide ethyl (meth)acrylate. In the mixture containing stearamide ethyl (meth)acrylate, the amount of stearamide ethyl (meth)acrylate relative to the total weight of the amide-containing monomer can 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 can be less than 90% by weight, 80% or less by weight, or 70% or less by weight. The remaining monomer can be, for example, palmitamide ethyl (meth)acrylate.

[0186] (a2) monomer

[0187] Monomer (a2) is a compound represented by the following formula:

[0188] CH2=C(-X a2 )-C(=O)-Y a2 -R a2

[0189] [In the formula, R] a2 Hydrocarbon groups with 2 to 40 carbon atoms

[0190] X a2 It can be a hydrogen atom, a monovalent organic group, or a halogen atom.

[0191] Y a2 It is either -O- or -NH-.

[0192] Monomer (a2) is Y a2 It is a long-chain acrylate monomer of -O- or Y- a2 It is a long-chain acrylamide monomer with -NH-.

[0193] R a2 Preferably, it is an aliphatic hydrocarbon group, particularly preferably a saturated aliphatic hydrocarbon group, and especially preferably an alkyl group. In R a2In this process, 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.

[0194] X a2 It can 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. Preferably, it is a hydrogen atom, a methyl group, or a chlorine atom.

[0195] Preferred examples of long-chain acrylate monomers are: lauryl (meth)acrylate, octadecyl (meth)acrylate, eicosyl (meth)acrylate, docosyl (meth)acrylate, octadecyl α-chloroacrylate, eicosyl α-chloroacrylate, and docosyl α-chloroacrylate.

[0196] Preferred examples of long-chain acrylamide monomers are: octadecyl (methyl)acrylamide, eicosyl (methyl)acrylamide, and docosyl (methyl)acrylamide.

[0197] The polymer (A) of the present invention may further comprise repeating units derived from the following monomers.

[0198] (b) Monomers containing hydrophilic groups

[0199] The polymer (A) of the present invention may comprise repeating units derived from a monomer (b) containing a hydrophilic group. The monomer (b) is a monomer other than monomer (a) and is a monomer having a hydrophilic group.

[0200] Monomer (b) preferably has a (meth)propenyl group as a group having an olefinic unsaturated double bond; for example, it may have a (meth)acrylate group or a (meth)acrylamide group as an olefinic unsaturated double bond. Monomer (a) may have one or two groups having an olefinic unsaturated double bond, but preferably only one group having an olefinic unsaturated double bond.

[0201] The hydrophilic group is preferably an oxyalkylene group (the alkylene group has 2 to 6 carbon atoms), and particularly preferably an oxyethylene. In particular, the 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, polyalkylene (or monoalkylene) glycol mono(meth)acrylamide.

[0202] Monomer (b) is preferably an oxoalkylene (meth)acrylate represented by the following formula.

[0203] CH2=CX b C(=O)-Y b -(R b O) n -A b

[0204] [In the formula,

[0205] X b It can be a hydrogen atom or a methyl group.

[0206] Y b It is -O- or -NH-.

[0207] R b Each is independently an alkylene group having 2 to 6 carbon atoms.

[0208] A b It consists of hydrogen atoms, unsaturated or saturated hydrocarbon groups with 1 to 22 carbon atoms, or CH2=CX. b C(=O)-,

[0209] n is an integer from 1 to 90.

[0210] Examples of monomer (b) are preferably compounds represented by the following formula:

[0211] CH2=CX b C(=O)-O-(R b O) n -A bi (b1)

[0212] and

[0213] CH2=CX b C(=O)-O-(R b O) n -C(=O)CX b =CH2(b2),

[0214] CH2=CX b C(=O)-NH-(R b O) n -A bi (b3)

[0215] [In the formula,

[0216] X b Each can be independently a hydrogen atom or a methyl group.

[0217] A bi Each is independently composed of a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms.

[0218] R b Each is independently an alkylene group having 2 to 6 carbon atoms.

[0219] n is an integer from 1 to 90.

[0220] n can be, for example, 1 to 50, particularly 1 to 30, especially 1 to 15 or 2 to 15. Or, n can be, for example, 1.

[0221] R b It can be a straight-chain or branched alkylene group, for example, it can be of the formula -(CH2). x -or-(CH2) x1 -(CH(CH3)) x2 - indicates a group, [where x1 and x2 are 0 to 6, for example 2 to 5, and the sum of x1 and x2 is 1 to 6. -(CH2)] x1 -and-(CH(CH3)) x2 The order of - is not limited to the recorded formula and can also be random.

[0222] In -(R b O) n In -, R can be two or more types (e.g., two to four types, especially two types), -(R b O) n -For example, it can be -(R) 1 O) n1 -and-(R) 2 O) n2 -[where R is in the formula] 1 and R 2 They are different from each other, being alkylene groups with 2 to 6 carbon atoms, where n1 and n2 are numbers greater than 1, and the sum of n1 and n2 is 2 to 90.

[0223] R in equations (b1), (b2) and (b3) b Particularly preferred are ethylene, propylene, or butylene, with butylene being particularly preferred. R in formulas (b1), (b2), and (b3) b It can be a combination of two or more alkylene groups. In this case, it is preferred that at least one of R is ethylene, propyleneene, or butylene. As R b Combinations can include: ethylene / propylene, ethylene / butylene, and propylene / butylene. Monomer (b) can be a mixture of two or more. In this case, at least one of the monomers (b) is preferably R from formula (b1), (b2), or (b3). b It is ethylene, propylene, or butylene. Furthermore, when using polyalkylene glycol di(meth)acrylate represented by formula (b2), it is not preferred to use it alone as monomer (b), but rather in combination with monomer (b1). In this case, it is also preferred that the compound represented by formula (b2) is limited to less than 30% by weight in the monomer (b) used.

[0224] Specific examples of monomers (b) may be illustrated by the following compounds, but are not limited to these.

[0225] CH2=CHCOO-CH2CH2O-H

[0226] CH2=CHCOO-CH2CH2CH2O-H

[0227] CH2=CHCOO-CH2CH(CH3)OH

[0228] CH2=CHCOO-CH(CH3)CH2O-H

[0229] CH2=CHCOO-CH2CH2CH2CH2O-H

[0230] CH2=CHCOO-CH2CH2CH(CH3)OH

[0231] CH2=CHCOO-CH2CH(CH3)CH2O-H

[0232] CH2=CHCOO-CH(CH3)CH2CH2O-H

[0233] CH2=CHCOO-CH2CH(CH2CH3)OH

[0234] CH2=CHCOO-CH2C(CH3)2O-H

[0235] CH2=CHCOO-CH(CH2CH3)CH2O-H

[0236] CH2=CHCOO-C(CH3)2CH2O-H

[0237] CH2=CHCOO-CH(CH3)CH(CH3)OH

[0238] CH2=CHCOO-C(CH3)(CH2CH3)OH

[0239] CH2=CHCOO-(CH2CH2O)2-H

[0240] CH2=CHCOO-(CH2CH2O)4-H

[0241] CH2=CHCOO-(CH2CH2O)5-H

[0242] CH2=CHCOO-(CH2CH2O)6-H

[0243] CH2=CHCOO-(CH2CH2O)5-CH3

[0244] CH2=CHCOO-(CH2CH2O)9-CH3

[0245] CH2=CHCOO-(CH2CH2O) 23 -CH3

[0246] CH2=CHCOO-(CH2CH2O) 90 -CH3

[0247] CH2=CHCOO-(CH2CH(CH3)O)9-H

[0248] CH2=CHCOO-(CH2CH(CH3)O)9-CH3

[0249] CH2=CHCOO-(CH2CH(CH3)O) 12 -CH3

[0250] CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)2-H

[0251] CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3

[0252] CH2=CHCOO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0253] CH2=CHCOO-(CH2CH2O) 23 -OOC(CH3)C=CH2

[0254] CH2=CHCOO-(CH2CH2O) 20 -(CH2CH(CH3)O)5-CH2-CH=CH2

[0255] CH2=CHCOO-(CH2CH2O)9-H

[0256] CH2=C(CH3)COO-CH2CH2O-H

[0257] CH2=C(CH3)COO-CH2CH2CH2O-H

[0258] CH2=C(CH3)COO-CH2CH(CH3)O-H

[0259] CH2=C(CH3)COO-CH(CH3)CH2O-H

[0260] CH2=C(CH3)COO-CH2CH2CH2CH2O-H

[0261] CH2=C(CH3)COO-CH2CH2CH(CH3)O-H

[0262] CH2=C(CH3)COO-CH2CH(CH3)CH2O-H

[0263] CH2=C(CH3)COO-CH(CH3)CH2CH2O-H

[0264] CH2=C(CH3)COO-CH2CH(CH2CH3)O-H

[0265] CH2=C(CH3)COO-CH2C(CH3)2O-H

[0266] CH2=C(CH3)COO-CH(CH2CH3)CH2O-H

[0267] CH2=C(CH3)COO-C(CH3)2CH2O-H

[0268] CH2=C(CH3)COO-CH(CH3)CH(CH3)O-H

[0269] CH2=C(CH3)COO-C(CH3)(CH2CH3)O-H

[0270] CH2=C(CH3)COO-(CH2CH2O)2-H

[0271] CH2=C(CH3)COO-(CH2CH2O)4-H

[0272] CH2=C(CH3)COO-(CH2CH2O)5-H

[0273] CH2=C(CH3)COO-(CH2CH2O)6-H

[0274] CH2=C(CH3)COO-(CH2CH2O)9-H

[0275] CH2=C(CH3)COO-(CH2CH2O)5-CH3

[0276] CH2=C(CH3)COO-(CH2CH2O)9-CH3

[0277] CH2=C(CH3)COO-(CH2CH2O) 23 -CH3

[0278] CH2=C(CH3)COO-(CH2CH2O) 90 -CH3

[0279] CH2=C(CH3)COO-(CH2CH(CH3)O)9-H

[0280] CH2=C(CH3)COO-(CH2CH(CH3)O)9-CH3

[0281] CH2=C(CH3)COO-(CH2CH(CH3)O) 12 -CH3

[0282] CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)2-H

[0283] CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3

[0284] CH2=C(CH3)COO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H

[0285] CH2=C(CH3)COO-(CH2CH2O) 23 -OOC(CH3)C=CH2

[0286] CH2=C(CH3)COO-(CH2CH2O) 20 -(CH2CH(CH3)O)5-CH2-CH=CH2

[0287] CH2=CH-C(=O)-NH-CH2CH2O-H

[0288] CH2=CH-C(=O)-NH-CH2CH2CH2O-H

[0289] CH2=CH-C(=O)-NH-CH2CH(CH3)O-H

[0290] CH2=CH-C(=O)-NH-CH(CH3)CH2O-H

[0291] CH2=CH-C(=O)-NH-CH2CH2CH2CH2O-H

[0292] CH2=CH-C(=O)-NH-CH2CH2CH(CH3)O-H

[0293] CH2=CH-C(=O)-NH-CH2CH(CH3)CH2O-H

[0294] CH2=CH-C(=O)-NH-CH(CH3)CH2CH2O-H

[0295] CH2=CH-C(=O)-NH-CH2CH(CH2CH3)OH

[0296] CH2=CH-C(=O)-NH-CH2C(CH3)2O-H

[0297] CH2=CH-C(=O)-NH-CH(CH2CH3)CH2O-H

[0298] CH2=CH-C(=O)-NH-C(CH3)2CH2O-H

[0299] CH2=CH-C(=O)-NH-CH(CH3)CH(CH3)OH

[0300] CH2=CH-C(=O)-NH-C(CH3)(CH2CH3)OH

[0301] CH2=CH-C(=O)-NH-(CH2CH2O)2-H

[0302] CH2=CH-C(=O)-NH-(CH2CH2O)4-H

[0303] CH2=CH-C(=O)-NH-(CH2CH2O)5-H

[0304] CH2=CH-C(=O)-NH-(CH2CH2O)6-H

[0305] CH2=CH-C(=O)-NH-(CH2CH2O)9-H

[0306] CH2=CH-C(=O)-NH-(CH2CH2O)5-CH3

[0307] CH2=CH-C(=O)-NH-(CH2CH2O)9-CH3

[0308] CH2=CH-C(=O)-NH-(CH2CH2O) 23 -CH3

[0309] CH2=CH-C(=O)-NH-(CH2CH2O) 90 -CH3

[0310] CH2=CH-C(=O)-NH-(CH2CH(CH3)O)9-H

[0311] CH2=CH-C(=O)-NH-(CH2CH(CH3)O)9-CH3

[0312] CH2=CH-C(=O)-NH-(CH2CH(CH3)O) 12 -CH3

[0313] CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H

[0314] CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3

[0315] CH2=CH-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0316] CH2=C(CH3)-C(=O)-NH-CH2CH2O-H

[0317] CH2=C(CH3)-C(=O)-NH-CH2CH2CH2O-H

[0318] CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)OH

[0319] CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2O-H

[0320] CH2=C(CH3)-C(=O)-NH-CH2CH2CH2CH2O-H

[0321] CH2=C(CH3)-C(=O)-NH-CH2CH2CH(CH3)OH

[0322] CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)CH2O-H

[0323] CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2CH2O-H

[0324] CH2=C(CH3)-C(=O)-NH-CH2CH(CH2CH3)OH

[0325] CH2=C(CH3)-C(=O)-NH-CH2C(CH3)2O-H

[0326] CH2=C(CH3)-C(=O)-NH-CH(CH2CH3)CH2O-H

[0327] CH2=C(CH3)-C(=O)-NH-C(CH3)2CH2O-H

[0328] CH2=C(CH3)-C(=O)-NH-CH(CH3)CH(CH3)OH

[0329] CH2=C(CH3)-C(=O)-NH-C(CH3)(CH2CH3)OH

[0330] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)2-H

[0331] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)4-H

[0332] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-H

[0333] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)6-H

[0334] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-H

[0335] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-CH3

[0336] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-CH3

[0337] CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 23 -CH3

[0338] CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 90 -CH3

[0339] CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)9-H

[0340] CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)9-CH3

[0341] CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O) 12 -CH3

[0342] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H

[0343] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3

[0344] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0345] As monomer (b), X is preferred. 2 The monomer (b) is an acrylate or acrylamide containing hydrogen atoms. Hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxyethyl acrylamide are particularly preferred.

[0346] (c) Monomers containing ionic groups

[0347] The polymer (A) of the present invention may comprise repeating units derived from a monomer (c) containing an ionic group. The monomer (c) is preferably a monomer (particularly an acrylic monomer) comprising an olefinic unsaturated double bond and an ionic group. The ionic group is an anionic group and / or a cationic group, or a salt thereof.

[0348] The monomer (c) preferably has a (meth)propene group as an olefinic unsaturated double bond, for example, it may have a (meth)acrylate group or a (meth)acrylamide group as an olefinic unsaturated double bond.

[0349] Monomers with anionic groups can be listed as those having carboxyl, sulfonic acid, or phosphate groups. Specific examples of monomers with anionic groups include (meth)acrylic acid, butenoic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinyl sulfonic acid, (meth)allyl sulfonic acid, styrene sulfonic acid, phosphate (meth)acrylate, vinylbenzene sulfonic acid, acrylamide tert-butyl sulfonic acid, etc., or their salts.

[0350] Salts that are anionic groups can be listed as: alkali metal salts, alkaline earth metal salts, or ammonium salts, such as methyl ammonium salts, ethanol ammonium salts, triethanolammonium salts, etc.

[0351] In monomers having cationic groups, examples of cationic groups are amino groups, preferably tertiary amine groups and quaternary ammonium groups. In tertiary amine groups, the two groups bonded to the nitrogen atom may be the same or different, preferably an aliphatic group (particularly alkyl) with 1 to 5 carbon atoms, an aromatic group (aryl) with 6 to 20 carbon atoms, or an aromatic aliphatic group (particularly aralkyl, for example, benzyl (C6H5-CH2-)) with 7 to 25 carbon atoms. In quaternary ammonium groups, the three groups bonded to the nitrogen atom may be the same or different, preferably an aliphatic group (particularly alkyl) with 1 to 5 carbon atoms, an aromatic group (aryl) with 6 to 20 carbon atoms, or an aromatic aliphatic group (particularly aralkyl, for example, benzyl (C6H5-CH2-)) with 7 to 25 carbon atoms. In tertiary amine and quaternary ammonium groups, the remaining group bonded to the nitrogen atom may have an olefinic unsaturated double bond. The cationic group may be in the form of a salt.

[0352] The cationic group of the salt is a salt of an acid (organic or inorganic). Organic acids are preferred, such as carboxylic acids having 1 to 20 carbon atoms (especially monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid). Dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate and their salts are preferred.

[0353] Specific examples of monomers having cationic groups are described below.

[0354] CH2=CHCOO-CH2CH2-N(CH3)2 and its salts (e.g., acetates)

[0355] CH2=CHCOO-CH2CH2-N(CH2CH3)2 and its salts (e.g., acetates)

[0356] CH2=C(CH3)COO-CH2CH2-N(CH3)2 and its salts (e.g., acetates)

[0357] CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2 and its salts (e.g., acetates)

[0358] CH2=CHC(O)N(H)-CH2CH2CH2-N(CH3)2 and its salts (e.g., acetates)

[0359] CH2=CHCOO-CH2CH2-N(-CH3)(-CH2-C6H5) and its salts (e.g., acetates)

[0360] CH2=C(CH3)COO-CH2CH2-N(-CH2CH3)(-CH2-C6H5) and its salts (e.g., acetates)

[0361] CH2=CHCOO-CH2CH2-N+ (CH3)3Cl -

[0362] CH2=CHCOO-CH2CH2-N + (-CH3)2(-CH2-C6H5)Cl -

[0363] CH2=C(CH3)COO-CH2CH2-N + (CH3)3Cl -

[0364] CH2=CHCOO-CH2CH(OH)CH2-N + (CH3)3Cl -

[0365] CH2=C(CH3)COO-CH2CH(OH)CH2-N + (CH3)3Cl -

[0366] CH2=C(CH3)COO-CH2CH(OH)CH2-N + (-CH2CH3)2(-CH2-C6H5)Cl -

[0367] CH2=C(CH3)COO-CH2CH2-N + (CH3)3Br -

[0368] CH2=C(CH3)COO-CH2CH2-N + (CH3)3I -

[0369] CH2=C(CH3)COO-CH2CH2-N + (CH3)3O - SO3CH3

[0370] CH2=C(CH3)COO-CH2CH2-N + (CH3)(-CH2-C6H5)2Br -

[0371] As a monomer containing an ionic group (c), methacrylic acid, acrylic acid, or dimethylaminoethyl methacrylate is preferred, and methacrylic acid or dimethylaminoethyl methacrylate is more preferred.

[0372] (d) Halogenated olefin monomers

[0373] The polymer (A) of the present invention may have repeating units derived from a haloolefin monomer (d). The haloolefin monomer (d) may also lack fluorine atoms. The haloolefin monomer (d) is preferably an olefin with 2 to 20 carbon atoms substituted with 1 to 10 chlorine, bromine, or iodine atoms. The haloolefin monomer (d) is preferably a chlorinated olefin with 2 to 20 carbon atoms, particularly an olefin with 2 to 5 carbon atoms having 1 to 5 chlorine atoms. Preferred specific examples of the haloolefin monomer (d) are vinyl halogenates, such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene haloethylene, such as vinylidene chloride, vinylidene bromine, and vinylidene iodide. Vinyl chloride or vinylidene chloride is preferred due to the increased water repellency (particularly water repellency durability). The wash durability provided by the polymer (A) can be improved by the presence of repeating units derived from the haloolefin monomer (d).

[0374] (e) Crosslinking monomers

[0375] The polymer (A) of the present invention may comprise repeating units derived from a crosslinking monomer (e). The crosslinking monomer (e) has a reactive group and / or an olefinic unsaturated double bond (preferably a (meth)acrylate group). The crosslinking monomer (e) may be a fluorine-free monomer. The crosslinking monomer (e) may be a compound having at least two olefinic unsaturated double bonds (preferably (meth)acrylate groups), or a compound having at least one olefinic unsaturated double bond and at least one reactive group. Examples of reactive groups are hydroxyl, epoxy, chloromethyl, terminal isocyanate, amino, carboxyl, etc.

[0376] Examples of crosslinkable monomers can be vinyl monomers with reactive groups, mono(meth)acrylates, di(meth)acrylates, or di(meth)acrylamides with reactive groups.

[0377] Examples of crosslinking monomers include: diacetone (meth)acrylamide, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetylacetoxyethyl (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, neopentyl glycol di(meth)acrylate, etc., but are not limited to these.

[0378] (f) Monomers containing cyclic hydrocarbon groups

[0379] The polymer (A) of the present invention may have repeating units derived from a cyclic hydrocarbon monomer (f). The cyclic hydrocarbon monomer (f) is a monomer having a cyclic hydrocarbon group, and may be a monomer having an olefinic unsaturated double bond and a cyclic hydrocarbon group. The polymer (A) of the present invention may be a styrene polymer having repeating units derived from styrene or styrene derivatives.

[0380] The cyclic hydrocarbon monomer (f) preferably has a (meth)propene group as an olefinic unsaturated double bond, for example, it may have a (meth)acrylate group or a (meth)acrylamide group as an olefinic unsaturated double bond.

[0381] The cyclic hydrocarbon group can be alicyclic or aromatic. The cyclic hydrocarbon group can be saturated or unsaturated. The cyclic hydrocarbon group can be monocyclic, polycyclic, or bridged, preferably bridged. The cyclic hydrocarbon group can have chain-like groups (e.g., halogen atoms, straight-chain or branched hydrocarbon groups (especially straight-chain or branched hydrocarbon groups with 1 to 20 carbon atoms)).

[0382] The number of carbon atoms in a cyclic hydrocarbon group can be 4 or more, 6 or more, or 8 or more, or less than 30, 26 or less, 22 or less, 18 or less, or less than 14.

[0383] Specific examples of cyclic hydrocarbon groups include: cyclohexyl, tert-butylcyclohexyl, adamantyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, borneol, isoborneol, norborneol, dicyclopentyl, dicyclopentenyl, benzyl, phenyl, naphthyl, 2-tert-butylphenyl, residues from which one or more hydrogen atoms have been removed (e.g., cyclohexene, adamantyl, phenylene, naphthylene, etc.), and groups that are substitutes for them.

[0384] Specific examples of monomers containing cyclic hydrocarbon groups (f) include: cyclohexyl methacrylate, tert-butylcyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, dicyclopentyl methacrylate, dicyclopentenyl methacrylate, dicyclopentoxyethyl methacrylate, tricyclopentyl methacrylate, adamantyl methacrylate, 2-methyl-2-adamantyl(meth)acrylate, 2-ethyl-2-adamantyl(meth)acrylate, and compounds in which these acrylates are replaced with acrylamides. These substances can be used alone or in combination with two or more.

[0385] As an example of a monomer containing a cyclic hydrocarbon group (f), styrene compounds can be cited. Styrene compounds can be modified with chain groups (e.g., halogen atoms, straight-chain or branched hydrocarbon groups (especially straight-chain or branched hydrocarbon groups with 1 to 20 carbon atoms)). Specific examples include: styrene, 4-tert-butylstyrene, 3,5-di-tert-butylstyrene, 2,4,6-tri-tert-butylstyrene, 4-methylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, etc. Styrene compounds can be α-methylstyrene compounds and α-chlorostyrene compounds with a chlorine atom at the α-position, or styrene compounds with a hydrogen atom at the α-position.

[0386] (g) Contains polysiloxane monomers

[0387] The polymer (A) of the present invention may have repeating units derived from a polysiloxane-containing monomer (g). The monomer (g) has an olefinic unsaturated double bond and a polysiloxane group.

[0388] The monomer (g) preferably has a (meth)propene group, for example, it may have a (meth)acrylate group or a (meth)acrylamide group as an olefinic unsaturated double bond.

[0389] Regarding the polysiloxane group present in monomer (g), the description of (polysiloxane group) above is cited. Monomer (g) may have a polydimethylsiloxane group on its side chain.

[0390] Unsaturated olefinic double bonds and polysiloxane alkyl groups can be bonded together by any linking group.

[0391] The monomer (g) is preferably a monomer represented by the following formula:

[0392] CH2=C(-X g )-C(=O)-Y g (R) g k

[0393] [In the formula, R] g It contains a polydimethylsiloxane group.

[0394] X g It can be a hydrogen atom, a monovalent organic group, or a halogen atom.

[0395] Y g It is a group consisting of at least one hydrocarbon group selected from divalent to tetravalent carbon atoms (especially -CH2-, -CH(-)2), -C6H4-, -O-, -C(=O)-, -S(=O)2- or -NH-.

[0396] k is 1 to 3.

[0397] Xg It can 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. X g Examples include hydrogen atoms, methyl groups, chlorine atoms, bromine atoms, iodine atoms, and cyano groups. X g Preferably, it contains hydrogen atoms, methyl groups, or chlorine atoms. X g Hydrogen atoms are particularly preferred.

[0398] Y g It consists of divalent to tetravalent groups. Y g Preferably, it has a divalent group.

[0399] Y g Preferably, it consists of at least one group selected from a hydrocarbon group having one carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2-, or -NH-. g Preferably, it is not a hydrocarbon group. Examples of hydrocarbon groups with one carbon atom include: -CH2-, -CH(-)2, or -C(-)3. Hydrocarbon groups with one carbon atom are arranged in a repeating sequence, such as -(CH2). m -(m is an integer from 1 to 5) in this way, hydrocarbon groups with more than 2 carbon atoms can be formed. Y g It can have an NH group.

[0400] Y g Can be -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'-

[0401] [In the formula, Y' represents a valence bond, -O-, -NH-, or -S(=O)2-,

[0402] R' is -(CH2) m -(m is an integer from 1 to 5) or -C6H4-(phenylene).

[0403] Y g Specific examples are -O-, -NH-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2)m -O-, -O-(CH2) m -O-C(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -O-C(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -O-C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, -NH-(CH2) m -NH-C6H4-, -NH-(CH2) m -NH-S(=O)2-, or -NH-(CH2) m -S(=O)2-NH- [where m is 1 - 5, especially 2 or 4].

[0404] Y g Preferably -O-, -NH-, -O-(CH2) m -O-C(=O)-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m-S(=O)2-NH-、-NH-(CH2) m -NH-S(=O)2- or -NH-(CH2) m -S(=O)2-NH- [where m is an integer from 1 to 5, especially 2 or 4.]

[0405] Y g More preferably, it is -O- or -O-(CH2). m -NH-C(=O)-, particularly preferred to be -O-(CH2). m -NH-C(=O)-.

[0406] R g The group having polydimethylsiloxane is referred to above for the description of polydimethylsiloxane.

[0407] Examples of monomers (g) are described below.

[0408] CH2=C(-X g )-C(=O)-Y g -[-Si(R s )2-O-] a -Si(R s )3

[0409] CH2=C(-X g )-C(=O)-Y g -L s1 -[-Si(R s )2-O-] a -Si(R s )3

[0410] CH2=C(-X g )-C(=O)-Y g -L s1 -OL s1 -[-Si(R s )2-O-] a -R s

[0411] CH2=C(-X g )-C(=O)-Y g -L s1 -[-Si(R s )2-O-] a -Si(R s )3

[0412] CH2=C(-X g )-C(=O)-Y g -L s1 -OLs1 -[-Si(R s )2-O-] a -R s

[0413] CH2=C(-X g )-C(=O)-Y g -L s1 -[-Si(R s )2-O-] a -Si(R s 3.

[0414] CH2=C(-X g )-C(=O)-Y g -L s1 -[-Si(R s )2-O-] a -R s

[0415] [In the formula, each symbol refers to the explanation above.]

[0416] (h) Other monomers

[0417] 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) can be used alone or in combination.

[0418] [Polymer Composition]

[0419] The combination of monomers (a) to (g) constituting the repeating unit of the polymer (A) of the present invention is not particularly limited, for example as described below (parentheses omitted).

[0420] a

[0421] a+b

[0422] a+b+c

[0423] a+c

[0424] a+d

[0425] a+b+c+d

[0426] a+b+c+d+e

[0427] a+b+c+d+e+f

[0428] In the above combination, monomer (a) can be used instead of monomer (a) or in combination with monomer (g) based on monomer (a). Other monomers (g) can also be used in combination with the above combination. In the case of pulp products, monomer (a), monomer (b) and monomer (c) are preferably used in combination.

[0429] The amount of repeating units derived from monomer (a) relative to polymer (A) can be 1% or more by weight, 5% or more by weight, 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, 70% or more by weight, 80% or more by weight, or 90% or more by weight. Alternatively, it can be 95% or less by weight, 85% or less by weight, 75% or less by weight, 65% or less by weight, 55% or less by weight, 45% or less by weight, 35% or less by weight, 25% or less by weight, 15% or less by weight, or 5% or less by weight.

[0430] The amount of monomer (a) (particularly monomer (a1)) relative to polymer (A) can be more than 90% by weight, more than 92% by weight, more than 94% by weight, more than 96% by weight, more than 98% by weight, more than 99% by weight, more than 99.5% by weight, or 100% by weight, for example, more than 93% by weight, preferably more than 97% by weight, and also less than 100% by weight, less than 99% by weight, less than 97% by weight, less than 95% by weight, or less than 93% by weight, and in one mode, more than 90% by weight and less than 100% by weight. The amount of monomer (a1) relative to polymer (A) can be 100% by weight.

[0431] In monomer (a), the amount of monomer (a1) can be 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, 70% or more by weight, or 80% or more by weight, preferably 30% or more by weight, and can also be 100% or less by weight, 90% or less by weight, 80% or less by weight, 50% or less by weight, or 30% or less by weight.

[0432] In monomer (a), the amount of monomer (a2) can be 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, 70% or more by weight, or 80% or more by weight. Alternatively, it can be less than 100% by weight, less than 90% by weight, less than 80% by weight, less than 50% by weight, or less than 30% by weight.

[0433] The amount of repeating units derived from monomer (b) relative to polymer (A) can be 1% or more by weight, 5% or more by weight, 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, 70% or more by weight, 80% or more by weight, or 90% or more by weight. Alternatively, it can be 95% or less by weight, 85% or less by weight, 75% or less by weight, 65% or less by weight, 55% or less by weight, 45% or less by weight, 35% or less by weight, 25% or less by weight, 15% or less by weight, or 5% or less by weight.

[0434] 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, 1000 parts by weight or more, or less than 3000 parts by weight, less than 2000 parts by weight, less than 1000 parts by weight, less than 750 parts by weight, less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 30 parts by weight, less than 10 parts by weight, or less than 1 part by weight, relative to the amount of repeating units derived from monomer (a) of 100 parts by weight.

[0435] The amount of repeating units derived from monomer (c) relative to polymer (A) can be 1% or more by weight, 5% or more by weight, 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, 70% or more by weight, 80% or more by weight, or 90% or more by weight. Alternatively, it can be 95% or less by weight, 85% or less by weight, 75% or less by weight, 65% or less by weight, 55% or less by weight, 45% or less by weight, 35% or less by weight, 25% or less by weight, 15% or less by weight, or 5% or less by weight.

[0436] 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, 1000 parts by weight or more, or less than 3000 parts by weight, less than 2000 parts by weight, less than 1000 parts by weight, less than 750 parts by weight, less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 30 parts by weight, less than 10 parts by weight, or less than 1 part by weight, relative to the amount of repeating units derived from monomer (a) of 100 parts by weight.

[0437] The amount of repeating units derived from monomer (d) relative to polymer (A) can be 1% or more by weight, 5% or more by weight, 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, 70% or more by weight, 80% or more by weight, or 90% or more by weight. In addition, the amount of repeating units derived from monomer (d) relative to polymer (A) can be 95% or less by weight, 85% or less by weight, 75% or less by weight, 65% or less by weight, 55% or less by weight, 45% or less by weight, 35% or less by weight, 25% or less by weight, 15% or less by weight, or 5% or less by weight.

[0438] 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, 1000 parts by weight or more, or less than 3000 parts by weight, less than 2000 parts by weight, less than 1000 parts by weight, less than 750 parts by weight, less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 30 parts by weight, less than 10 parts by weight, or less than 1 part by weight, relative to the amount of repeating units derived from monomer (a) of 100 parts by weight.

[0439] The amount of repeating units derived from monomer (e) relative to polymer (A) can be 1% or more by weight, 5% or more by weight, 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, 70% or more by weight, 80% or more by weight, or 90% or more by weight. Alternatively, it can be 95% or less by weight, 85% or less by weight, 75% or less by weight, 65% or less by weight, 55% or less by weight, 45% or less by weight, 35% or less by weight, 25% or less by weight, 15% or less by weight, or 5% or less by weight.

[0440] 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, 1000 parts by weight or more, or less than 3000 parts by weight, less than 2000 parts by weight, less than 1000 parts by weight, less than 750 parts by weight, less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 30 parts by weight, less than 10 parts by weight, or less than 1 part by weight, relative to the amount of repeating units derived from monomer (a) of 100 parts by weight.

[0441] The amount of repeating units derived from monomers (f) relative to polymer (A) can be 1% or more by weight, 5% or more by weight, 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, 70% or more by weight, 80% or more by weight, or 90% or more by weight. Alternatively, it can be 95% or less by weight, 85% or less by weight, 75% or less by weight, 65% or less by weight, 55% or less by weight, 45% or less by weight, 35% or less by weight, 25% or less by weight, 15% or less by weight, or 5% or less by weight.

[0442] 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, 1000 parts by weight or more, or less than 3000 parts by weight, less than 2000 parts by weight, less than 1000 parts by weight, less than 750 parts by weight, less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 30 parts by weight, less than 10 parts by weight, or less than 1 part by weight, relative to the amount of repeating units derived from monomer (a) of 100 parts by weight.

[0443] The amount of repeating units derived from monomers (g) relative to polymer (A) can be 1% or more by weight, 5% or more by weight, 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, 70% or more by weight, 80% or more by weight, or 90% or more by weight. Alternatively, it can be 95% or less by weight, 85% or less by weight, 75% or less by weight, 65% or less by weight, 55% or less by weight, 45% or less by weight, 35% or less by weight, 25% or less by weight, 15% or less by weight, or 5% or less by weight.

[0444] The amount of repeating units derived from 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, 1000 parts by weight or more, or less than 3000 parts by weight, less than 2000 parts by weight, less than 1000 parts by weight, less than 750 parts by weight, less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 30 parts by weight, less than 10 parts by weight, or less than 1 part by weight, relative to the amount of repeating units derived from monomer (a) of 100 parts by weight.

[0445] The amount of repeating units derived from monomers (h) relative to polymer (A) can be 1% or more by weight, 5% or more by weight, 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, 70% or more by weight, 80% or more by weight, or 90% or more by weight. Alternatively, it can be 95% or less by weight, 85% or less by weight, 75% or less by weight, 65% or less by weight, 55% or less by weight, 45% or less by weight, 35% or less by weight, 25% or less by weight, 15% or less by weight, or 5% or less by weight.

[0446] The amount of repeating units derived from monomer (h) can 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, 1000 parts by weight or more, or less than 3000 parts by weight, less than 2000 parts by weight, less than 1000 parts by weight, less than 750 parts by weight, less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 30 parts by weight, less than 10 parts by weight, or less than 1 part by weight, relative to the amount of repeating units derived from monomer (a) of 100 parts by weight.

[0447] 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 description of the amounts of each monomer can also be read as “100 parts by weight of repeating units derived from monomer (g)”.

[0448] [Aggregation Methods]

[0449] Polymer (A) can be manufactured using known polymerization methods, and the conditions of the polymerization reaction can be arbitrarily chosen. Examples of such polymerization methods include: solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization.

[0450] In solution polymerization, the following method is used: the monomer is dissolved in an organic solvent in the presence of a polymerization initiator, nitrogen is replaced, and the solution is heated and stirred at 30–120°C for 1–10 hours. Examples of polymerization initiators include: azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxypentanoate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in the range of 0.01–20 parts by weight, for example, 0.01–10 parts by weight, relative to 100 parts by weight of the monomer.

[0451] Organic solvents are solvents that are inert to monomers and capable of dissolving these substances. Examples 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 isopropanol). Specific examples of organic solvents include: acetone, chloroform, HCHC225, isopropanol, 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 the range of 10 to 3000 parts by weight, for example 50 to 2000 parts by weight, relative to a total of 100 parts by weight of monomers.

[0452] In emulsion polymerization, the following method is used: In the presence of a polymerization initiator and an emulsifier, the monomer is emulsified in water, nitrogen-replaced, and then polymerized by stirring at 50–80°C for 1–20 hours. The polymerization initiator can be water-soluble substances such as benzoyl peroxide, lauroyl peroxide, tert-butyl peroxide, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, sodium peroxide, potassium persulfate, and ammonium persulfate; or oil-soluble substances such as azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxypentanoate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in the range of 0.01–10 parts by weight relative to 100 parts by weight of the monomer.

[0453] To obtain a polymer aqueous dispersion with excellent storage stability, it is preferable to use an emulsification device, such as a high-pressure homogenizer or an ultrasonic homogenizer, which can impart strong abrasive energy, to micronize the monomers in water before polymerization. Furthermore, various anionic, cationic, or nonionic emulsifiers can be used as emulsifiers, in the range of 0.5 to 20 parts by weight relative to 100 parts by weight of the monomers. Anionic and / or nonionic and / or cationic emulsifiers are preferred. In cases where the monomers are not completely miscible, it is preferable to add a compatibilizer, such as a water-soluble organic solvent and / or a low molecular weight monomer, to ensure sufficient miscibility. Adding a compatibilizer can improve emulsification and copolymerization properties.

[0454] As water-soluble organic solvents, the aforementioned organic solvents can be used. Examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol, which can be used in the range of 1 to 50 parts by weight, or for example, 10 to 40 parts by weight, relative to 100 parts by weight of water. Additionally, as low molecular weight monomers, examples include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate, which can be used in the range of 1 to 50 parts by weight, or for example, 10 to 40 parts by weight, relative to 100 parts by weight of the total monomer.

[0455] Chain transfer agents can be used in polymerization. Depending on the amount of chain transfer agent used, the molecular weight of the polymer can be changed. Examples of chain transfer agents include: mercapto-containing compounds such as lauryl thiols, thioethylene glycol, and thioglycerol (especially alkyl thiols with 1 to 40 carbon atoms), and inorganic salts such as sodium hypophosphite and sodium bisulfite. Regarding the amount of chain transfer agent used, it can be used in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, relative to 100 parts by weight of the total monomer.

[0456] [(B) Organosilicon compounds]

[0457] The organosilicon compound (B) of the present invention will be described. Organosilicon compound (B) is a polyorganosiloxane compound having siloxane bonds. Organosilicon compound (B) may consist of one polyorganosiloxane compound or may contain two or more polyorganosiloxane compounds. Organosilicon compound (B) comprises silicone resin and silicone oil.

[0458] In the GPC plot of organosilicon compound (B), a peak is present in the region with a molecular weight above 1500. The presence of a peak in the region with a molecular weight above 1500 in the GPC plot obtained by GPC determination can be confirmed by the following analysis.

[0459] Organosilicon compounds were confirmed to have peaks in the region above 1500 molecular weight (converted to polystyrene) using gel permeation chromatography.

[0460] For gel permeation chromatography, an HLC-8420GPC EcoSEC Elite-WS (Tosoh Corporation) was used. A column with two TSKgel SuperMultipore HZ-M electrodes was used. An RI detector was used. Standard polystyrene (SRM706a NIST) was used as the reference material.

[0461] For the analytical sample, the silicone resin was dissolved in tetrahydrofuran to prepare a 0.1% by weight solution, which was then passed through a 0.5 μm filter. When determining the average molecular weight, the column was maintained at 40°C, tetrahydrofuran was used as the eluent, the flow rate was set to 0.35 mL / min, and 10 μL of the analytical sample was injected.

[0462] Furthermore, organosilicon compounds were prepared by GPC separation to obtain components with a molecular weight of 1500 or higher. An Agilent 1260 Infinity II LC system (manufactured by Agilent) was used as the gel permeation chromatography method. One SHODEX KF-G column and two SHODEX KF-806L columns were used in series. An ELSD detector was used. Polymethyl methacrylate (PMMA) was used as the standard.

[0463] For the analytical sample, the organosilicon compound was dissolved in tetrahydrofuran to prepare a 0.1% by weight solution, which was then passed through a 0.5 μm filter. When determining the average molecular weight, the column was maintained at 30°C, tetrahydrofuran was used as the eluent, and the flow rate was set to 0.50 mL / min, with 100 μL of the analytical sample injected.

[0464] Components with a molecular weight greater than 1500 were concentrated, and organosilicon compounds (Mn > 1500) were extracted. The organosilicon compounds (Mn > 1500) were then analyzed... 1 H-NMR, 29 Si-NMR was used to confirm the presence of silicone oil in the region.

[0465] Organosilicon compounds containing components with a molecular weight of 1500 or higher contain silicone oils other than amino-modified silicones. A component with a molecular weight of 1500 or higher refers to a component with a molecular weight of 1500 or higher per molecule (i.e., silicone resins and / or silicone oils). The presence of silicone resins and / or silicone oils with a molecular weight of 1500 or higher can be confirmed using methods such as GPC.

[0466] Silicone oils other than amino-modified silicones in organosilicon compounds with a molecular weight of 1500 or higher may be the silicone oils described in [Silicone Oils] below.

[0467] The following descriptions relating to organosilicon compounds (B) may be applied independently in silicone resins and silicone oils.

[0468] The number of silicon atoms in the organosilicon compound (B) can 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. Alternatively, it can 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.

[0469] The organosilicon compound (B) has a number average molecular weight of 250 or more, preferably 300 or more, and more preferably 500 or more. The number average molecular weight of the organosilicon compound (B) can be 50,000 or less, or 10,000 or less. For example, the number average molecular weight of the organosilicon compound (B) can be in the range of 250 to 50,000, or in the range of 250 to 10,000, or for example, 1,000 to 7,000 or 2,000 to 6,000. The number average molecular weight of the organosilicon compound (B) can be determined using GPC.

[0470] [unit]

[0471] The organosilicon compound (B) is composed of at least one combination selected from M-units, D-units, T-units and Q-units.

[0472] M-cell represents (R) M )3SiO 0.5 Unit. R M In organosilicon compound (B), each group is independently a hydrocarbon group or a reactive group having 1 to 40 carbon atoms.

[0473] The ratio of M units contained in the organosilicon compound (B) of the present invention can 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 molecule. Alternatively, it can be 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less.

[0474] Compared to the amount of D unit, T unit, or Q unit, the amount of M unit can be above 0 mol%, above 10 mol%, above 20 mol%, above 30 mol%, above 40 mol%, above 50 mol%, or below 150 mol%, below 130 mol%, below 100 mol%, below 80 mol%, below 60 mol%, below 50 mol%, below 40 mol%, below 30 mol%, below 20 mol%, or below 10 mol%.

[0475] D unit represents (R) D )2SiO unit. R D In organosilicon compound (B), each group is independently a hydrocarbon group or a reactive group having 1 to 40 carbon atoms.

[0476] The ratio of D units contained in the organosilicon compound (B) of the present invention can 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 molecule; alternatively, it can 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. The organosilicon compound (B) of the present invention may also be free of D units.

[0477] T unit represents R T SiO 1.5 Unit. R T In organosilicon compound (B), each group is independently a hydrocarbon group or a reactive group having 1 to 40 carbon atoms.

[0478] The proportion of T units in the organosilicon compound (B) of the present invention can 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 molecule; alternatively, it can 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. The organosilicon compound (B) of the present invention may also be free of T units.

[0479] Q unit represents SiO2 unit.

[0480] The ratio of Q units contained in the organosilicon compound (B) of the present invention can 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 molecule; alternatively, it can 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. The organosilicon compound (B) of the present invention may also be free of Q units.

[0481] Examples of hydrocarbon groups with 1 to 40 carbon atoms include hydrocarbon groups with 1 to 5 carbon atoms and hydrocarbon groups with 6 to 40 carbon atoms.

[0482] Examples of hydrocarbon groups with 1 to 5 carbon atoms include: methyl, ethyl, propyl, butyl, pentyl, etc. (especially aliphatic hydrocarbon groups, especially alkyl groups, such as methyl or ethyl, especially methyl).

[0483] The hydrocarbon group having 2 to 40 carbon atoms can be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, and particularly preferably a saturated aliphatic hydrocarbon group (alkyl). The hydrocarbon group can be cyclic, linear, or branched, preferably linear. The number of carbon atoms in the hydrocarbon group can 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. Alternatively, it can 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.

[0484] Examples of reactive groups are groups having functional groups (e.g., hydroxyl, amino, mercapto, epoxy, carboxyl, haloalkyl, vinyl, (meth)propenyl, (meth)acryloyloxy, oxoalkylene, isocyanate, and (meth)acrylamido, hydrogen atoms directly bonded to silicon atoms, etc.). These functional groups can be directly bonded to silicon atoms or bonded to organic groups directly bonded to silicon atoms. The organic group can be a hydrocarbon group, for example, an alkylene group or a divalent aromatic group. The hydrocarbon group can have 2 to 12 carbon atoms, and as an alkylene group, it is preferred to have 2 to 10 carbon atoms. As a divalent aromatic group, it is preferred to have 6 to 12 carbon atoms. The reactive group can be a group selected from hydroxyl, epoxy, carboxyl, (meth)propenyl, and amino, for example, it can be at least one selected from epoxy, hydroxyl, (meth)propenyl, and carboxyl.

[0485] Organosilicon compound (B) can be unmodified organosilicon (polyalkylsiloxane, polyalkylphenylsiloxane, polydimethylsiloxane, etc.) whose reactive groups are not modified, or modified organosilicon (amino-modified, polyether-modified, epoxy-modified silicone, carboxyl-modified silicone, methylhydrosilicon, methanol-modified silicone, carboxyl-modified silicone, mercapto-modified silicone, etc.).

[0486] [Amount of organosilicon compounds]

[0487] The total amount of organosilicon compound (B) relative to the amount of polymer (A) and organosilicon compound (B) is 1 to 49% by weight, which can be 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, or 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, or 5% or less, and can be 1 to 25% by weight.

[0488] [Ratio of resin to oil]

[0489] The amount of silicone resin relative to 100 parts by weight of silicone oil can be more than 0.01 parts by weight, more than 0.1 parts by weight, more than 1 part by weight, more than 3 parts by weight, more than 5 parts by weight, more than 10 parts by weight, more than 15 parts by weight, more than 20 parts by weight, more than 50 parts by weight, more than 75 parts by weight, or more than 100 parts by weight. Alternatively, it can be less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, less than 5 parts by weight, less than 3 parts by weight, or less than 1 part by weight.

[0490] [Silicone resin]

[0491] Organosilicon compound (B) can be a silicone resin. Silicone resin refers to a resin whose main chain has siloxane bonds. Silicone resin is an organopolysiloxane with a three-dimensional structure.

[0492] Silicone resin can be a resin composed of one or more units consisting of MQ, MT, MDT, MDQ, MTQ, DT or MDTQ.

[0493] The molar ratio of M units to D units, T units, or Q units (M unit / D unit, M unit / T unit, or M unit / Q unit) can 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. Alternatively, it can 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. It can be 0.6 or more and 1.7 or less, and preferably 0.8 or more and 1.5 or less.

[0494] Silicone resins can also be obtained as solutions by dissolving silicone resins in alkyl polysiloxanes or liquid media other than alkyl polysiloxanes. Examples of solvents other than alkyl polysiloxanes include n-hexane, isopropanol, dichloromethane, 1,1,1-trichloroethane, and mixtures of these solvents.

[0495] Examples of solutions obtained by dissolving silicone resin in alkyl polysiloxanes include: KF7312J (a 50:50 mixture of trimethylsilyl polysiloxane and decamethylcyclopentasiloxane), KF7312F (a 50:50 mixture of trimethylsilyl polysiloxane and octamethylcyclotetrasiloxane), KF9021L (a 50:50 mixture of trimethylsilyl polysiloxane and low-viscosity methyl polysiloxane), and KF7312L (a 50:50 mixture of trimethylsilyl polysiloxane and low-viscosity methyl polysiloxane) sold by Shin-Etsu Chemical Co., Ltd.

[0496] Commercially available silicone resins can be used as standalone products. Examples of commercially available products include: MQ-1600 and MQ-1640 (manufactured by Dow Chemical Company, Japan).

[0497] KR-220L, KR-251, KR-311, and X-40-2406M (manufactured by Shin-Etsu Chemical Industry Co., Ltd., respectively).

[0498] R2701 (manufactured by Asahi Kasei Wacker Silicon Co., Ltd.)

[0499] Silmer HQ20 (made by Siltech Corporation), and

[0500] SILDFORM FLEXIBLE RESIN (Made by MOMENTIVE Corporation).

[0501] Silicone resins can also be used in the form of silicone resin emulsions. Examples of silicone resin emulsions include:

[0502] X-52-8005, X-52-8432, X-52-8407, X-52-8407, X-52-8499DA, X-52-8500DA, KR-4000GE (manufactured by Shin-Etsu Chemical Industry Co., Ltd., respectively)

[0503] R2701 (manufactured by Asahi Kasei Wacker Silicon Co., Ltd.), and

[0504] Siltech E-2199 (Made by Siltech Corporation).

[0505] The aforementioned commercially available products may include MQ, MDQ, MT, MTQ, MDT, or MDTQ.

[0506] (molecular weight)

[0507] The number average molecular weight (Mn) of silicone resin can be above 200, above 300, above 500, above 700, above 1000, above 1500, above 2000, above 2500, above 3000, above 4000, above 5000, above 6000, above 8000, or above 10000. Alternatively, it can be below 100000, below 80000, below 60000, below 50000, below 40000, below 30000, below 25000, below 20000, below 15000, or below 10000.

[0508] The number-average molecular weight (Mn) of silicone resin can be obtained using GPC (gel permeation chromatography) (conversion to polystyrene).

[0509] For gel permeation chromatography, an HLC-8420GPC EcoSEC Elite-WS (Tosoh Corporation) was used. A column with two TSKgel SuperMultipore HZ-M electrodes was used. An RI detector was used. Standard polystyrene (SRM706a NIST) was used as the reference material.

[0510] For the analytical sample, the silicone resin was dissolved in tetrahydrofuran to prepare a 0.1% by weight solution, which was then passed through a 0.5 μm filter. When determining the average molecular weight, the column was maintained at 40°C, tetrahydrofuran was used as the eluent, the flow rate was set to 0.35 mL / min, and 10 μL of the analytical sample was injected.

[0511] Commercially available silicone resins can be used. Examples of commercially available products include MQ-1600 solid resin (manufactured by Toray D. Corning) and MQ-1640 Flake Resin (manufactured by Toray D. Corning). These commercially available products may contain trimethylsilyl alkyl polysiloxanes and may contain MQ, MDQ, MT, MTQ, MDT, or MDTQ.

[0512] Silicone oil

[0513] The organosilicon compound (B) can be a silicone oil. The silicone oil can be, for example, either linear or cyclic. Silicone oil is liquid at 25°C.

[0514] Silicone oil, as a main component, can be composed of M and D units, and may also contain T and / or Q units. Dimethyl silicone oil is an example of a silicone oil.

[0515] The viscosity of silicone oil can be 0.1 mm. 2 / s or more, 1.0mm 2 / s or higher, 5.0mm 2 / s or more, 10mm 2 / s or higher, 50mm 2 / s or more, 100mm 2 / s or higher, 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, 300,000 mm 2 / s or more, 500,000 mm 2 / s or higher, and can also be up to 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 / s or less.

[0516] The aforementioned linear silicone oils can be classified as either ordinary silicone oils or modified silicone oils. Examples of ordinary silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil. Examples of modified silicone oils include silicone oils modified from ordinary silicone oils using alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, methanol (Carbinol), and mercapto groups. Examples of cyclic silicone oils include, for instance, cyclic dimethylsiloxane oil.

[0517] Straight-chain silicone oils (in other words, chain-like polyorganosiloxanes) can be compounds with side chains and saturated hydrocarbon groups at the ends. For example, a silicone oil can be a compound represented by the following formula (1).

[0518]

[0519] [In the formula,

[0520] R 11 R 12 R13 R 14 R 15 and R 16 Each is independently a monovalent saturated hydrocarbon group having 1 to 18 carbon atoms.

[0521] a is an integer greater than or equal to 1.

[0522] R 11 R 12 R 13 R 14 R 15 and R 16 Each is an independently monovalent saturated hydrocarbon group having 1 to 18 carbon atoms. The number of carbon atoms in the monovalent saturated hydrocarbon group can 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 can also be less than 18, less than 16, less than 14, less than 12, less than 10, less than 8, less than 6, less than 4, or less than 2.

[0523] R 11 R 12 R 13 R 14 R 15 and R 16 The monovalent saturated hydrocarbon groups can be either straight-chain or branched, preferably straight-chain, and more preferably straight-chain alkyl groups.

[0524] In one approach, R 11 R 12 R 13 R 14 R 15 and R 16 The monovalent saturated hydrocarbon group is preferably methyl or ethyl, more preferably methyl.

[0525] a is an integer greater than or equal to 1. The value of a can be selected such that the kinematic viscosity of the silicone oil, as shown in equation (1), falls within the range of the kinematic viscosity of the silicone oil described below.

[0526] In one embodiment, 'a' can 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. Alternatively, it can be less than 10000, less than 7500, less than 5000, less than 3000, less than 1500, less than 1000, less than 500, less than 300, less than 200, less than 100, or less than 50, preferably less than 1000.

[0527] Examples of silicone oils represented by formula (1) include dimethylpolysiloxane, diethylpolysiloxane, etc.

[0528] Cyclic silicone oils (in other words, cyclic organopolysiloxanes) can be compounds with saturated hydrocarbon side chains. As silicone oils, they can be, for example, compounds represented by the following formula (2).

[0529]

[0530] [In the formula,

[0531] R 17 and R 18 Each is independently a monovalent saturated hydrocarbon group having 1 to 18 carbon atoms.

[0532] w is an integer from 2 to 20.

[0533] R 17 and R 18 Each is independently a monovalent saturated hydrocarbon group having 1 to 18 carbon atoms. The number of carbon atoms in the saturated hydrocarbon group can 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 can 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, preferably 1 to 10.

[0534] R 17 and R 18 The saturated hydrocarbon groups in the form can be either straight-chain or branched, preferably straight-chain, and more preferably straight-chain alkyl groups.

[0535] In one approach, R 17 and R 18 The saturated hydrocarbon group is preferably methyl or ethyl, more preferably methyl.

[0536] b is an integer from 2 to 20. B is preferably 3 to 10, and more preferably 4 or 5.

[0537] Examples of compounds represented by formula (2) include decamethylcyclopentasiloxane and octamethylcyclotetrasiloxane.

[0538] Silicone oil can be used alone or in combination of two or more types.

[0539] (molecular weight)

[0540] In a GPC chromatogram obtained by GPC determination, silicone oil may have a peak in the region with a molecular weight of 1500 or higher. Furthermore, it may contain at least silicone oils other than amino-modified silicones. Silicone oils with peaks in the region with molecular weights of 1500 or higher may be silicone oils other than amino-modified silicones, and may be, for example, ordinary silicone oils or modified silicone oils (excluding amino-modified ones) as exemplified above.

[0541] The silicone oil in organosilicon compound (B) can be a silicone oil with a molecular weight of 1500 or higher, excluding amino-modified silicone. A silicone oil with a molecular weight of 1500 or higher refers to a silicone oil where the molecular weight of a single molecule is 1500 or higher. The presence of silicone oils with a molecular weight of 1500 or higher can be confirmed using methods such as GPC.

[0542] The number average molecular weight (Mn) of silicone oil can be above 200, above 300, above 500, above 700, above 1000, above 1500, above 2000, above 2500, above 3000, above 4000, above 5000, above 6000, above 8000, or above 10000. Alternatively, it can be below 100000, below 80000, below 60000, below 50000, below 40000, below 30000, below 25000, below 20000, below 15000, or below 10000.

[0543] The number-average molecular weight (Mn) of silicone oil can be obtained using GPC (gel permeation chromatography) (converted to polystyrene).

[0544] For gel permeation chromatography, an HLC-8420GPC EcoSEC Elite-WS (Tosoh Corporation) was used. A column with two TSKgel SuperMultipore HZ-M electrodes was used. An RI detector was used. Standard polystyrene (SRM706a NIST) was used as the reference material.

[0545] For the analytical sample, the silicone resin was dissolved in tetrahydrofuran to prepare a 0.1% by weight solution, which was then passed through a 0.5 μm filter. When determining the average molecular weight, the column was maintained at 40°C, tetrahydrofuran was used as the eluent, the flow rate was set to 0.35 mL / min, and 10 μL of the analytical sample was injected.

[0546] Commercially available silicone oils can be used. Examples of commercially available silicone oils include KF-96-30CS (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), KF-96-50CS (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), KF-96-300CS (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), and KF-96-1000CS (manufactured by Shin-Etsu Chemical Industry Co., Ltd.).

[0547] [Silicone emulsion]

[0548] The organosilicon compound (B) can be an organosilicon emulsion obtained by emulsification with dispersants, surfactants, etc. That is, the organosilicon compound (B) can be combined with dispersants, surfactants, etc., and included in the water-repellent composition in an emulsified state.

[0549] The dispersant and surfactant can be the [dispersant] of the present invention. Emulsification of the organosilicon compound (B) can be carried out using known methods. When the organosilicon compound (B) is emulsified, it is readily and uniformly dispersed in the water-repellent composition, readily imparting appropriate liquid-repellent properties.

[0550] The silicone emulsion can be either an oil-in-water emulsion (O / W type) or an oil-in-water emulsion (W / O type). As the liquid medium for the silicone emulsion, the liquid medium described in the [Liquid Medium] section of this invention can be used.

[0551] The organosilicon emulsion contained in the water-repellent composition of the present invention can be anionic, cationic or nonionic, preferably a nonionic surfactant.

[0552] The water-repellent composition of the present invention may also contain the silicone resin and / or silicone oil exemplified above.

[0553] The water-repellent composition of the present invention may be free of amino-modified silicone.

[0554] The water-repellent composition of the present invention can be an aqueous dispersion.

[0555] The pH of the water-repellent composition of the present invention is not particularly limited and can be 3.0 to 7.0.

[0556] [wax]

[0557] The water-repellent composition of the present invention may contain 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., an alkyl group) having 6 to 40 carbon atoms.

[0558] The wax in this invention adheres to a substrate (particularly a pulp substrate) and imparts liquid-repellent properties, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance to the substrate.

[0559] [Properties of wax, etc.]

[0560] The following shows the properties of wax, etc.

[0561] The wax can be in granular form (powder). The average particle size of the wax can 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; alternatively, it can 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. By setting them within the above range, the particle stability is excellent, and the liquid repellency is good. The average particle size can be measured using a microscope (scanning electron microscope). Specifically, the wax particle sample is observed using a microscope at any magnification. Next, if the particle shape is spherical, its diameter is taken as the particle size; if the particle shape is non-spherical, the average of the longest and shortest diameters is taken as the particle size. The particle size of all particles present in the field of view is measured, the field of view is shifted and the particle size is measured again, and the above operation is repeated. In this way, the particle size is measured at more than 100 locations, and the average value of these measurements is taken as the average particle size.

[0562] The HD (n-hexadecane) contact angle of the wax can 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 can also be 100° or less, 90° or less, or 75° or less. By having an HD contact angle of 10° or more than the lower limit mentioned above, the wax can impart good liquid repellency (especially oil repellency) to the substrate. The HD contact angle refers to the static contact angle of the spin-coated film of the wax, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle after 1 second.

[0563] The water contact angle of a wax can be 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. Alternatively, it can be below 160°, 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 above or below the lower limit of the above-mentioned values, the wax can impart good liquid repellency (especially water repellency) to the substrate. The water contact angle refers to the static contact angle of a spin-coated wax film, and is obtained by adding 2 μL of water to the spin-coated film and measuring the contact angle after 1 second.

[0564] Waxes can be low molecular weight (e.g., molecular weight below 1000 or below 500) or high molecular weight. When the wax is a high molecular weight, its weight-average molecular weight can be above 1000, above 3000, above 5000, above 7500, above 10000, above 30000, above 100000, above 300000, or above 500000. Alternatively, it can be below 10000000, below 7500000, below 500000, below 300000, below 100000, below 750000, below 500000, below 300000, below 100000, below 75000, below 50000, below 30000, below 10000, below 7500, below 50000, below 30000, below 10000, below 7500, below 5000, or below 3000.

[0565] The melting point of the wax can be above 30°C, above 40°C, above 50°C, above 60°C, above 80°C, above 100°C, or above 120°C, preferably above 40°C, and particularly preferably above 55°C. Alternatively, it can be below 250°C, below 225°C, below 200°C, below 150°C, below 130°C, below 120°C, below 110°C, below 100°C, below 80°C, or below 50°C, preferably below 120°C. The melting point of the wax can be determined according to JIS K 2235-1991. The melting point is generally equivalent to the peak temperature of the endothermic peak at the maximum temperature before melting observed in DSC (differential scanning calorimetry).

[0566] [Types of wax, etc.]

[0567] Examples of waxes include: mineral waxes (petroleum waxes) such as paraffin wax, microcrystalline wax, lignite 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 invention can be a hydrocarbon wax, preferably a chain-like aliphatic hydrocarbon, such as a straight-chain or branched hydrocarbon, especially a straight-chain hydrocarbon.

[0568] [Isocyanate derivatives]

[0569] The water-repellent composition of the present invention may contain an isocyanate derivative. This isocyanate derivative has a hydrocarbon group having 2 to 40 carbon atoms, particularly a monovalent hydrocarbon group having 2 to 40 carbon atoms.

[0570] Isocyanate derivatives are compounds obtained by reacting active hydrogen compounds with raw isocyanates, and have portions derived from compounds containing active hydrogen and portions derived from the raw isocyanate. It should be noted that isocyanate derivatives differ from isocyanate-based curing agents and typically do not contain isocyanate groups.

[0571] Isocyanate derivatives possess the -NHCO- group (which can be part of a urethane or urea group) formed by the reaction of an active hydrogen compound with a reactant isocyanate. The -NHCO- group is formed by the reaction of the active hydrogen-containing group (typically a hydroxyl group) of the active hydrogen compound with the reactive group (typically an isocyanate group) of the reactant isocyanate. Isocyanate derivatives are typically urethanes (especially polyurethanes).

[0572] The isocyanate derivative preferably has a monovalent hydrocarbon group with 2 to 40 carbon atoms. Regarding hydrocarbon groups with 2 to 40 carbon atoms, the explanation already provided above (hydrocarbon groups with 2 to 40 carbon atoms) is relevant.

[0573] The hydrocarbon group can be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, and particularly preferably a saturated aliphatic hydrocarbon group (alkyl). The hydrocarbon group can be branched, cyclic, or linear, more preferably linear, and particularly linear. The number of carbon atoms in the hydrocarbon group can 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. Alternatively, it can 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.

[0574] The weight average molecular weight of the isocyanate derivative can be above 3000, above 5000, above 10000, above 30000, above 100000, above 300000, or above 500000. Alternatively, it can be below 1000000, below 750000, below 500000, below 300000, below 100000, below 75000, below 50000, below 30000, below 10000, or below 5000.

[0575] [Active hydrogen compounds]

[0576] Active hydrogen compounds contain active hydrogen groups that react with isocyanate groups.

[0577] Examples of active hydrogen groups include hydroxyl, amino, and carboxyl groups, with hydroxyl being a typical example.

[0578] (α1) Hydroethanol

[0579] Active hydrogen compounds can be active hydrogen compounds composed of hydrocarbon groups and hydroxyl groups (α1).

[0580] The hydrocarbon group in the active hydrogen compound (α1) is a hydrocarbon group with 2 to 40 carbon atoms as described above, citing the above description.

[0581] In addition, the active hydrogen compound (α1) preferably has one hydroxyl group per molecule.

[0582] Examples of active hydrogen compounds (α1) include: alcohols containing straight-chain saturated hydrocarbon groups such as n-tetranol, n-tetradecanool, n-pentadecanool, n-hexadecanool, n-heptadecanool, n-octadecanool (stearyl alcohol), n-nonadecanol, and eicosanool; alcohols containing branched saturated hydrocarbon groups such as isotetradecylol, isohexadecylol, isooctadecylol, and isoeicosanool; alcohols containing straight-chain unsaturated hydrocarbon groups such as tetradecenol, hexadecenol, oleyl alcohol, eicosenoenol, dodecenol, dodecenol, dodecenol, dodecenol, dodecenol, and dodecenol; and active hydrogen compounds containing branched unsaturated hydrocarbon groups such as phytol.

[0583] Here, alcohols containing straight-chain saturated hydrocarbon groups and alcohols containing straight-chain unsaturated hydrocarbon groups can also be used together. When alcohols containing straight-chain saturated hydrocarbon groups and alcohols containing straight-chain unsaturated hydrocarbon groups are used together, the proportion of alcohols containing straight-chain saturated hydrocarbon groups 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 for example, 90 parts by mass or less, preferably 80 parts by mass or less, relative to the total amount of alcohols containing straight-chain saturated hydrocarbon groups and alcohols containing straight-chain unsaturated hydrocarbon groups, is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, and for example, 60 parts by mass or less, preferably 45 parts by mass or less, more preferably 30 parts by mass or less, relative to the total amount of alcohols containing straight-chain saturated hydrocarbon groups and alcohols containing straight-chain unsaturated hydrocarbon groups. As long as the proportion of alcohols containing straight-chain saturated hydrocarbon groups is above the lower limit mentioned above, the crystallinity of the hydrocarbon groups is improved, which in turn improves the liquid-repellent properties of the treated product treated by the water-repellent composition.

[0584] (α2) Sugar alcohol / hydroxy acid modified form

[0585] The active hydrogen compound can be a sugar alcohol / hydroxy acid modifier (α2) of a sugar alcohol / hydroxy acid (sugar alcohol and / or hydroxy acid) with a hydrocarbon group having 2 to 40 carbon atoms. There are no limitations on the type of sugar alcohol / hydroxy acid; it can be cyclic or acyclic. Examples of sugar alcohols include monosaccharides, reducing sugars, amino sugars, aldonic acids, and aldonic acid lactones. Examples of hydroxy acids include hydroxy polycarboxylic acids. Sugar alcohols / hydroxy acids can be substances present in living organisms. Examples of sugar alcohols / hydroxy acids include compounds derived from aldoses and ketoses, such as tetrasaccharides, pentoses, hexoses, and heptoses, but are not limited to these. Specific examples include: glucose, glyceraldehyde, erythrose, arabinose, ribose, pentose, allose, azoose, mannose, xylose, lysose, gulose, galactose, tarose, fructose, ribulose, mannoheptulose, sedoheptulose, threose, erythritol, threitol, pyranose, and pyranose. Mannose, pyrantrolose, pyranolose, pyranolose, pyranidolose, pyranolol, glucol, mannitol, erythritol, sorbitol, arabinol, xylitol, ribitol, galactitol, fucitol, idolol, inositol, pentaerythritol, dipentaerythritol, heptaheptaol, gluconic acid, glyceric acid, xylanic acid, mucoic acid, ascorbic acid, citric acid, gluconolactone, glycerolactone, xylanolactone, glucosamine, galactosamine, or mixtures thereof. The number of carbon atoms in the sugar alcohol / hydroxy acid can be 2 or more, 4 or more, or 6 or more, and can be 30 or less, 20 or less, or 10 or less. The average OH value of the compound (α2) can be greater than 0 to about 230, preferably about 10 to about 175, and most preferably in the range of about 25 to about 140.

[0586] The number of hydrocarbon groups with 2 to 40 carbon atoms in the sugar alcohol / hydroxy acid modifier (α2) can be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more. Alternatively, it can be 12 or less, 9 or less, 6 or less, or 3 or less.

[0587] In the sugar alcohol / hydroxy acid modified (α2), at least one active hydrogen atom (e.g., hydrogen in the OH group or carboxyl group) of the sugar alcohol and / or hydroxy acid can be selected from -R α2 -C(O)R α2 -(CH2CH2O) n (CH(CH3)CH2O) m R α2 -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 The active hydrogen substituents in, or mixtures thereof, are substituted. Here, R α2The group consists of a hydrocarbon group with 2 to 40 hydrogen atoms or carbon atoms, where each n is independently 0 to 20, each m is independently 0 to 20, and m+n can be greater than 0. It should be noted that compound (α2) has at least one active hydrogen atom. For example, in a sugar alcohol / hydroxy acid modified form, at least one (one or more) of the active hydrogen atom of the sugar alcohol / hydroxy acid may be unmodified. This active hydrogen atom (e.g., -OH group) can react with the active hydrogen reactive group (particularly isocyanate group) of compound (b) to form -NHCO-.

[0588] (α21) Sorbitan Modifier

[0589] The sugar alcohol / hydroxy acid modifier (α2) can be a sorbitan anhydride modifier (α21) that modifies sorbitan anhydride with a hydrocarbon group having 2 to 40 carbon atoms, particularly an alkyl sorbitan anhydride, or a sorbitan anhydride modified with a -R group. a2 -C(O)R α2 -(CH2CH2O) n (CH(CH3)CH2O) m R α2 -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 The compound obtained by substituting, or a mixture thereof, is (here, R) α2 (A hydrocarbon group with 2 or more carbon atoms (40). For example, sorbitan anhydride can be made using -C(O)R α2 Compounds that have undergone mono-, di-, or tri-substitution. Here, the sorbitan may contain a certain amount of sorbitol, isosorbitol, or other intermediates or byproducts. Commercially available sorbitan anhydrides such as SPAN can be used as the aforementioned alkyl sorbitan anhydrides.

[0590] In one embodiment, at least one active hydrogen substituent can be -C(O)R α2 R α2 It can be a straight-chain / branched alkyl group with 6 to 40 carbon atoms, more preferably 7 to 21, and most preferably 11 to 21. Preferred compounds include monosubstituted, disubstituted, and trisubstituted sorbitan anhydrides derived from octanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, tetracosanoic acid, and mixtures thereof. Particularly preferred compounds include monosubstituted, disubstituted, and trisubstituted sorbitan anhydride stearates or sorbitan anhydride behenicates.

[0591] In one approach, R a2 It may contain at least one unsaturated bond. As an example of the above compounds (at least one active hydrogen substituent is selected from -C(O)R), α2 Ra2 Containing at least one unsaturated bond, examples include trioleic sorbitan (i.e., where R is an unsaturated bond). α2 -C7H 14 CH=CHC8H 17 (but not limited to these.) Other examples may include mono-, di-, and tri-substituted sorbitan anhydrides derived from palmitoleic acid, linoleic acid, arachidonic acid, and erucic acid, but are not limited to these.

[0592] In one embodiment, the sorbitan anhydride-modified (α21) has at least one active hydrogen substituent, which may independently be -(CH2CH2O). n (CH(CH3)CH2O) m R α2 Or -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 Each of the above compounds has an independent m value of 0–20 and an independent n value of 0–20, where m+n is greater than 0. These compounds are known as polysorbates and are commercially available under the trademark TWEEN. These sorbitan anhydrides can be processed using R… α2 Mono-, di-, or tri-substituted substitutions can be performed. Commercially available polysorbates are known to contain substances derived from each R... 2 Various polysorbates of H (unsubstituted) to each R α2 This refers to various mixtures of polysorbates having 6 to 40 carbon atoms (completely substituted) in straight or branched alkyl groups, and mixtures of their various substituted derivatives. Examples of the aforementioned sorbitan anhydride modifier (α21) include polysorbates such as polysorbate tristearate and polysorbate monostearate. As for m+n greater than 0, R... α2 Examples of sorbitan anhydride modifiers (α21) containing at least one unsaturated bond are not limited, but can be cited as polysorbate trioleate (here, R α2 C7H 14 CH=CHC8H 17 It is commercially available under the name polysorbate 80. The sorbitan anhydride modifier (α21) can comprise a mixture of various compounds with active hydrogen substituents. Additionally, R... α2 It can contain compounds with at least one unsaturated bond and R a2 A mixture of fully saturated compounds.

[0593] (α22)citric acid modified form

[0594] The sugar alcohol / hydroxy acid modifier (α2) can be a citric acid modifier (α22) in which citric acid is modified with a hydrocarbon group having 6 to 40 carbon atoms, and particularly can be an alkyl ester of citric acid. For example, the citric acid modifier (α22) can exist in the form of a monosubstituted, disubstituted, or trisubstituted form having an alkyl group. A mixture of citric acid esters with various values ​​of active hydrogen substituents can be used, and R can also be included. α2 Compounds having a hydrocarbon group comprising at least one unsaturated bond and R α2 A mixture of compounds that are entirely saturated hydrocarbons. The citric acid-modified form (α22) may have a composition selected from -(CH2CH2O). n (CH(CH3)CH2O) m R α2 Or, -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 The active hydrogen substituent (here, R) α2 (A hydrocarbon group with 6 to 40 carbon atoms). Examples of citric acid modifiers (α22) include trialkyl citrates, but are not limited to these.

[0595] (α23) pentaerythritol modified form

[0596] The sugar alcohol / hydroxy acid modifier (α21) can be a pentaerythritol modifier (α23) that modifies pentaerythritol with a hydrocarbon group having 6 to 40 carbon atoms. It can be a monosubstituted, disubstituted, or trisubstituted derivative of a hydrocarbon group (especially an alkyl group) having 6 to 40 carbon atoms, for example, a dipentaerythritol ester. The active hydrogen substituent can contain -CH2C[CH2OR] α2 ]3(Here, R α2 (A hydrocarbon group with 6 to 40 carbon atoms). Additionally, the pentaerythritol modifier (α23) can contain compounds with a mixture of chain lengths of hydrocarbon groups, or R... α2 Compounds containing at least one unsaturated bond and R α2 A mixture of fully saturated compounds.

[0597] (α3) Cationic active hydrogen compounds

[0598] The active hydrogen compound can be a cationic active hydrogen compound (α3) having both active hydrogen groups and cationic groups.

[0599] In addition, the cationic active hydrogen compound (α3) preferably has more than two hydroxyl groups per molecule.

[0600] Examples of cationic groups include, for instance, tertiary amine groups.

[0601] That is, the cationic active hydrogen compound (α3) preferably has two or more hydroxyl groups per molecule as active hydrogen groups and tertiary amine groups as cationic groups.

[0602] By utilizing this cationic active hydrogen compound, good dispersibility in liquid media (such as water) can be imparted. In addition, cationic groups with affinity for fibrous products (described later) can be introduced into the resin, thereby improving wash durability.

[0603] More preferably, the cationic active hydrogen compound has two hydroxyl groups per molecule as active hydrogen groups and a tertiary amine group as a cationic group.

[0604] Examples of such cationic active hydrogen compounds include alkyl dialkyl alcoholamines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, N-methyldipropanolamine, and propanolamine, as well as trialkyl alcoholamines such as N-triethanolamine and N-triisopropanolamine, with N-methyldiethanolamine being the preferred example.

[0605] Cationic active hydrogen compounds (or the portion of hydrophobic compounds derived from cationic active hydrogen compounds) can form salts with acid compounds.

[0606] 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. Organic acids are preferred as acid compounds. If the acid compound contains an organic acid, the acid volatilizes upon heat treatment, thereby improving the liquid-repellent properties of the treated product from the water-repellent composition. Furthermore, from the viewpoint that the acid volatilizes upon heat treatment and the cationic groups become more readily adsorbed onto the fiber product, the wash durability of the fiber product can be improved.

[0607] (α4) Other compounds containing active hydrogen

[0608] The active hydrogen compound (α) may include other active hydrogen compounds (α4).

[0609] (α41) compound

[0610] The active hydrogen compound (α4) can be a compound represented by the following formula (α41).

[0611] R α41 -X α41

[0612] [In the formula,

[0613] In the formula, Rα41 C1 to C2 can contain at least one unsaturated group. 30 Straight-chain or branched alkyl, hydroxyl functionalities C1-C 30 Straight-chain or branched alkyl, hydroxyl functional straight-chain or branched C1-C 30 Polyethers, hydroxyl-functional linear or branched polyesters, hydroxyl-functional linear or branched organosiloxanes, and thiol-functional C1-C64 polymers. 30 Straight-chain or branched alkyl, amine functionality C1-C 30 Straight-chain or branched alkyl groups, Y - R α411 R α412 R α413 N + -R α414 -(Here, Y is a halide ion, for example, Cl-) － . ), HOS(=O)2-R α414 - or R α411 R α412 C = N - (where R is the value of N) α411 R a412 R α413 Each is independently -H, C1 to C6 alkyl, R α414 It is a divalent alkyl group with 1 to 20 carbon atoms. α41 For -OH, -C(O)OH, -SH, -NH(R'), -O-(CH2CH2O) s (CH(CH3)CH2O) t -H or -C(O)-O-(CH2CH2O) s (CH(CH3)CH2O) t -H and other isocyanate reactive functional groups (here, R' is -H or a 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).

[0614] Compound (α41) can be a hydrophilic, water-soluble material containing at least one hydroxyl-terminated polyether, where X α41 It is -O-(CH2CH2O) s (CH(CH3)CH2O) t -H or -C(O)-O-(CH2CH2O) s (CH(CH3)CH2O) t -H. -(CH2CH2O)- represents oxyethylidene (EO), and -(CH(CH3)CH2O)- represents oxypropylene (PO). These polyethers may contain only EO groups, only PO groups, or mixtures thereof. Additionally, these polyethers may exist in the form of a specified PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol) triblock copolymer.

[0615] In one manner, X a41 For -OH, -C(O)OH, -SH, -NH(R'), R α41 Selected from C1 to C2 groups, optionally containing at least one unsaturated group. 30 Straight-chain or branched alkyl, hydroxyl functionalities C1-C 30 Straight-chain or branched alkyl, hydroxyl functional straight-chain or branched C1-C 30 Polyethers, hydroxyl-functional linear or branched polyesters, hydroxyl or amine-functional linear or branched organosiloxanes, and thiols-functional C1-C64... 30 Straight-chain or branched alkyl, amine functionality C1-C 30 Straight-chain or branched alkyl groups.

[0616] X α41 It can be -OH. Examples of the compounds (α41) mentioned above include: alkyl alcohols such as propanol and butanol, or aliphatic alcohols including octadecyl alcohol (R...). a41 C1 to C2, optionally containing at least one unsaturated group 30 Alkyl glycols or polyols such as straight-chain or branched alkyl groups, ethylene glycol, propylene glycol, butanediol, or hexanediol (R... α41 Hydroxyl functional C1~C 30 Alkylene glycol ethers such as straight-chain or branched alkyl groups, triethylene glycol, tetraethylene glycol, poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), poly(tetrahydrofuran), etc., or glycol ethers of mixtures having PEG, PPG, or THF units (R α41 It is a hydroxyl-functional straight-chain or branched C1-C1 chain. 30 Polyether), polyester polyol (R) α41 Hydroxyl-functional linear or branched polyesters), silicone prepolymer polyols (R α41 (hydroxyl-functional linear or branched organosiloxanes), N,N-dimethylaminoethanol (R...) α41 Amine functional C1~C 30 (straight-chain or branched alkyl groups), choline chloride or betaine HCl (R) α41 For Y - R α411 R α412 R α413 N + -R α414 -), Butyl ketone oxime (R) α41 For R α411 R α412C = N-), but not limited to these. Polyether polyols may contain only EO groups, only PO groups, only THF groups, or mixtures thereof. Furthermore, these polyethers may exist in the form of block copolymers such as those specified by PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol). The polyether diol preferably has an average molecular weight of about 200 or more, most preferably 350 to 2000.

[0617] X α41 It can be -C(O)OH. Examples of the above-mentioned compounds (α41) include: octanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, tetracosanoic acid, palmitoleic acid, linoleic acid, arachidonic acid, oleic acid, or erucic acid, etc., fatty acids (R... α41 C1 to C2, optionally containing at least one unsaturated group 30 Acids containing hydroxyl groups, such as straight-chain or branched alkyl groups, hydroxyoctanoic acid, hydroxydecanoic acid, hydroxylauric acid, hydroxymyristic acid, hydroxypalmitic acid, hydroxystearic acid, hydroxyarachidic acid, hydroxybenzeneic acid, hydroxytetracosanoic acid, hydroxypalmitoic acid, hydroxylinoleic acid, hydroxyarachidonic acid, hydroxyoleic acid, or hydroxyerucic acid, are considered to contain hydroxyl groups. α41 Hydroxyl functional C1~C 30 (straight-chain or branched alkyl), and mercaptoalkyl acids such as mercaptopropionic acid (R α41 It is a thiol functional C1~C 30 (Straight-chain or branched alkyl groups), but not limited to these.

[0618] X α41 It can be -SH. Examples of the compounds mentioned above (α41) include alkyl thiols such as lauryl thiol or dodecyl thiol (R...). α41 C1 to C2, optionally containing at least one unsaturated group 30 (Straight-chain or branched alkyl groups), but not limited to these.

[0619] X α41 It can be -NH(R'), and examples of the above-mentioned compounds (α41) include: diisopropylamine, propylamine, hexylamine, or laurylamine and other alkylamines (R'). α41 C1 to C2, optionally containing at least one unsaturated group 30 Alkylamines (R) such as straight-chain or branched alkyl groups, ethanolamines, or propanolamines. α41 Hydroxyl functional C1~C 30 (Linear or branched alkyl), silicone prepolymer polyamine (R) α41 (Amine-functional linear or branched organosiloxanes), alkyl diamines (R...) α41 Amine functional C1~C 30 Aminoalkylsulfonic acids (R) such as straight-chain or branched alkyl groups and 2-aminoethanesulfonic acid.α41 for HO-S(O)2R α414 -), but not limited to these.

[0620] (α42) compound

[0621] Compound (α42) can be represented by the following formula:

[0622] R α421 -(OCH2CH(OR α422 CH2) z -OR α423

[0623] [In the formula,

[0624] Regarding R α421 R α422 and R α423 In other words, at least one R α421 R α422 or R α423 For -H, independently for -H and -R respectively. α424 -C(O)R α424 R α424 Independently, it is a straight-chain or branched alkyl group having 5 to 29 carbons, which may contain at least one unsaturated bond, and z is 1 to 15.

[0625] Compound (α42) can be a compound commonly referred to as polyglycerol. Other specific examples include, but are not limited to, triglyceride monostearate, triglyceride distearate, hexaglyceride monostearate, hexaglyceride distearate, decaglyceryl mono(caprylate / capricate), decaglyceryl di(caprylate / capricate), decaglycerol, polyglycerol-3 and C18 diglycerides.

[0626] (α43) Chain extender

[0627] Compound (α4) can be a chain extender (α43). A chain extender (α43) is a compound having two or more (e.g., two) functional groups containing active hydrogen in its molecule. As chain extenders, known chain extenders can be used, such as: aliphatic or aromatic diols or polyols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol, and cyclohexanediethanolamine; aliphatic or aromatic diamines or polyamines such as ethylenediamine, piperazine, aminoethylpiperazine, phenylenediamine, and diethyltoluenediamine; compounds containing phenolic hydroxyl groups such as resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxyphenyl)-1-phenylethane), bisphenol F, bisphenol K, bisphenol M, tetramethylbiphenol, and o,o'-diallyl-bisphenol A; and alcoholamines such as aminoethylethanolamine, aminopropylethanolamine, aminohexylethanolamine, aminoethylpropanolamine, aminopropylpropanolamine, and aminohexylpropanolamine.

[0628] [Raw material isocyanate]

[0629] Fluorinated compounds contain a portion derived from the raw material isocyanate.

[0630] Examples of isocyanates used as raw materials include: toluene diisocyanate (2,4- or 2,6-toluene diisocyanate or mixtures thereof) (TDI), phenylene diisocyanate (m- or p-phenylene diisocyanate or mixtures thereof), 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or mixtures thereof) (MDI), 4,4'-toluidine isocyanate (TODI), 4,4'-diphenyl ether diisocyanate, phenyl dimethyl diisocyanate (1,3- or 1,4-phenyl dimethyl diisocyanate or mixtures thereof) (XDI), tetramethylphenyl dimethyl diisocyanate, etc. Aromatic polyisocyanates including esters (1,3- or 1,4-tetramethylphenyl dimethyl diisocyanate or mixtures thereof) (TMXDI), ω,ω'-diisocyanate-1,4-diethylphenyl, naphthalene diisocyanate (1,5-, 1,4- or 1,8-naphthalene diisocyanate or mixtures thereof) (NDI), triphenylmethane triisocyanate, tri(isocyanate phenyl) 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;

[0631] Noncyclic aliphatic polyisocyanates selected from trimethylene diisocyanate, 1,2-propylidene diisocyanate, butylidene diisocyanate (tetramethylene diisocyanate, 1,2-butylidene diisocyanate, 2,3-butylidene diisocyanate, 1,3-butylidene diisocyanate), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylhexanoate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecyl triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, and decamethylene diisocyanate;

[0632] Selected from 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), methylene bis(cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylene bis(cyclohexyl isocyanate or mixtures thereof) (hydrogenated MDI), methyl Cyclohexane 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 mixtures thereof) (hydrogenated XDI), dimer acid diisocyanates, trans-cyclohexane 1,4-diisocyanate, hydrogenated toluene diisocyanate (hydrogenated TDI), hydrogenated tetramethylphenyl dimethyl diisocyanate (hydrogenated TMXDI) are cyclic alicyclic polyisocyanates;

[0633] Bridged cyclic alicyclic polyisocyanates selected from norbornene diisocyanate, norbornane diisocyanate methyl ester, bicycloheptane triisocyanate, diisocyanate methyl bicycloheptane, and di(diisocyanate methyl)tricyclodecane.

[0634] Selected from

[0635]

[0636]

[0637] Compounds in;

[0638] And the above-mentioned biuret modified isocyanates, polymers of polyisocyanates (e.g., dimers, trimers (e.g., isocyanurate derivatives, iminooxadiazine dione derivatives), pentamers, heptamers, etc.), urea carbamate derivatives (e.g., urea carbamate derivatives generated by the reaction of the above-mentioned polyisocyanates with monohydric or dihydric alcohols, etc.), polyol derivatives (e.g., polyol derivatives (alcohol adducts, preferably trimethylolpropane adducts) generated by the reaction of the above-mentioned polyisocyanates with trihydric alcohols (e.g., trimethylolpropane, etc.), etc.), biuret derivatives (e.g., biuret derivatives generated by the reaction of the above-mentioned polyisocyanates with water or amines, etc.), urea derivatives (e.g., urea derivatives generated by the reaction of the above-mentioned polyisocyanates with diamines, etc.), oxadiazine trione derivatives (e.g., oxadiazine trione generated by the reaction of the above-mentioned polyisocyanates with carbon dioxide, etc.), carbodiimide derivatives (carbodiimide derivatives generated by the decarboxylation condensation reaction of the above-mentioned polyisocyanates, etc.), urea dione derivatives, urea ketone imide derivatives, etc.

[0639] The average number of isocyanate groups in the raw material isocyanate is 2 or more, preferably 2.5, more preferably 2.9, and, for example, 3.8 or less. The raw material isocyanate can be a polyisocyanate having multiple isocyanate groups.

[0640] [Synthetic methods for isocyanate derivatives]

[0641] Furthermore, to obtain isocyanate derivatives, an active hydrogen compound is reacted with a starting isocyanate. The reaction can be carried out in one stage or in multiple stages sequentially. For example, if unreacted active hydrogen groups or reactive active hydrogen groups are present in the product, the synthesis can be carried out sequentially. Sequential reactions are particularly useful when using substituted sugar alcohols with high OH numbers. 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 can be combined in such a way that the equivalence ratio (active hydrogen reactive group / active hydrogen group) of the active hydrogen reactive group (isocyanate group) to the active hydrogen group is, for example, 1.2 or more, preferably 1.5 or more, and also, for example, 2.0 or less.

[0642] [Composition of isocyanate derivatives]

[0643] The amount of the portion derived from the active hydrogen compound, relative to the isocyanate derivative, can be 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight. Alternatively, it can be less than 75% by weight, less than 65% by weight, less than 55% by weight, less than 45% by weight, less than 35% by weight, less than 25% by weight, or less than 15% by weight.

[0644] The amount of the portion derived from hydrocarbon alcohols (α1) relative to the portion derived from active hydrogen compounds can be 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight. Alternatively, it can be less than 75% by weight, less than 65% by weight, less than 55% by weight, less than 45% by weight, less than 35% by weight, less than 25% by weight, or less than 15% by weight.

[0645] The amount of the portion derived from the sugar alcohol / hydroxy acid modifier (α2), relative to the portion derived from the active hydrogen compound, can be 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight. Alternatively, it can be less than 75% by weight, less than 65% by weight, less than 55% by weight, less than 45% by weight, less than 35% by weight, less than 25% by weight, or less than 15% by weight.

[0646] The amount of the portion derived from cationic active hydrogen compounds (α3) relative to the portion derived from active hydrogen compounds can be 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight. Alternatively, it can be less than 75% by weight, less than 65% by weight, less than 55% by weight, less than 45% by weight, less than 35% by weight, less than 25% by weight, or less than 15% by weight.

[0647] The amount of the portion derived from other compounds containing active hydrogen (α4), relative to the portion derived from active hydrogen compounds, can be 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight. Alternatively, it can be less than 75% by weight, less than 65% by weight, less than 55% by weight, less than 45% by weight, less than 35% by weight, less than 25% by weight, or less than 15% by weight.

[0648] The amount of the portion derived from the isocyanate source relative to the isocyanate derivative can be 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight. Alternatively, it can be less than 75% by weight, less than 65% by weight, less than 55% by weight, less than 45% by weight, less than 35% by weight, less than 25% by weight, or less than 15% by weight.

[0649] [Dispersant]

[0650] The water-repellent composition of this invention may contain a dispersant. The dispersant may be at least one selected from organic and inorganic dispersants. The dispersant may be at least one selected from anionic, nonionic, cationic, amphoteric, and inorganic dispersants. In particular, the water-repellent composition of this invention may contain a nonionic dispersant, or a combination of a nonionic surfactant and a cationic surfactant. By containing a dispersant, it is possible to achieve a good balance of water repellency, anti-slip properties, and storage stability.

[0651] Dispersants can be organic dispersants and inorganic dispersants, or a combination of organic and inorganic dispersants.

[0652] Organic dispersants can be used as dispersants. Organic dispersants can be classified as nonionic dispersants, anionic dispersants, cationic dispersants, and amphoteric dispersants. Organic dispersants can also refer to surfactants.

[0653] Dispersants may also not have fluorine atoms.

[0654] [Nonionic Dispersant]

[0655] Dispersants may also include nonionic dispersants. Nonionic dispersants can be nonionic surfactants.

[0656] Nonionic dispersants can be low molecular weight (e.g., molecular weight below 2000, especially below 10000) or high molecular weight (e.g., molecular weight above 2000). The molecular weight of nonionic dispersants can be above 100, above 500, above 1000, above 2000, above 4000, or above 6000. Alternatively, it can be below 1,000,000, below 750,000, below 500,000, below 250,000, below 100,000, below 50,000, below 10,000, below 7,500, below 5,000, below 25,000, below 750, or below 250.

[0657] Examples of nonionic dispersants include: ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides.

[0658] Examples of ethers are compounds having an oxyalkylene group (preferably, a polyoxyethylene group).

[0659] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are alcohols with 1 to 30 carbon atoms (especially 2 to 10 carbon atoms) and 1 to 50 carbon atoms (especially 10 to 30 carbon atoms). Examples of fatty acids are saturated or unsaturated fatty acids with 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0660] Examples of ester ethers are compounds obtained by adding an epoxide (particularly ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are alcohols with 1 to 30 carbon atoms (particularly 2 to 10 carbon atoms) and 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms), such as aliphatic alcohols. Examples of fatty acids are saturated or unsaturated fatty acids with 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0661] Examples of alkanolamides are formed from fatty acids and alkanolamines. Alkanolamides can be monoalkanolamides or dialkanolamines. Examples of fatty acids are saturated or unsaturated fatty acids with 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. Alkanolamines can be alkanols with 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0662] Polyols can be alcohols with 2 to 5 carbon atoms and 10 to 30 carbon atoms.

[0663] The amine oxide can be an oxide of an amine (secondary amine or preferably tertiary amine) (e.g., having 5 to 50 carbon atoms).

[0664] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably polyoxyethylene). The number of carbon atoms in the alkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic dispersant is usually preferably 2 to 100.

[0665] The nonionic dispersant is selected from ethers, esters, ester ethers, alkanolamides, polyols and amine oxides, and is preferably a nonionic dispersant with oxyalkylene groups.

[0666] Nonionic dispersants can be epoxy alkane adducts of linear and / or branched aliphatic (saturated and / or unsaturated) groups, polyalkylene glycol esters of linear and / or branched fatty acids (saturated and / or unsaturated), sorbitan esters of linear and / or branched fatty acids (saturated and / or unsaturated), glycerides of linear and / or branched fatty acids (saturated and / or unsaturated), polyglycerol esters of linear and / or branched fatty acids (saturated and / or unsaturated), sucrose esters of linear and / or branched fatty acids (saturated and / or unsaturated), polyethylene oxide (POE) / polypropylene oxide (POP) copolymers (random copolymers or block copolymers), epoxy alkane adducts of acetylene glycol, etc. Among these compounds, those with the epoxy alkane addition portion and the polyalkylene glycol portion preferably having the structure of polyoxyethylene (POE) or polyoxypropylene (POP) or POE / POP copolymer (which can be a random copolymer or a block copolymer) are preferred.

[0667] In addition, nonionic dispersants may also be free of aromatic groups.

[0668] Nonionic dispersants can be compounds represented by the following formula:

[0669] R 1 O-(CH2CH2O) p -(R 2 O) q -R 3

[0670] [In the formula, R] 1 It is an alkyl group having 1 to 22 carbon atoms, or an alkenyl or acyl group having 2 to 22 carbon atoms.

[0671] R 2 Each and every one of them is either identical or different, and is an alkylene group having 3 or more carbon atoms (e.g., 3 to 10).

[0672] R 3 It consists of hydrogen atoms, alkyl groups with 1 to 22 carbon atoms, or alkenyl groups with 2 to 22 carbon atoms, where p is 2 or more.

[0673] q is a number that is 0 or greater than 1.

[0674] R 1 Preferably, it has 8 to 20 carbon atoms, and particularly preferably 10 to 18. As R 1 Preferred specific examples may include: octyl, nonyl, trimethylnonyl, lauryl, tridecyl, oleyl, and octadecyl.

[0675] R 2 Examples include propylidene and butylidene.

[0676] In nonionic dispersants, p can be a number greater than 3 (e.g., 5–200). q can be a number greater than 2 (e.g., 5–200). That is, -(R 2 O) q - It can form polyoxyalkylene chains.

[0677] The nonionic dispersant can be a polyoxyethylene alkylene ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (especially a polyoxyalkylene chain) in the center. Examples of hydrophobic oxyalkylene chains include oxypropylene chains, oxybutylene chains, and styrene chains, among which oxypropylene chains are preferred.

[0678] Specific examples of nonionic dispersants include ethylene oxide with hexylphenol, isooctylphenol, hexadecyl alcohol, oleic acid, and alkanes (C). 12 -C 16 Thiols, sorbitan monofatty acids (C7-C5) 19 ) or alkyl (C 12 -C 18Condensation products of amines, etc.; sorbitan fatty acid esters; glycerol fatty acid esters; polyglycerol fatty acid esters; sucrose fatty acid esters; propylene glycol fatty acid esters; polyoxyethylene alkyl ethers; polyoxyethylene polyoxypropylene alkyl ethers; polyoxyethylene glycerol fatty acid esters; polyoxyethylene sorbitan fatty acid esters; lecithin derivatives, etc. Examples of nonionic dispersants include: polyoxyethylene alkyl ethers; polyoxyethylene polyoxypropylene alkyl ethers; polyoxyethylene polyoxybutene alkyl ethers; polyoxyethylene polyoxypropylene glycol; polyethyleneimine ethoxylates, etc.

[0679] The proportion of polyoxyethylene blocks relative to the molecular weight of the nonionic dispersant (copolymer) can be 5 to 80% by weight, for example 30 to 75% by weight, and particularly 40 to 70% by weight.

[0680] The average molecular weight of nonionic dispersants is typically 300 to 5,000, for example, 500 to 3,000.

[0681] Nonionic dispersants can be a single type or a mixture of two or more. Nonionic dispersants can contain compounds with an HLB (hydrophilicity-hydrophobicity balance) of 10 or less, or a mixture of compounds with an HLB of less than 15 (particularly less than 5) and compounds with an HLB of 15 or more. Specifically, they are preferably selected from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, polyoxypropylene, and sorbitan fatty acid esters, glycerol fatty acid esters, polyglycerol fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerol fatty acid esters, and polyoxyethylene sorbitan fatty acid esters with an HLB of 1 to 18.

[0682] [Catonic dispersant]

[0683] Dispersants may also include cationic dispersants. Cationic dispersants can be cationic surfactants. Cationic dispersants can be compounds that do not have amide groups.

[0684] Cationic dispersants can be low molecular weight (e.g., molecular weight below 2000, especially below 10000) or high molecular weight (e.g., molecular weight above 2000). The molecular weight of cationic dispersants can be above 100, above 500, above 1000, above 2000, above 4000, or above 6000. Alternatively, it can be below 1,000,000, below 750,000, below 500,000, below 250,000, below 100,000, below 50,000, below 10,000, below 7,500, below 5,000, below 25,000, below 750, or below 250.

[0685] Cationic dispersants can be aliphatic or aromatic, and examples include ammonium salts (e.g., quaternary ammonium salts). Cationic dispersants can be addition-type ammonium salts of ethylene oxide. Specifically, examples include: amine salt dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazoline; quaternary ammonium salt dispersants such as alkyl trimethylammonium salts, dialkyl dimethylammonium salts, alkyl dimethyl benzylammonium salts, pyridinium salts, alkyl isoquinoline onion salts, benzalkonium chloride, and benzyl chloride; and high molecular weight cationic dispersants such as polyquaternium salts-1 to 47. Examples of cationic dispersants include alkylamine salts and quaternary ammonium salts.

[0686] Low-molecular-weight cationic dispersants can be compounds represented by the following formula:

[0687] R 21 -N + (-R 22 (-R) 23 (-R) 24 )X -

[0688] [In the formula, R] 21 R 22 R 23 and R 24 X is a hydrogen group or a hydrocarbon group with 1 to 40 carbon atoms, where X is an anionic group. 21 R 22 R 23 and -R 24 Specific examples of X include alkyl groups (e.g., methyl, butyl, octadecyl, hexadecyl), aromatic groups (e.g., benzyl, phenyl), etc. Specific examples of X include halogens (e.g., chlorine), acids (e.g., hydrochloric acid, acetic acid), etc. Examples of cationic dispersants include monoalkyl trimethylammonium salts (alkyl groups with 4 to 40 carbon atoms) and benzalkonium chloride, etc.

[0689] Specifically, low-molecular-weight cationic dispersants can be ammonium salts represented by the following formula, R 1 p -N + R 2 q X -

[0690] [In the formula, R] 1 C 12 The above (e.g., C) 12 ~C 50 Straight-chain and / or branched aliphatic (saturated and / or unsaturated) groups,

[0691] R 2 For H or C 1～4Alkyl, benzyl, polyoxyethylene (the number of oxyethylene groups is, for example, 1 (especially 2, especially 3) to 50) (especially preferably CH3, C2H5),

[0692] X is a halogen atom (e.g., chlorine), or a C1-C4 fatty acid salt, or a C1-C4 sulfonate.

[0693] If p is 1 or 2, q is 2 or 3, then p + q = 4. 1 The number of carbon atoms can be 12 to 50, for example 12 to 30.

[0694] Low molecular weight cationic dispersants may include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyl di(hydrogenated polyoxyethylene)ammonium chloride, benzyldodecyl di(hydrogenated polyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride, etc.

[0695] High molecular weight cationic dispersants can be various polymers (e.g., polyquaternium salts-1 to 47) containing cationic groups (e.g., ammonium groups, quaternary ammonium groups). Examples of high molecular weight cationic dispersants include: cationic starch, cationic cellulose (e.g., O-(2-hydroxy-3-(trimethylammonium)propylhydroxyethyl cellulose chloride), cationic guar gum, cationic xanthan gum, chitosan, and other cationic natural products (especially cationic sugars); polymers of monomers containing cationic groups such as aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternized dimethylammonium ethyl methacrylate, diallyl dimethylammonium chloride, dimethylaminopropylamine, and quaternized vinylimidazole.

[0696] [Anionic dispersant]

[0697] Dispersants may also contain anionic dispersants. Anionic dispersants can be anionic surfactants. Dispersants may also not contain anionic dispersants.

[0698] Anionic dispersants can be low molecular weight (e.g., molecular weight below 2000, especially below 10000) or high molecular weight (e.g., molecular weight above 2000). The molecular weight of anionic dispersants can be above 100, above 500, above 1000, above 2000, above 4000, or above 6000. Alternatively, it can be below 1,000,000, below 750,000, below 500,000, below 250,000, below 100,000, below 50,000, below 10,000, below 7,500, below 5,000, below 25,000, below 750, or below 250.

[0699] Examples of anionic dispersants include: alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonyl fatty acid salts, N-acyl amino acid type dispersants, phosphate mono- or diester type dispersants, and sulfosuccinates. Examples of anionic dispersants include carboxylates (e.g., fatty acid salts).

[0700] [Amphoteric Dispersant]

[0701] Dispersants may include amphoteric dispersants. Amphoteric dispersants may be amphoteric surfactants.

[0702] Amphoteric dispersants can be low molecular weight (e.g., molecular weight below 2000, especially below 10000) or high molecular weight (e.g., molecular weight above 2000). The molecular weight of amphoteric dispersants can be above 100, above 500, above 1000, above 2000, above 4000, or above 6000. Alternatively, it can be below 1,000,000, below 750,000, below 500,000, below 250,000, below 100,000, below 50,000, below 10,000, below 7,500, below 5,000, below 25,000, below 750, or below 250.

[0703] Examples of amphoteric dispersants include: alanine derivatives, imidazoline betaines, amide betaines, and acetate betaines. More specifically, examples include: lauryl betaine, octadecyl betaine, lauryl carboxymethyl hydroxyethyl imidazoline betaine, lauryl dimethyl aminoacetic acid betaine, and fatty acid amide propyl dimethyl aminoacetic acid betaine.

[0704] [Inorganic dispersant]

[0705] Dispersants may also include inorganic dispersants.

[0706] The average primary particle size of inorganic dispersants can be 5 nm or more, 30 nm or more, 100 nm or more, 1 μm or more, 10 μm or more, or 25 μm or more. Alternatively, it can be less than 100 μm, 50 μm or less, 10 μm or less, 1 μm or less, 500 nm or less, or 300 nm or less. The average primary particle size can be determined, for example, by observation using a microscope (scanning electron microscope or transmission electron microscope). Inorganic dispersants can be hydrophilic particles.

[0707] Examples of inorganic dispersants include: tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, hydroxyapatite and other polyvalent metal salts of phosphate; calcium carbonate, magnesium carbonate and other carbonates; calcium metasilicate and other silicates; calcium sulfate, barium sulfate and other sulfates; calcium hydroxide, magnesium hydroxide, aluminum hydroxide and other hydroxides, etc.

[0708] [Amount of dispersant]

[0709] The amount of dispersant relative to 100 parts by weight of polymer (A) can 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 less. Alternatively, it can be less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, less than 5 parts by weight, less than 3 parts by weight, or less than 1 part by weight.

[0710] [Liquid medium]

[0711] The water-repellent composition of this invention may contain 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. Preferably, the water-repellent composition of this invention is an aqueous dispersion.

[0712] 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 isopropanol), aromatic solvents (e.g., toluene and xylene), and petroleum-based solvents (e.g., alkanes with 5 to 10 carbon atoms, specifically naphtha and kerosene). Water-soluble organic solvents are preferred. Water-soluble organic solvents may also contain compounds having at least one hydroxyl group (e.g., alcohols, diols, polyols, ethers of polyols (e.g., monoethers)). These organic solvents can be used alone or in combination of two or more.

[0713] [Amount of liquid medium]

[0714] The amount of liquid medium relative to 1 part by weight of polymer (A) can be 1 or more parts by weight, 3 or more parts by weight, 5 or more parts by weight, 10 or more parts by weight, 20 or more parts by weight, 30 or more parts by weight, 40 or more parts by weight, or 50 or more parts by weight, 100 or more parts by weight, 200 or more parts by weight, 300 or more parts by weight, 500 or more parts by weight, or 1000 or more parts by weight. Alternatively, it can be less than 3000 parts by weight, less than 2000 parts by weight, less than 1000 parts by weight, less than 500 parts by weight, less than 200 parts by weight, less than 175 parts by weight, less than 150 parts by weight, less than 125 parts by weight, less than 100 parts by weight, less than 80 parts by weight, less than 60 parts by weight, less than 40 parts by weight, less than 20 parts by weight, or less than 10 parts by weight.

[0715] The amount of water relative to 1 part by weight of polymer (A) can be 1 or more parts by weight, 3 or more parts by weight, 5 or more parts by weight, 10 or more parts by weight, 20 or more parts by weight, 30 or more parts by weight, 40 or more parts by weight, 50 or more parts by weight, 100 or more parts by weight, 200 or more parts by weight, 300 or more parts by weight, 500 or more parts by weight, or 1000 or more parts by weight. Alternatively, it can be less than 3000 parts by weight, less than 2000 parts by weight, less than 1000 parts by weight, less than 500 parts by weight, less than 200 parts by weight, less than 175 parts by weight, less than 150 parts by weight, less than 125 parts by weight, less than 100 parts by weight, less than 80 parts by weight, less than 60 parts by weight, less than 40 parts by weight, less than 20 parts by weight, or less than 10 parts by weight.

[0716] The amount of organic solvent relative to 1 part by weight of polymer (A) can 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. Alternatively, it can be less than 3000 parts by weight, less than 2000 parts by weight, less than 1000 parts by weight, less than 500 parts by weight, less than 200 parts by weight, less than 175 parts by weight, less than 150 parts by weight, less than 125 parts by weight, less than 100 parts by weight, less than 80 parts by weight, less than 60 parts by weight, less than 40 parts by weight, less than 20 parts by weight, or less than 10 parts by weight.

[0717] [Organic acids]

[0718] The water-repellent composition of the present invention may contain an organic acid. Known organic acids can be used as the organic acid. Carboxylic acids, sulfonic acids, sulfinic acids, etc., are preferred examples of the organic acid, with carboxylic acids being particularly preferred. Examples of the carboxylic acid 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 the present invention, 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.

[0719] [Amount of organic acids]

[0720] The amount of organic acid relative to 100 parts by weight of polymer (A) can 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. Alternatively, it can be less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 40 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight. The amount of organic acid can 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 can be acidic (pH 7 or less, for example 6 or less).

[0721] [Inorganic acids]

[0722] The water-repellent composition of the present invention may contain an inorganic acid. Known inorganic acids can be used as the inorganic acid. Examples of inorganic acids include: hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, boric acid, sulfuric acid, and phosphoric acid. In the present invention, one inorganic acid may be used, or two or more may be used in combination. By adding an inorganic acid, the stability of the aqueous dispersion can be improved.

[0723] [Amount of inorganic acid]

[0724] The amount of inorganic acid relative to 100 parts by weight of polymer (A) can 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. Alternatively, it can be less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 40 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight. The amount of inorganic acid can 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 can be acidic (pH 7 or less, for example 6 or less).

[0725] [Curing agent]

[0726] The water-repellent composition of the present invention may contain a curing agent (an active hydrogen reactive compound or a compound containing active hydrogen). When the water-repellent composition is for paper (e.g., an oil-resistant agent for paper), it may not contain a curing agent.

[0727] The curing agent (crosslinking agent) in the water-repellent composition enables the water-repellent composition to cure well. The curing agent can be an active hydrogen reactive compound or a compound containing active hydrogen that reacts with active hydrogen or active hydrogen reactive groups. Examples of active hydrogen reactive compounds include isocyanate compounds, epoxy compounds, chloromethyl compounds, carboxyl compounds, and acylhydrazine compounds. Examples of compounds containing active hydrogen include hydroxyl compounds, amino compounds, carboxyl compounds, ketone compounds, acylhydrazine compounds, melamine compounds, and urea compounds.

[0728] 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 terminal-capped isocyanate compound (e.g., a terminal-capped polyisocyanate compound). A terminal-capped isocyanate compound is a compound in which the isocyanate groups of the isocyanate compound are masked by a capping agent, thereby inhibiting the reaction.

[0729] 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-diisocyanate. Aliphatic diisocyanates of methylhexanoates, as well as lysine triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyano-4-isocyanate methyl octane, 1,3,6-triisocyanate hexane, 2,5,7-trimethyl-1,8-diisocyano-5-isocyanate methyl octane, and other aliphatic triisocyanates, etc. These compounds can be used alone or in combination of two or more.

[0730] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include: 1,3-cyclopentene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,3,5-triisocyanate cyclohexane, 4,4'-methylenebis(cyclohexyl isocyanate), and 1,3-bis(isocyanate methyl)cyclohexane. These compounds can be used alone or in combination of two or more.

[0731] Examples of aromatic aliphatic polyisocyanates are aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of aromatic aliphatic polyisocyanates include: 1,3- or 1,4-phenylenedimethyl diisocyanate or mixtures thereof, 1,3- or 1,4-bis(1-isocyanate-1-methylethyl)benzene (tetramethylphenyldimethyl diisocyanate) or mixtures thereof, and 1,3,5-triisocyanate-methylbenzene. These compounds can be used alone or in combination of two or more.

[0732] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include: m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or mixtures thereof, 2,4- or 2,6-toluene diisocyanate or mixtures thereof, triphenylmethane-4,4',4”-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate, etc. These compounds can be used alone or in combination of two or more.

[0733] Examples of polyisocyanate derivatives include dimers, trimers, biurets, urethanes, carbodiimides, urea diketones, urea ketone imides, isocyanurates, iminooxadiazine diketones, and various other derivatives of the aforementioned polyisocyanate compounds. These compounds can be used alone or in combination of two or more.

[0734] These polyisocyanates can be used in one or in combination of two or more.

[0735] As a polyisocyanate compound, it is preferable to use a compound in which the isocyanate group of the polyisocyanate compound is capped with a capping agent, i.e., a capped polyisocyanate compound (capped isocyanate). Capped polyisocyanate compounds are preferred because they are relatively stable in solution and can be used in the same solution as the water-repellent composition.

[0736] End-capping agents are substances that block free isocyanate groups. End-capped polyisocyanate compounds can be regenerated by heating to, for example, 100°C or higher, such as 130°C or higher, allowing the isocyanate groups to readily react with hydroxyl groups. Examples of end-capping 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.

[0737] Epoxy compounds are compounds containing epoxy groups. Examples of epoxy compounds include: epoxy compounds containing polyoxyalkylene groups, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether, etc.

[0738] Compounds containing chloromethyl groups are compounds that have a chloromethyl group. Examples of compounds containing chloromethyl groups include chloromethyl polystyrene.

[0739] Compounds containing a carboxyl group are compounds that have a carboxyl group. Examples of compounds containing a carboxyl group include (poly)acrylic acid and (poly)methacrylic acid.

[0740] Specific examples of compounds containing ketone groups include: (poly)diacetone acrylamide, diacetone alcohol, etc.

[0741] Specific examples of acylhydrazide compounds include: hydrazine, carbonylhydrazide, adipic hydrazide, etc.

[0742] Specific examples of melamine compounds include melamine resin and methyl etherified melamine resin.

[0743] Specific examples of urea compounds include: dihydroxymethyl dihydroxyethylene urea (DMDHEU), dimethyl dihydroxyethylene urea, etc.

[0744] [Amount of curing agent]

[0745] The amount of curing agent relative to 100 parts by weight of polymer (A) can 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. Alternatively, it can be less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 40 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight.

[0746] [Other ingredients]

[0747] The water-repellent composition may contain other components besides those mentioned above. Other components may also be added after manufacturing the hydrocarbon-based water-repellent resin. Examples of other components include: water-repellent and / or oil-repellent agents, antislip agents, antistatic agents, preservatives, antibacterial agents, deodorants, penetrants, etc. These substances may be used alone or in combination of two or more. In addition to the components mentioned above, other components may include: hand feel modifiers, softeners, antibacterial agents, flame retardants, anti-wrinkle agents, crosslinking agents, film-forming aids, compatibilizers, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, anti-shrinkage agents, anti-wrinkle agents, shape-retaining agents, drape-retaining agents, ironing agents, polymeric dispersants, scum dispersants, fluorescent whitening agents, dye fixatives, and defoaming agents. These substances may be used alone or in combination of two or more.

[0748] (Antistatic agent)

[0749] Examples of antistatic agents include: quaternary ammonium salts, pyridinium salts, and cationic antistatic agents with cationic functional groups such as primary, secondary, and tertiary amine groups; anionic antistatic agents with anionic functional groups such as sulfonates, sulfates, phosphonates, and phosphates; amphoteric antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, and alanine and its derivatives; and nonionic antistatic agents such as amino alcohols and their derivatives, glycerol and its derivatives, and polyethylene glycol and its derivatives. Ionically conductive polymers can be obtained by polymerizing or copolymerizing monomers with cationic, anionic, and amphoteric ionic conductive groups. These substances can be used alone, or two or more can be used in combination.

[0750] (preservative)

[0751] Preservatives are mainly used to enhance preservative and bactericidal properties and maintain long-term preservation. Examples of preservatives include isothiazolone organosulfur compounds, benzisothiazolidinone organosulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol. The content of the preservative relative to the total weight of the water-repellent composition is preferably 0.0001 to 1% by weight. When the content of the preservative is above the lower limit of the above range, the effect of adding the preservative can be fully obtained; when it is below the upper limit, the preservation stability of the water-repellent composition is good.

[0752] (Antibacterial agent)

[0753] Antimicrobial agents are ingredients that inhibit the proliferation of bacteria on fibers and also suppress the production of unpleasant odors from microbial decomposition products. Examples of antimicrobial agents include: cationic bactericides such as quaternary ammonium salts, zinc bis-(2-pyridylthio-1-oxide), polyhexamethylene biguanide hydrochloride, 8-oxyquinoline, polylysine, etc.

[0754] (Deodorant)

[0755] Examples of deodorants include: cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamide propyl dimethylamine oxide, and aminocarboxylic acid metal coordination compounds (such as the zinc complex of sodium methylglycine diacetate as described in International Publication No. 2012 / 090580).

[0756] (Anti-slip agent)

[0757] This ingredient has the effect of suppressing uneven stitching and misalignment of the sewn parts during sewing and wearing. Examples of anti-slip agents include: polysiloxane compounds, colloidal silica, silicone resin derivatives, colloidal organosilicone systems, and amino-modified silicones.

[0758] (softener)

[0759] Fabric softener is a component that imparts a soft and smooth feel to fabric. Examples of fabric softener components include: cationic surfactants such as quaternary ammonium salts and amine salts; anionic surfactants such as soaps, sulfated oils, higher alcohol sulfates and sulfonates; nonionic surfactants such as polyols and polyethylene glycols; amphoteric surfactants such as betaine-type and amino acid-type surfactants; and siloxane resins.

[0760] [Amount of other ingredients]

[0761] Relative to 100 parts by weight of polymer (A), the amounts or total amounts 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 less. Alternatively, they may be less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 40 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight.

[0762] <Uses of the water-repellent composition>

[0763] Examples of uses of the water-repellent composition in this invention include external treatment agents (surface treatment agents) or internal treatment agents, repellents (water-repellent agents, oil-repellent agents or water-repellent and oil-repellent agents, etc., especially water-repellent agents), antifouling agents, dirt removers, stripping agents, mold release agents (external mold release agents or internal mold release agents), etc.

[0764] <Method for manufacturing processed products>

[0765] The method for manufacturing the treated article in this invention includes a step of treating the substrate with a water-repellent composition.

[0766] [Processed Products]

[0767] Examples of substrates treated with the water-repellent composition of the present invention include: fiber products, stone, 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 industrial products, plastics, coatings, and plaster. Various examples of fiber products can be cited. Examples include: natural plant and animal 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 fiber, carbon fiber, and asbestos fiber; or blends thereof. As an example of a substrate treated with the water-repellent composition, woven fabrics will be described in detail.

[0768] (woven fabric)

[0769] Manufacturing methods for woven fabrics

[0770] Woven fabrics can be obtained by weaving yarns containing the aforementioned long and short fibers to obtain a greige fabric, followed by post-processing and water-repellent finishing. Known looms and knitting machines can be used for weaving, and known equipment can also be used for the preparatory processes before weaving.

[0771] The woven fabric can be post-processed using known refining and dyeing methods and equipment suitable for the fiber raw materials used in the woven fabric.

[0772] After post-processing, the woven fabric can undergo a water-repellent treatment. In this treatment, firstly, an aqueous solution containing a water-repellent agent (which can be the water-repellent agent composition of this invention) is prepared. Then, the post-processed woven fabric is coated with this aqueous solution using methods such as padding, spraying, contact roller coating, or slot coating, and then subjected to dry heat treatment after drying. The aqueous solution may also contain cross-linking agents, softeners, antistatic agents, etc., as needed. After the water-repellent treatment, the woven fabric can be calendered.

[0773] Woven fabrics are suitable for clothing applications requiring water repellency, especially for outdoor and sportswear such as skiing, snowboarding, and golf, as well as uniforms.

[0774] •Layered billets

[0775] The material can be provided as a laminated preform with a breathable and waterproof layer on one side of the woven fabric of the present invention. The breathable and waterproof layer can be directly laminated onto the woven fabric, or it can be laminated onto the woven fabric via an adhesive layer. It should be noted that when the laminated preform of the present invention is used for clothing or similar applications, the woven fabric side is positioned on the side exposed to rainwater, etc.

[0776] • Breathable waterproof layer

[0777] A breathable and waterproof layer is a layer that covers one side of a woven fabric and is formed of a resin or membrane with waterproof and breathable properties.

[0778] A breathable and waterproof layer can be formed by directly applying resin (the resin that constitutes the breathable and waterproof layer) to the woven fabric, or by laminating it onto one side of the woven fabric via an adhesive layer described later.

[0779] There are no particular limitations on the resin used to form the breathable and waterproof layer; both non-porous and porous resins can be used. For non-porous resins to achieve breathability, polyurethane resins and polyester elastomer resins with hydrophilic components can be used. In addition to polyurethane resins that form wet porous membranes and polyurethane resins that are porousized through electrospinning, porous resins such as PTFE porous membranes, PE, and PP porous membranes can also be used.

[0780] As a polyurethane resin, a known resin obtained by reacting a polyisocyanate component with a polyol component can be used.

[0781] A breathable and waterproof membrane with a microporous structure can be obtained by wet coagulation of a polyurethane resin DMF solution containing inorganic micropowder.

[0782] Examples of inorganic micropowders include those composed of silicon dioxide, aluminum dioxide, or titanium dioxide. Furthermore, the average primary particle size of the inorganic micropowder is preferably around 7 to 40 nm. The content of the inorganic micropowder relative to the total amount of the breathable and waterproof layer is preferably 3 to 50% by weight, more preferably 5 to 50% by weight.

[0783] The thickness of the breathable waterproof layer is preferably 5 μm or more, and more preferably 10 to 30 μm. When the thickness is within the above range, it becomes a breathable waterproof layer with an excellent balance between water repellency and moisture permeability, thus having an advantage in terms of feel.

[0784] Adhesive layer

[0785] The laminated preform preferably includes an adhesive layer. That is, the woven fabric and the breathable waterproof layer are preferably laminated through an adhesive layer. In addition, in terms of breathability, the adhesive layer is preferably a discontinuous layer such as a dotted or grid-like structure.

[0786] There are no particular restrictions on the type of adhesive used to form the adhesive layer, but an adhesive with excellent adhesion to the breathable and waterproof layer is preferred. For example, when a resin with polyurethane resin as the main component is selected as the resin constituting the breathable and waterproof layer, an adhesive layer containing a polyurethane-based adhesive is preferred. The polyurethane-based adhesive can be any type of adhesive, such as ether-based, ester-based, or polycarbonate-based adhesives.

[0787] The adhesive layer can be formed on one side of the woven fabric, or it can be formed in a pattern, considering factors such as breathability or hand feel. There are no particular limitations on the form of the pattern; examples include dots, lines, grids, checkerboard patterns, tortoise shell patterns, etc. Regardless of the pattern, it is preferable that it be evenly distributed throughout the fabric.

[0788] The thickness of the adhesive layer is preferably about 10 to 100 μm, and more preferably 20 to 80 μm.

[0789] Lining made of fiber fabric

[0790] With regard to the laminated preform of the present invention, a lining fabric can be laminated on the breathable waterproof layer (on the side opposite to the side of the woven fabric of the present invention within the breathable waterproof layer). The lining fabric can protect the breathable waterproof layer, thereby improving its waterproofness (water pressure resistance) and strength.

[0791] Various woven and knitted fabrics can be listed as lining materials. Among them, knitted fabrics are preferred because the yarns on the surface tend to protrude rather than form a flat surface, which is beneficial for enhancing the anchoring effect and preventing peeling from the breathable and waterproof layer.

[0792] In addition, warp-knitted (Tricot) fabrics can produce long greige fabrics with fewer seams during weaving, and can be evenly layered on a breathable and waterproof layer, which is also preferable.

[0793] There are no particular limitations on the raw materials of the fibers constituting the lining fabric, and appropriate selections can be made, with nylon fibers being preferred. This is because acid dyes are typically used in nylon fibers, thus reducing the likelihood of the problem of disperse dyes transferring and sublimating into the breathable and waterproof layer, which is a problem in polyester fibers using disperse dyes. There are also no particular limitations on the morphology (long fibers, short fibers, or yarn) or fineness of the fibers constituting the lining fabric islands, and appropriate selections can be made without impairing the effects of the present invention.

[0794] Characteristics of laminated blanks

[0795] The laminated blank has excellent water resistance. As a preferred example of the water resistance of the laminated blank of the present invention, the water level measured according to the water resistance test specified in JIS L 1092:2009A (low water pressure method) can be, for example, 10,000 mm or more, preferably 15,000 mm or more, further preferably 16,000 mm or more, and particularly preferably 20,000 mm or more.

[0796] The laminated preform exhibits excellent moisture permeability. A preferred example of the moisture permeability of the laminated preform of the present invention is a permeability of 10,000 g / m³, measured according to the JIS L 1099:2021B-1 method (potassium acetate method). 2 • 24 hours or more, preferably 15000g / m 2 • More than 24 hours, further optimized to 20000g / m 2 • More than 24 hours. There is no specific upper limit to the permeability; for example, 40,000 g / m³. 2 ·24h or 35000g / m 2 • 24h • mm. Additionally, permeability measured according to JIS L1099:2021A-1 method (calcium chloride method) can be exemplified by, for example, 4000 g / m³. 2 • 24 hours or more, preferably 8000g / m 2 • More than 24 hours, further optimized to 10000g / m 2 • More than 24 hours. Regarding the upper limit of this permeability, as the boundary of the measurement method, it is set at 13000–15000 g / m³. 2 Approximately 24 hours.

[0797] Regarding the laminated preform, in the laminated preform of the present invention, if the peel strength between the woven fabric and the breathable waterproof layer is 2.55 N / 2.54 cm or more as measured according to the method of JIS K 6404-2, it is preferred for clothing applications, and sometimes 5 N / 2.54 cm or more is preferred for general use.

[0798] • Manufacturing method of laminated billets

[0799] There are no particular restrictions on the manufacturing method of the laminated blanks; examples such as the first manufacturing method and the second manufacturing method shown below can be cited.

[0800] First manufacturing method: includes the process of forming the above-mentioned breathable and waterproof layer by coating the surface of the woven fabric with a resin constituting the above-mentioned breathable and waterproof layer.

[0801] The second manufacturing method includes a process of forming an adhesive layer on a woven fabric or a breathable waterproof layer, and a process of bonding the woven fabric and the breathable waterproof layer via the adhesive layer.

[0802] In the first manufacturing method, a method for coating the surface of the woven fabric with a resin that forms a breathable and waterproof layer can be exemplified by, for example, a coating method. In the coating method, a doctor blade or a comma-type coating can be used. Furthermore, from the viewpoint of possessing excellent breathability, a wet method is preferred for obtaining the breathable and waterproof layer.

[0803] In the second manufacturing method, a method for forming an adhesive layer on a woven fabric or a breathable waterproof layer can be exemplified by, for example, lamination. In lamination, the adhesive layer can be formed using a resin solution or by heat fusion. First, a resin composition for forming a breathable waterproof layer (e.g., a resin composition containing resin and organic solvent) is applied to the surface of a release material (release paper, release cloth, or release film, etc.) with gaps provided. The thickness is adjusted while forming the breathable waterproof layer, followed by drying and heat treatment to obtain a film. The release material can be appropriately removed after lamination or curing. Alternatively, in the case of lamination using a heat fusion method, the release material can be peeled off, and the film monomer can be used for lamination.

[0804] In addition, breathable and waterproof membranes can be laminated with membranes made by solventless extrusion methods such as T-die method and blow molding, porous membranes made by electrospinning, and porous membranes such as PTFE and / or PE and PP.

[0805] Then, an adhesive layer is formed on the woven fabric or the breathable waterproof layer. For example, in the case of a method using a resin solution, a two-component curing polyurethane resin solution with a viscosity adjusted to the range of 500 to 5000 mPa·s can be applied to the entire surface or in a pattern. The solution is then dried to form the adhesive layer, and the woven fabric and the breathable waterproof layer are bonded together via the adhesive layer. The two are then pressed or heat-pressed together, thereby enabling the second manufacturing method.

[0806] On the other hand, in the case of hot melting, a moisture-curing resin that reacts with moisture in the air is preferred, and practically, a resin that melts in a temperature range of approximately 80–150°C is more preferable. In this case, the hot-melt resin is first melted while taking into account the resin's melting point and viscosity during melting. Then, the molten resin is coated onto the woven fabric or the breathable waterproof layer to form an adhesive layer, and the woven fabric and the breathable waterproof layer are then bonded together by pressing, thereby enabling the second manufacturing method. Alternatively, if a good feel is desired, the breathable waterproof membrane can be patterned and bonded to the woven fabric.

[0807] Then, a lining of fibrous fabric can be layered on top of the breathable and waterproof layer using appropriate known methods.

[0808] Applications of laminated blanks

[0809] Due to its excellent waterproof and breathable properties, laminated fabrics do not peel off even in harsh environments, making them suitable for use in outdoor uniforms, sportswear, and other outdoor products.

[0810] [Solution]

[0811] The water-repellent composition of the present invention, as a treatment agent (particularly a surface treatment agent), can be applied to a substrate using existing known methods. This can be achieved by dispersing and diluting the water-repellent composition of the present invention in an organic solvent or water as needed, adhering it to the surface of the substrate using known methods such as dip coating, spray coating, foam coating, etc., and then drying it. After drying, a fibrous article with the solid components of the water-repellent composition adhering to it is obtained. Alternatively, if desired, it can be applied and cured together with a suitable crosslinking agent. Furthermore, the water-repellent composition of the present invention can be used in combination with various additives such as water-repellent and / or oil-repellent agents, anti-slip agents, antistatic agents, hand feel modifiers, softeners, antibacterial agents, flame retardants, coating fixatives, anti-wrinkle agents, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, freeze protectants, viscosity modifiers, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, and defoamers. Examples of various additives include those described in the "Other Components" section of the above-described water-repellent composition. The concentration of the hydrocarbon-based water-repellent resin in the treatment agent that comes into contact with the substrate can be appropriately varied depending on the application, and can be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0812] [Fiber Products]

[0813] Various examples of fiber products that serve as base materials can be cited, such as cloth products and paper products.

[0814] Examples of textile products include: natural plant and animal 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 fiber, carbon fiber, and asbestos fiber; or blends of these fibers. Textile products include woven fabrics, knitted fabrics, non-woven fabrics, clothing fabrics, and blankets. Processing can also be performed on fibers, yarns, and intermediate fiber products (such as yarn strips or rovings) in their state before they are made into fabric.

[0815] Examples of paper products include: paper made from bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp; bleached or unbleached high-yield pulp such as wood pulp, mechanical pulp or thermomechanical pulp; waste paper pulp such as old newspapers, old magazines, old corrugated paper or deinked waste paper; containers made from paper; and molded objects made from paper. Specific examples of paper products include food packaging paper, gypsum board base paper, coated base paper, medium-quality paper, general liner paper and core paper, neutral pure white roll paper, neutral liner paper, rust-proof liner paper and metal composite 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).

[0816] The water-repellent composition can be applied to fibrous articles (e.g., fabrics) using any known method for treating fibrous articles with a liquid. The fibrous article can be impregnated with the water-repellent composition, or the solution can be adhered to or sprayed onto the fibrous article. To exhibit water-repellent and oil-repellent properties, the treated fibrous article is preferably dried and cured by heating. Heating temperatures can be, for example, 100°C–200°C, 100°C–170°C, or 100°C–120°C. In this invention, good performance can be obtained even with low-temperature heating (e.g., 100°C–140°C). In this invention, the heating time can be from 5 seconds to 60 minutes, for example, from 30 seconds to 3 minutes.

[0817] Alternatively, the polymer can be applied to fibrous products using washing methods, such as washing applications or dry cleaning.

[0818] The treated fiber products can be fabrics, including woven fabrics (woven cloth), knitted fabrics (knitted cloth), and nonwoven fabrics, as well as fabrics and blankets in the form of clothing products, and can be fiber, yarn, or intermediate fiber products (e.g., yarn strips or rovings). The water-repellent composition of the present invention is particularly effective in making fiber products (e.g., synthetic fibers) water-repellent.

[0819] The fibers that make up fiber products can be natural fibers, synthetic fibers, semi-synthetic fibers, regenerated fibers, or inorganic fibers. A single type of fiber can be used, or two or more can be used in combination.

[0820] Examples of natural fibers include: cellulose fibers such as cotton, flax, and pulp; chitin; chitosan; wool; and silk. Specific examples of wood pulp include: mechanical pulps such as groundwood pulp (GP), pressure groundwood pulp (PGW), and thermomechanical pulp (TMP); chemical pulps such as high-yield unbleached kraft pulp (HNKP; N material), bleached kraft pulp (NBKP; N material, NB material), unbleached kraft pulp (LUKP; L material), and bleached kraft pulp (LBKP, L material); waste paper pulps such as deinked pulp (DIP) and waste paper pulp (WP) or semi-chemical pulp (CP), etc.

[0821] Examples of synthetic fibers include: polyesters such as polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, and copolyester; 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.

[0822] Examples of semi-synthetic fibers include acetate and triacetate. Examples of regenerated fibers include rayon, cuprammonium fiber, polynosic synthetic fiber, lyocell, and Tencel. Examples of inorganic fibers include glass fiber and carbon fiber.

[0823] Alternatively, the fiber product can be leather. To make the leather hydrophobic and oleophobic, the manufacturing polymer can be applied from an aqueous solution or aqueous emulsion to the leather at various stages of leather processing, such as during the wetting process or during the finishing process.

[0824] Alternatively, the fibrous product can be paper. The manufacturing polymer can be applied to pre-formed paper or at various stages of papermaking, such as during the paper drying process.

[0825] The term "treatment" refers to applying the water-repellent composition to a substrate through methods such as impregnation, spraying, or coating. Through treatment, the polymer, as the active ingredient in the water-repellent composition, penetrates into the interior of the substrate and / or adheres to its surface.

[0826] [Pretreatment of fiber products]

[0827] The fiber articles can be pretreated before being treated with the water-repellent composition of the present invention. By pretreating the fiber articles, the water-repellent composition can impart excellent durability to the treated fiber articles.

[0828] Examples of pretreatment for fiber products include: cationization treatment by reaction with reactive quaternary ammonium salts, anionization treatment such as sulfonation, carboxylation, and phosphorylation, acetylation treatment after anionization treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, and polymer coating treatment.

[0829] There are no limitations on the method for pretreating fiber products; any currently known method can be used. One possible method is to disperse the pretreatment solution in an organic solvent or water as needed, dilute it, and then apply it to the surface of the fiber product using known methods such as dip coating, spray coating, or foam coating, followed by drying. The pH and temperature of the pretreatment solution can be adjusted according to the desired degree of treatment. As an example of a method for pretreating fiber products, a method using a hydrocarbon-based water-repellent agent will be described in detail.

[0830] The pretreatment method for fiber products can include the following steps: imparting the fiber with a substance selected from SO3M 1 (where M is in the formula) 1 The monovalent group (representing a monovalent cation) is shown as -COOM. 2 (where M is in the formula) 2 The monovalent group (representing a monovalent cation) and -OP(O)(OX) are shown. 1 (OX) 2 (where X) 1 and X 2 At least one functional group (hereinafter sometimes referred to as "specific functional group") of a monovalent group (each independently representing a hydrogen atom or an alkyl group having 1 to 22 carbon atoms).

[0831] As M 1 Examples include H, K, Na, or ammonium ions that may have substituents. As M... 2 Examples include H, K, Na, or ammonium ions that may have substituents. In X 1 or X 2 When the alkyl group is used, it is preferably an alkyl group with 1 to 22 carbon atoms, and more preferably an alkyl group with 4 to 12 carbon atoms.

[0832] Fibers containing the aforementioned specific functional groups (hereinafter, sometimes referred to as "fibers containing functional groups") can be prepared, for example, by the following methods.

[0833] (i) To attach a compound having the specific functional groups described above to a fibrous material. It should be noted that the attachment of the compound can be a state in which a portion of the compound and a portion of the fiber are chemically bonded, with a sufficient amount of the specific functional groups remaining.

[0834] (ii) Prepare fibers in which the aforementioned specific functional groups are directly introduced into the materials constituting the fibers.

[0835] In case (i), for example, by treating the fiber material with a pretreatment liquid containing one or more compounds having the aforementioned specific functional groups in a functional group introduction process, fibers containing functional groups can be obtained.

[0836] There are no particular restrictions on the raw materials used for fiber materials. 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, as well as their composite fibers and blended fibers. Fiber materials can take any form, including fibers (slivers, carded fibers, etc.), yarns, knitted fabrics (including cross-knitted fabrics), woven fabrics (including interwoven fabrics), non-woven fabrics, and paper.

[0837] In this embodiment, from the viewpoint that the water repellency of the obtained fiber product is good, it is preferable to use fiber materials containing polyamide and polyester as raw materials, and particularly preferable to use nylon 6, nylon 6,6 and other nylons, polyethylene terephthalate (PET), polypropylene terephthalate, polylactic acid and other polyesters, and mixed fibers containing these substances.

[0838] As having the above-mentioned -SO 3 M 1 For compounds, phenolic polymers can be used. Examples of such phenolic polymers include substances containing at least one compound represented by the following general formula.

[0839]

[0840] In equation (2), X 2 It represents -SO3M3 (where M is the number of molecules in the formula). 3 [A cation with a monovalent charge (or a group represented by the following general formula), where n is an integer from 20 to 3000.]

[0841]

[0842] [In the formula, M] 4 This represents a cation with a monovalent charge.

[0843] As for the above M 3 Examples include: H, K, Na, or ammonium ions that may have substituents.

[0844] As for the above M 4 Examples include: H, K, Na, or ammonium ions that may have substituents.

[0845] The compounds represented by the above general formula can be, for example, formaldehyde condensates of phenol sulfonic acid or formaldehyde condensates of sulfonated bisphenol S.

[0846] As having the above-mentioned -COOM 2 Compounds that can be listed include polycarboxylic acid polymers.

[0847] As a polycarboxylic acid polymer, for example, polymers synthesized by existing known free radical polymerization methods using acrylic acid, methacrylic acid, maleic acid, etc. as monomers can be used, or commercially available polymers can be used.

[0848] One method for manufacturing polycarboxylate polymers is as follows: A free radical polymerization initiator is added to an aqueous solution of the monomer and / or its salt, and the reaction is carried out at 30–150°C for 2–5 hours. During this process, alcohols such as methanol, ethanol, and isopropanol, and / or aqueous solvents such as acetone, can be added to the aqueous solution of the monomer and / or its salt. Examples of free 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 free radical polymerization initiators can be used alone or in combination of two or more. Furthermore, during free radical polymerization, a chain transfer agent (e.g., octyl thioglycolate) can be added to adjust the degree of polymerization.

[0849] In free 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; acrylamide; acrylates; and methacrylates. Acrylates and methacrylates preferably have 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 can be used alone or in combination of two or more.

[0850] In polycarboxylic acid polymers, the carboxyl groups can be free or neutralized by alkali metals, amine compounds, etc. Examples of alkali metals include sodium, potassium, and lithium, while examples of amine compounds include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0851] From the viewpoint that the resulting fiber product has good water repellency, the weight-average molecular weight of the polycarboxylate polymer is preferably 1,000 to 20,000, more preferably 3,000 to 15,000.

[0852] Polycarboxylate polymers can be commercially available products such as "NEO CRYSTAL 770" (manufactured by Nichika Chemical Co., Ltd., trade name) and "SELOPOL PC-300" (manufactured by Sanyo Chemical Co., Ltd., trade name).

[0853] As having the above-mentioned -OP(O)(OX) 1 (OX) 2 Compounds of which can be represented by, for example, phosphate ester compounds represented by the following general formula.

[0854]

[0855] [In the formula, X] 1 or X 2 Same meaning as above, X 3 This refers to alkyl groups having 1 to 22 carbon atoms.

[0856] As the aforementioned phosphate ester compounds, phosphate monoesters, diesters, and triesters, as well as mixtures thereof, can be used, wherein the alkyl ester portion is an alkyl group having 1 to 22 carbon atoms.

[0857] From the viewpoint that the resulting fiber products have good water repellency, lauryl phosphate and decyl phosphate are preferred.

[0858] Phosphate compounds can be commercially available products such as "PHOSPHANOL ML-200" (manufactured by Toho Chemical Industry Co., Ltd., trade name).

[0859] The pretreatment solution containing one or more compounds having the specific functional groups described above can be, for example, an aqueous solution of the aforementioned compounds. Furthermore, the pretreatment solution may contain acids, bases, surfactants, chelating agents, etc.

[0860] Methods for treating fibrous materials with the aforementioned pretreatment solution include, for example, padding, impregnation, spraying, and coating. For padding, methods using padding apparatuses described in the *Dictionary of Fiber Dyeing and Processing* (1963, Nikkan Kogyo Shimbun) and *Color Dyeing Chemistry III* (1975, Jitsukyo Publishing Co., Ltd.) are examples. For coating, methods using coating machines described in the *General Overview of Dyeing and Finishing Equipment* (1981, Fiber Co., Ltd.) are examples. For impregnation, methods using intermittent dyeing machines described in the *General Overview of Dyeing and Finishing Equipment* (1981, Fiber Co., Ltd.) are examples, including liquid flow dyeing machines, airflow dyeing machines, drum dyeing machines, skein dyeing machines, washing dyeing machines, and package dyeing machines. Examples of spray treatment methods include air jetting, which uses compressed air to atomize the treatment liquid and then sprays it out, and air jetting using hydraulic atomization. The concentration of the treatment liquid and subsequent heat treatment conditions can be appropriately adjusted considering various factors such as the intended purpose and performance. Furthermore, if the pretreatment liquid contains water, drying is preferable to remove moisture after adhesion to the fibrous material. There are no particular limitations on the drying method; either dry heat or wet heat methods can be used. The drying temperature is also not particularly limited; for example, drying at room temperature to 200°C for 10 seconds to several days is sufficient. If necessary, after drying, a heat treatment at 100–180°C for approximately 10 seconds to 5 minutes can be performed.

[0861] To clarify, when the fiber material is to be dyed, the pretreatment with the pretreatment solution can be performed before dyeing or in the same bath as dyeing. However, when performing reduction soaping, the compounds with the above-mentioned specific functional groups (such as phenolic polymers) adsorbed during the process may be detached. Therefore, it is preferable to perform the treatment after reduction soaping following dyeing.

[0862] The immersion treatment temperature can be set to 60–130℃. The treatment time can be set to 5–60 minutes.

[0863] The functional group introduction process using the pretreatment liquid is preferably carried out in an amount of 1.0 to 7.0 parts by weight relative to 100 parts by weight of the fiber material. Within this range, a high level of both durable water repellency and hand feel can be achieved.

[0864] It is preferable to adjust the pH of the pretreatment solution to 3-5. pH adjustment can be achieved using pH adjusters such as acetic acid or malic acid.

[0865] In the pretreatment solution, in order to utilize the salting-out effect to effectively adsorb compounds with the aforementioned specific functional groups onto the fiber material, salts may also be used. Examples of usable salts include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate.

[0866] In the functional group introduction process using the pretreatment liquid, it is preferable to remove excess of the compound having the aforementioned specific functional groups. Washing with water is an example of such removal method. By ensuring thorough removal, obstacles to water repellency during subsequent water-repellent processing can be suppressed, and the resulting fiber product has a better hand feel. Furthermore, the obtained functional group-containing fibers are preferably thoroughly dried before contact with the hydrocarbon-based water-repellent agent.

[0867] As an example of (ii) a fiber in which the aforementioned specific functional groups are directly introduced into the material constituting the fiber, cationic dyeable polyester (CD-PET) can be cited.

[0868] For fibers containing functional groups, from the viewpoint of improving the water repellency of the resulting fiber products, the surface ZETA potential is preferably -100 to -0.1 mV, more preferably -50 to -1 mV. The surface ZETA potential of the fiber can be measured, for example, using a ZETA potential-particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0869] Example

[0870] The present invention will be described in detail below with examples, but the present invention is not limited to these examples.

[0871] <Experimental Methods>

[0872] The experimental procedure is as follows.

[0873] [Water repellency test]

[0874] The water repellency of the test fabric was evaluated according to the spray method of JIS-L-1092 (AATCC-22).

[0875] Evaluate water repellency according to the criteria shown below. Note that a higher score indicates better water repellency, and intermediate values ​​(95, 85, 75) are given depending on the condition.

[0876] No wetting or water droplet adhesion was observed on the surface.

[0877] 90% of the surface was not wet, but small water droplets were observed adhering to it.

[0878] 80 Wetting was observed on each small water droplet on the surface.

[0879] 70 shows wetness on half of the surface, and the state of each small wetted permeable cloth is observed.

[0880] 50 Wetting was observed across the entire surface.

[0881] Moisture was observed on both the surface and the back side.

[0882] [Durable Water Repellency]

[0883] Regarding the test fabric, after washing 20 times according to JIS L1930 Appendix F C4M, it was dried in a drum dryer (at 60°C for 30 minutes) and the water repellency of the resulting test fabric was evaluated.

[0884] [Feel]

[0885] The test fabric was evaluated by touch using the five stages shown below. Intermediate values ​​(3-4, 4-5) were given based on the condition.

[0886] 1: Hard ~ 5: Soft

[0887] [Chalk Mark Resistance]

[0888] Each test piece was placed on a flat surface. The surface of the test cloth was gently scratched with a fingernail, and the traces of the scratching with a fingernail were visually evaluated to determine the chalk residue.

[0889] ○: Almost no trace is visible

[0890] ○△: Faint traces can be seen

[0891] △: Traces are visible

[0892] △×: Slightly deeper marks can be seen.

[0893] ×: Deep marks can be seen.

[0894] [Peel strength]

[0895] For the test fabric, a heat-sealing device was used to heat-bond the hot-melt adhesive tape (MELCO tape manufactured by SAN Chemical Co., Ltd.) at 160°C for 15 seconds. The peel strength between the test fabric and the heat-sealing tape was then measured using a universal testing machine (AGS-J, manufactured by Shimadzu Corporation). The clamps were pulled at a moving speed of 200 mm / min, and the average stress was taken as the peel strength [N / inch].

[0896] [Preparation of raw materials]

[0897] (Example of manufacturing an aqueous dispersion containing acrylic polymer)

[0898] Manufacturing Example 1

[0899] Add 30g of water-soluble glycol solvent as an organic solvent, 120g of pure water as a liquid medium, 48g of stearyl acrylate (meth)acrylate containing long-chain aliphatic hydrocarbon groups, 2.0g of cationic emulsifier as a surfactant, 2.0g of sorbitan fatty acid ester, 6.0g of polyoxyethylene alkyl ether, and 0.1g of acetic acid to a 500ml plastic container. Heat at 60℃, stir at 2000rpm for 1 minute using a homogenizer, and then emulsify and disperse using ultrasound for 15 minutes.

[0900] The emulsified dispersion was then transferred to a 500 ml autoclave. After nitrogen purging, 0.2 g of lauryl mercaptan and 12 g of vinyl chloride were added as chain transfer agents. Subsequently, 1.0 g of a water-soluble initiator containing an azo group was added, and the mixture was heated to 60 °C and 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%.

[0901] Manufacturing Examples 2 and 3

[0902] Except for changing the formulation according to Table 1, the same procedure as in Manufacturing Example 1 was followed to prepare an aqueous dispersion containing an acrylic polymer, a surfactant, and a liquid medium.

[0903] Manufacturing Example 4

[0904] In a 500ml plastic container, add 30g of water-soluble glycol solvent as an organic solvent, 120g of pure water as a liquid medium, 60g of stearyl acrylate, 2.0g of cationic emulsifier as a surfactant, 2.0g of sorbitan fatty acid ester, and 6.0g of polyoxyethylene alkyl ether. Heat at 80℃, stir at 2000rpm for 1 minute using a homogenizer, and then emulsify and disperse using ultrasound for 15 minutes.

[0905] The emulsified dispersion was transferred to a 500cc four-necked flask equipped with a nitrogen inlet tube, thermometer, stir bar, and reflux tube. After nitrogen replacement, 0.2g of lauryl mercaptan was added and stirred. Then, 1.0g of a water-soluble initiator containing an azo group was added, and the mixture was heated to 60°C and reacted for 4 hours to obtain an aqueous dispersion of the polymer. Then, pure water was added to prepare an aqueous dispersion with a non-volatile component concentration of 30%.

[0906] Manufacturing Example 5

[0907] 1. Synthesis of Aliphatic Polyisocyanate Derivatives

[0908] In a reactor equipped with a thermometer, stirrer, nitrogen inlet pipe, and cooling pipe, under a nitrogen atmosphere, 500 parts by weight of 1,6-hexamethylene diisocyanate (HDI, manufactured by Mitsui Chemicals Co., Ltd., trade name: Takenate 700), 0.25 parts by weight of 2,6-di-tert-butyl-4-methylphenol (also known as butylated hydroxytoluene, BHT, hindered phenolic antioxidant), and 0.25 parts by weight of tetraphenyl-dipropylene glycol diphosphite (organophosphite, catalyst promoter) were mixed. Then, 10.7 parts by weight of 1,3-butanediol were added to the mixture, and nitrogen was introduced into the liquid phase for 1 hour. The mixture was then heated to 80°C and reacted for 3 hours, followed by cooling to 60°C. Then, as an isocyanurate esterification catalyst, 0.2 parts by weight of trimethyl-N-2-hydroxypropylammonium 2-ethylhexanoate was added, and the reaction was continued for 1.5 hours. Then, 0.04 parts by mass of o-toluenesulfonamide were added relative to 100 parts by mass of HDI. The reaction mixture was then passed through a thin-film distillation apparatus (temperature 150°C, vacuum 93.3 Pa) and distilled until the residual HDI monomer content was below 0.5%, yielding an aliphatic polyisocyanate derivative (an isocyanurate derivative of hexamethylene diisocyanate). The obtained aliphatic polyisocyanate derivative had an isocyanate group content of 20.9% and an average isocyanate functional group number of 3.0.

[0909] 2. Manufacturing of hydrocarbon-based polyurethanes

[0910] In a reactor equipped with a stirrer, thermometer, cooler, and nitrogen inlet pipe, 100.20 g of the above-mentioned aliphatic polyisocyanate derivative, 67.60 g of Kalkol 8098 (stearyl alcohol, manufactured by Kao Corporation) as a long-chain active hydrogen compound, and 22.30 g of oleyl alcohol were mixed and reacted at 110°C under a nitrogen atmosphere for 4 hours until the concentration of isocyanate groups reached 3.67%.

[0911] Next, the reaction solution was cooled to 80°C, and 9.90 g of N-methyldiethanolamine was added as a cationic active hydrogen compound. The reaction was carried out at 80°C for 1 hour.

[0912] Then, 50.00 g of methyl ethyl ketone was added as a solvent, and the reaction was carried out at 80 °C until the disappearance of the isocyanate group could be confirmed by infrared absorption spectroscopy.

[0913] 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. Then, the mixture was cooled to 75°C.

[0914] Then, 18.96g of acetic acid was added as an acid compound for neutralization.

[0915] Next, while maintaining the reaction solution at 75°C, 800.0g of ion-exchange water heated to 70°C was slowly added to emulsify (internal emulsification).

[0916] Next, using an evaporator, under reduced pressure at a water bath temperature of 60°C, the solvent was removed until the concentration of the solid component reached more than 20% by weight.

[0917] Next, an aqueous dispersion containing polyurethane was obtained by adjusting the concentration of solid components other than the acid compound (acetic acid) with ion-exchanged water to 20% by weight.

[0918] Preparation Example 1

[0919] 9.0 g of MQ-1600 (manufactured by Dow Toray Industries, Inc.) as the silicone resin, 9.0 g of KF-96-6CS (polydimethylsiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.) as the silicone oil, and 22 g of KF-96-50CS (polydimethylsiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.) as the silicone oil with a number average molecular weight of 1500 or higher were mixed until MQ-1600 dissolved. 4.0 g of polyoxyethylene alkyl ether was added and mixed. Then, 89 g of pure water as an aqueous medium was added to the mixture in small increments to obtain a dispersion containing a total of 30.0% by mass of silicone resin and silicone oil.

[0920] Preparation Examples 2-5

[0921] Except for changing the formulation according to Table 1, the same procedure as in Preparation Example 1 was followed to obtain a dispersion containing a total of 30.0% by mass of silicone resin and silicone oil.

[0922] Comparative Preparation Example 1

[0923] 9.0 g of MQ-1600 (manufactured by Dow Toray Industries, Inc.) as the silicone resin, 9.0 g of KF-96-6CS (polydimethylsiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.) as the silicone oil with a number average molecular weight less than 1500, and 22 g of FZ-3710 (manufactured by Dow Toray Industries, Inc.) as the amino-modified silicone oil were mixed until MQ-1600 dissolved. 4.0 g of polyoxyethylene alkyl ether was added and mixed. Then, 89 g of pure water as an aqueous medium was added to the mixture in small increments to obtain a dispersion containing a total of 30.0% by mass of silicone resin and silicone oil.

[0924] Example 1

[0925] The fluorine-free acrylic polymer dispersion, the organosilicon compound dispersion, and tap water were mixed in the manner shown in Table 3 (the values ​​in the table represent (wt%)) to obtain treatment solutions of the water-repellent composition. Polyester fabric, nylon fabric, polyester / polyurethane (PU) fabric, and cotton fabric were then soaked in this treatment solution and pressed using a padding machine. The treated fabric was then passed through a pin-plate tenter frame at 170°C for 1 minute for drying and curing. For cotton fabric, the process was repeated at 170°C for 3 minutes to dry and cure.

[0926] The test fabric obtained through this treatment was used to conduct tests on water repellency, durable water repellency, hand feel, chalk mark resistance, and peel strength. The results are shown in Table 3.

[0927] Examples 2-12, Comparative Examples 1-4

[0928] Except for modifying the formulation according to Table 3, the procedure was the same as in Example 1, and the fabric was treated in the same way. Tests were conducted on water repellency, durable water repellency, hand feel, chalk mark resistance, and peel strength. The results are shown in Table 3.

[0929] [Table 1]

[0930]

[0931] The numbers in the table represent the amount of feed added (g) [Table 2]

[0932]

[0933] The numbers in the table represent the amount of feed added (g) [Table 3]

[0934]

Claims

1. A water-repellent composition, characterized in that: The compound comprises a polymer (A) and an organosilicon compound (B) comprising silicone oil and silicone resin, wherein the polymer (A) comprises repeating units derived from a hydrocarbon-containing monomer (a) having a hydrocarbon group having 2 to 40 carbon atoms. In the GPC plot of the organosilicon compound (B), peaks are present in the region with molecular weights above 1500. The organosilicon compound containing components with a molecular weight of 1500 or higher contains silicone oils other than amino-modified silicones. The amount of the organosilicon compound (B) is 1 to 49% by weight, relative to the total amount of the polymer (A) and the organosilicon compound (B).

2. The water-repellent composition according to claim 1, characterized in that: The hydrocarbon group in the hydrocarbon-containing monomer (a) is a straight-chain alkyl group with 10 or more carbon atoms.

3. The water-repellent composition according to claim 1, characterized in that: The hydrocarbon-containing monomer (a) is a monomer represented by the following formula. CH2=C(-X a )-C(=O)-Y a (R a ) k In the formula, R a Each is independently a hydrocarbon group with 2 to 40 carbon atoms. X a It can be a hydrogen atom, a monovalent organic group, or a halogen atom. Y a It is a group consisting of at least one selected from hydrocarbon groups with 1 carbon atom in the range of 2 to 4 valence, -C6H4-, -O-, -C(=O)-, -S(=O)2- or -NH-, where k is 1 to 3.

4. The water-repellent composition according to claim 1, characterized in that: The amount of the organosilicon compound (B) is 1 to 25% by weight, relative to the total amount of the polymer (A) and the organosilicon compound (B).

5. The water-repellent composition according to claim 1, characterized in that: It contains surfactants.

6. The water-repellent composition according to claim 5, characterized in that: The surfactants include nonionic surfactants.

7. The water-repellent composition according to claim 1, characterized in that: It is an aqueous dispersion.

8. A method for manufacturing a fiber product, characterized in that, include: The step of applying the water-repellent composition according to any one of claims 1 to 7 to the fiber substrate.

9. The method for manufacturing fiber products according to claim 8, characterized in that, include: The process of imparting functional groups to the fibers, selected from one or more monovalent groups shown in the following formula, prior to applying the water-repellent composition to the fiber substrate: -SO3M 1 The monovalent group shown in the formula, where M 1 Indicates a monovalent cation; -COOM 2 The monovalent group shown in the formula, where M 2 Indicates a monovalent cation; -OP(O)(OX 1 (OX) 2 The monovalent group shown in the formula is X, where X is a monovalent group. 1 and X 2 Alkyl groups, which can be independently represented by 1 to 22 hydrogen atoms or carbon atoms respectively.

10. A fiber product, characterized in that: The polymer (A) and the organosilicon compound (B) of any one of claims 1 to 7 are attached to a fiber substrate.

11. The fiber product according to claim 10, characterized in that: Compounds having attached functional groups having one or more monovalent groups selected from the following formulas: -SO3M 1 The monovalent group shown in the formula, where M 1 Indicates a monovalent cation; -COOM 2 The monovalent group shown in the formula, where M 2 Indicates a monovalent cation; -OP(O)(OX 1 (OX) 2 The monovalent group shown in the formula is X, where X is a monovalent group. 1 and X 2 Alkyl groups, which can be independently represented by 1 to 22 hydrogen atoms or carbon atoms respectively.

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