Polymer, water repellent, fibrous product and method of manufacturing a fibrous product

Abstract

A polymer comprising repeating units derived from monomer (1) shown in formula (1-1) or formula (1-2) below, and having an adhesion of 800 gf or less. [In each formula, R] a X is a polymerizable organic group, X is a single bond or a divalent group, Y is independently a hydrocarbon group with 1 to 10 hydrogen atoms, α is an integer from 1 to 3, β is an integer of 1 or 2, and Z is independently -Z 1 -SiZ 2 3－m Z 3 m Z 1 Z is a single bond or a divalent group. 2 Each is an independent hydrocarbon group with 1 to 10 carbon atoms, where m is an integer from 1 to 3, and Z 3 They are independently -(O-SiZ) 31 2) p -(CH2) q -Z 32 -SiZ 33 3, Z 31 Each is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 311 3, Z 311 Each is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 3111 3, Z 3111 Each is an independent hydrocarbon group having 1 to 10 carbon atoms, Z 32 For O or CH2, Z 33 Each is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 331 3, Z 331 Each group is an independent hydrocarbon group with 1 to 10 carbon atoms, where p is an integer from 0 to 196 and q is an integer from 0 to 10. a -X-CY 3－α Z α (1-1)R a -X-NY 2－β Z β (1-2)

Description

Technical Field

[0001] This invention relates to polymers, water-repellent agents, fiber products, and methods for manufacturing fiber products. Background Technology

[0002] The development of non-fluorinated water-repellent agents is underway as a means of imparting water-repellent properties to base materials (especially fiber products).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: International Publication No. 2023 / 086692

[0006] Patent Document 2: International Publication No. 2023 / 019044

[0007] Patent Document 3: International Publication No. 2023 / 197350

[0008] Patent Document 4: Japanese Patent Application Publication No. 2017 / 218713 Summary of the Invention

[0009] The technical problem to be solved by the present invention

[0010] Patent Document 1 discloses a method for treating textile products and other materials with a composition obtained by dissolving an organosilicon copolymer containing structural units derived from (meth)acrylate monomers in a solvent, thereby imparting good chalk stain resistance. However, the water-repellent and oil-repellent properties are not satisfactory. Furthermore, viscosity is a desirable requirement for water-repellent agents. Materials with high viscosity tend to have increased adhesion, which can contaminate equipment during textile product processing. Therefore, materials with low viscosity are desirable for water-repellent agents.

[0011] The purpose of this invention is to provide a polymer with low adhesion and the ability to impart excellent water-repellent and oil-repellent properties to a substrate.

[0012] Technical means for solving technical problems

[0013] The present invention includes the following methods.

[0014] [Item 1] A polymer comprising repeating units derived from monomer (1) shown in formula (1-1) or formula (1-2) below, wherein the viscosity of the polymer is 800 gf or less.

[0015] R a -X-CY 3－α Z α (1-1)

[0016] R a -X-NY 2－β Z β (1-2)

[0017] [Among the various forms,]

[0018] R a It is a polymerizable organic group.

[0019] X is a single bond or a divalent group.

[0020] Y can be independently a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms.

[0021] α is an integer from 1 to 3.

[0022] β is an integer of 1 or 2.

[0023] Z is independently -Z 1 -SiZ 2 3－m Z 3 m ,

[0024] Z 1 It is a single bond or a divalent group.

[0025] Z 2 Each is independently a hydrocarbon group having 1 to 10 carbon atoms.

[0026] m is an integer from 1 to 3.

[0027] Z 3 They are independently -(O-SiZ) 31 2) p -(CH2) q -Z 32 -SiZ 33 3,

[0028] Z 31 Each is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 311 3,

[0029] Z 311 Each is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 3111 3,

[0030] Z 3111 Each is independently a hydrocarbon group having 1 to 10 carbon atoms.

[0031] Z 32 It is O or CH2.

[0032] Z 33Each is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 331 3,

[0033] Z 331 Each is independently a hydrocarbon group having 1 to 10 carbon atoms.

[0034] p is an integer from 0 to 196.

[0035] q is an integer from 0 to 10.

[0036] [Item 2] The polymer as described in Item 1 has an adhesion of 600 gf or less.

[0037] [Item 3] The polymer as described in Item 1 or 2 has an adhesion of less than 300 gf.

[0038] [Item 4] The polymer as described in any one of items 1 to 3, wherein,

[0039] X is selected from X 1 and X 2 One or more divalent groups constituted,

[0040] X 1 It is a directly bonded group composed of one or more groups selected from -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, and -C(OR')R'- (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms each time it appears).

[0041] X 2 It can be a hydrocarbon group with 1 to 22 carbon atoms that is directly bonded or can have substituents.

[0042] [Item 5] The polymer as described in any one of items 1 to 4, wherein,

[0043] X is a hydrocarbon group with 1 to 22 carbon atoms that is directly bonded or may have substituents.

[0044] [Item 6] The polymer as described in any one of items 1 to 5, wherein,

[0045] Z 1 The source is Z. 11 and Z 12 One or more divalent groups constituted,

[0046] Z 11 It is a directly bonded group composed of one or more groups selected from -O-, -C(=O)-, -C(=NR'')-, -S-, -S(=O)2-, -NR''-, and -C(OR'')R''- (where R'' is independently a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms each time it appears).

[0047] Z 12 It can be a hydrocarbon group with 1 to 22 carbon atoms that is directly bonded or can have substituents.

[0048] [Item 7] The polymer as described in any one of items 1 to 6, wherein,

[0049] Z 1 It can be a hydrocarbon group with 1 to 22 carbon atoms that is directly bonded or can have substituents.

[0050] [Item 8] A polymer as described in any one of items 1 to 7, wherein,

[0051] R a It is an organic group containing an olefinic polymeric group.

[0052] [Item 9] The polymer as described in any one of items 1 to 8, wherein,

[0053] R a It is acryloyl or methacryloyl.

[0054] [Item 10] The polymer as described in any one of items 1 to 9, wherein,

[0055] It also contains repeating units derived from hydrophobic monomers (2) having 2 to 40 carbon atoms.

[0056] [Item 11] The polymer as described in Item 10, wherein,

[0057] The hydrophobic monomer (2) mentioned above is the monomer shown in the following formula (2).

[0058] CH2=C(-R b )-C(=O)-R c -(R) d ) k (2)

[0059] [In the formula,]

[0060] R b It can be a hydrogen atom, a monovalent organic group, or a halogen atom.

[0061] R c It is a direct bond, a hydrocarbon group with 1 carbon atom in the 2-4 valence, and composed of -C6H4-, -O-, -S-, -C(=O)-, -S(=O)2- and -NR-. C1 - (R) C1 A divalent to tetravalent group consisting of at least one of a hydrocarbon group having 1 to 4 carbon atoms (either a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms).

[0062] k is 1 to 3

[0063] Rd It consists of hydrocarbon groups with 2 to 40 carbon atoms.

[0064] [Item 12] The polymer as described in Item 10 or 11, wherein,

[0065] The amount of repeating units derived from the above-mentioned hydrophobic monomer (2) is 20% by weight or more relative to the polymer.

[0066] [Item 13] The polymer as described in any one of items 10 to 13, wherein,

[0067] The amount of repeating units derived from the monomer unit (1) is 0.5% by weight or more relative to the polymer.

[0068] [Item 14] The polymer as described in any one of items 1 to 13 is a non-fluorinated polymer.

[0069] [Item 15] The polymer as described in Item 1, wherein,

[0070] R a It can be CH2=CHC(=O)-O- or CH2=CCH3C(=O)-O-.

[0071] X is a directly bonded or alkylene group having 1 to 5 carbon atoms.

[0072] Y can be an alkyl chain with 1 to 3 carbon atoms, or either a hydrogen atom or a carbon atom.

[0073] [Item 16] The polymer as described in Item 1, wherein,

[0074] α is 1,

[0075] β is 1,

[0076] Z is independently -Z 1 -SiZ 2 3－m Z 3 m ,

[0077] Z 1 It is a single bond or -(CH2). s -,

[0078] s is an integer from 1 to 3.

[0079] Z 2 Each is independently an alkyl group having 1 to 3 carbon atoms.

[0080] m is an integer from 1 to 3.

[0081] Z 3 They are independently -(O-SiZ) 31 2) p-(CH2) q -Z 32 -SiZ 33 3,

[0082] p can be 0 or 1 independently.

[0083] q can be 0 or 1 independently.

[0084] Z 31 Each is independently an alkyl group having 1 to 3 carbon atoms.

[0085] Z 32 It is -O- or -CH2-.

[0086] Z 33 Each is independently an alkyl group having 1 to 3 carbon atoms or -OSiZ 331 3,

[0087] Z 331 Each is independently an alkyl group having 1 to 3 carbon atoms.

[0088] The viscosity of the above polymer is below 300 gf.

[0089] [Item 17] The polymer as claimed in claim 1, wherein,

[0090] R a It can be CH2=CHC(=O)-O- or CH2=CCH3C(=O)-O-.

[0091] X is a directly bonded or alkylene group having 1 to 5 carbon atoms.

[0092] Y is either a hydrogen atom or an alkyl chain with 1 to 3 carbon atoms.

[0093] α is 1,

[0094] β is 1,

[0095] Z is independently -Z 1 -SiZ 2 3－m Z 3 m ,

[0096] Z 1 It is a single bond or -(CH2). s -,

[0097] s is an integer from 1 to 3.

[0098] Z 2 Each is independently an alkyl group having 1 to 3 carbon atoms.

[0099] m is an integer from 1 to 3.

[0100] Z 3 They are independently -(O-SiZ) 31 2) p -(CH2) q -Z 32 -SiZ 33 3,

[0101] p can be 0 or 1 independently.

[0102] q can be 0 or 1 independently.

[0103] Z 31 Each is independently an alkyl group having 1 to 3 carbon atoms.

[0104] Z 32 It is -O- or -CH2-.

[0105] Z 33 Each is independently an alkyl group having 1 to 3 carbon atoms or -OSiZ 331 3,

[0106] Z 331 Each is independently an alkyl group having 1 to 3 carbon atoms.

[0107] The viscosity of the above polymer is below 300 gf.

[0108] [Item 18] A composition comprising the polymer and emulsifier described in any one of items 1 to 17.

[0109] [Item 19] The composition as described in Item 18 contains water.

[0110] [Item 20] A water-repellent agent comprising any one of items 1 to 17, or a composition described in item 18 or 19.

[0111] [Item 21] A water-repellent fiber article having the polymer described in any one of items 1 to 17 attached to a fiber substrate.

[0112] [Item 22] The water-repellent fiber product as described in Item 21, wherein,

[0113] An ingredient selected from SO3M is attached to the above-mentioned fiber substrate. 1 (where M) 1 The monovalent group (representing a monovalent cation) and -COOM are indicated by the 1-valent group. 2 (where M) 2 The monovalent group (representing a monovalent cation) and -O-P(O)(OX) are shown. 1 (OX) 2 (where X) 1 and X 2A compound that contains one or more functional groups (each representing a hydrogen atom or an alkyl group with 1 to 22 carbon atoms) that are monovalent groups.

[0114] [Item 23] A method for manufacturing a water-repellent fiber article, comprising the step of applying the water-repellent agent described in Item 20 to a fiber substrate.

[0115] [Item 24] A method for manufacturing a water-repellent fiber product as described in Item 23, wherein,

[0116] Before applying the above-mentioned water-repellent agent to the fiber substrate, the fiber substrate is subjected to a coating selected from SO3M. 1 (where M) 1 The monovalent group (representing a monovalent cation) and -COOM are indicated by the 1-valent group. 2 (where M) 2 The monovalent group (representing a monovalent cation) and -O-P(O)(OX) are shown. 1 (OX) 2 (where X) 1 and X 2 A process of performing one or more functional groups (each independently representing a hydrogen atom or an alkyl group with 1 to 22 carbon atoms) in a monovalent group.

[0117] Invention Effects

[0118] The polymer of the present invention has low viscosity and can impart excellent water-repellent and oil-repellent properties to the substrate. Detailed Implementation

[0119] <Definition of Terms>

[0120] In this specification, "n-valent group" refers to a group having n valence bonds, that is, a group forming n bonds. Additionally, "n-valent organic group" refers to an n-valent group containing carbon, and "organic group" refers to a group containing carbon. There is no particular limitation on such organic groups; they can be hydrocarbon groups or their derivatives. Derivatives of hydrocarbon groups refer to groups having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc., at the end of the hydrocarbon group or in the molecular chain.

[0121] In the context of this specification, "hydrocarbon group" refers to a group containing carbon and hydrogen, specifically a group that has had a hydrogen atom removed from a hydrocarbon. There is no particular limitation on the type of hydrocarbon group; it can be a C1-20 hydrocarbon group, such as an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aforementioned "aliphatic hydrocarbon group" can be linear, branched, or cyclic, and can be saturated or unsaturated. Furthermore, the hydrocarbon group can contain one or more ring structures. The hydrocarbon group can be substituted by one or more substituents.

[0122] In this specification, whether or not the expressions "independent each time it appears", "independent of each other", "independent of each other" or the same are explicitly stated, unless otherwise stated, when a term (symbol) that may appear multiple times is defined in a chemical structure, that definition applies independently each time it appears.

[0123] It should be understood that the chemical structures described in this specification do not include chemical structures that are considered chemically impossible or extremely unstable by those skilled in the art.

[0124] <Polymer>

[0125] The polymer of the present invention comprises repeating units derived from monomer (1) shown in formula (1-1) or formula (1-2) below, and has an adhesion of 800 gf or less.

[0126] R a -X-CY 3－α Z α (1-1)

[0127] R a -X-NY 2－β Z β (1-2)

[0128] [Among the various forms,]

[0129] R a It is a polymerizable organic group.

[0130] X is a single bond or a divalent group.

[0131] Y can be independently a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms.

[0132] α is an integer from 1 to 3.

[0133] β is an integer of 1 or 2.

[0134] Z is independently -Z 1 -SiZ 2 3－m Z 3 m ,

[0135] Z 1 It is a single bond or a divalent group.

[0136] Z 2 Each is independently a hydrocarbon group having 1 to 10 carbon atoms.

[0137] m is an integer from 1 to 3.

[0138] Z 3 They are independently -(O-SiZ) 31 2)p -(CH2) q -Z 32 -SiZ 33 3,

[0139] Z 31 Each is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 311 3,

[0140] Z 311 Each is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 3111 3,

[0141] Z 3111 Each is independently a hydrocarbon group having 1 to 10 carbon atoms.

[0142] Z 32 It is O or CH2.

[0143] Z 33 Each is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 331 3,

[0144] Z 331 Each is independently a hydrocarbon group having 1 to 10 carbon atoms.

[0145] p is an integer from 0 to 196.

[0146] q is an integer from 0 to 10.

[0147] The polymers of the present invention possess the above-described characteristics, enabling them to impart liquid-repellent properties (water-repellent, oil-repellent, oil-resistant, and / or water-resistant) to substrates (e.g., fiber substrates, paper substrates). The polymers of the present invention can function as at least one selected from water-repellent agents, oil-repellent agents, oil-resistant agents, and water-resistant agents. The repellent agents of the present invention can impart good oil resistance (oil repellency) and / or water resistance (water repellency) to the substrate, for example, imparting both good oil resistance and water resistance.

[0148] The polymers of the present invention possess the above-mentioned characteristics, enabling them to impart excellent water-repellent and oil-repellent properties to substrates (e.g., fiber substrates, paper substrates).

[0149] The polymer of the present invention possesses the above-described characteristics, resulting in reduced viscosity. The viscosity of compositions containing the polymer of the present invention and water-repellent agents is also reduced. Therefore, equipment contamination can be reduced.

[0150] [Adhesion]

[0151] Adhesion is an indicator of the strength of adhesive force. A higher adhesion value indicates stronger adhesion, while a lower adhesion value indicates weaker adhesion. From the perspective of reducing equipment contamination, a lower adhesion value is preferable.

[0152] The polymer of the present invention has a viscosity of 800 gf or less. From the viewpoint of reducing equipment contamination, the viscosity of the polymer of the present invention can be 700 gf or less, 600 gf or less, 500 gf or less, 450 gf or less, 400 gf or less, 350 gf or less, 300 gf or less, 250 gf or less, or 200 gf or less, preferably 600 gf or less, and more preferably 300 gf or less.

[0153] Adhesion can be obtained using the following measurement method.

[0154] The product obtained by drying the water-repellent composition (e.g., a solution or dispersion containing a polymer) at 50–60°C for 2 hours, or by extracting the water-repellent composition (e.g., a solution or dispersion containing a polymer) with alcohol, is placed on a metal sample stage with a diameter of 80 mm and heated at 40°C for 3 minutes. Evaluation is then performed using a probe with a diameter of 50 mm. The viscosity is calculated as the average of three measurements, or, if fluctuations are observed, five measurements are taken, removing the upper and lower limits, and the average of the remaining values ​​is used.

[0155] The machine name and test conditions can be carried out under the following conditions.

[0156] Machine Name: RHESCA Viscosity Testing Machine TAC-II

[0157] Test conditions:

[0158] constant load

[0159] (1) Descent speed: 120 mm / min.

[0160] (2) Test speed: 600 mm / min.

[0161] (3) Preload: 500gf

[0162] (4) Holding time: 10 seconds

[0163] (5) Distance: 5mm

[0164] The higher the measured value, the greater the adhesion.

[0165] The viscosity of the polymer of this invention can be controlled by adjusting the polymer's molecular structure, molecular weight, and molecular weight distribution. The higher the molecular weight of the polymer, the easier it is to reduce viscosity. In the polymer's molecular weight distribution, the smaller the proportion of low molecular weight polymers, the easier it is to reduce viscosity. The polymer's molecular weight and molecular weight distribution can be controlled using known methods. For example, the polymer's molecular weight and molecular weight distribution can be controlled by adjusting the type and amount of initiator, using chain transfer agents, polymerization temperature, monomer concentration, etc.

[0166] [Weight-average molecular weight]

[0167] The weight-average molecular weight of the polymer can be above 100,000, above 120,000, above 130,000, above 140,000, above 150,000, or above 200,000. The weight-average molecular weight of the polymer can be below 1,000,000, below 750,000, below 500,000, below 400,000, or below 300,000.

[0168] [Number Average Molecular Weight]

[0169] The number average molecular weight of the polymer can be above 30,000, above 40,000, 50,000, or above 60,000. The number average molecular weight of the polymer can be below 100,000, below 75,000, below 50,000, below 40,000, or below 30,000.

[0170] The average molecular weight (weight-average molecular weight Mw and / or number-average molecular weight Mn) of the polymers of the present invention can be obtained by the following determination methods.

[0171] Average molecular weight:

[0172] The average molecular weight of the copolymer was determined by GPC (gel permeation chromatography) (converted from polystyrene).

[0173] For gel permeation chromatography, an HLC-8420GPC EcoSEC Elite-WS (manufactured by Tosoh Corporation) was used. For the column, a column consisting of two TSKgel Super Multipore HZ-M columns connected together was used. For the detector, an RI detector was used. For the reference material, standard polystyrene (SRM706a NIST) was used.

[0174] The analytical sample was prepared by dissolving the copolymer in tetrahydrofuran to prepare a 0.1% by weight solution, which was then passed through a 0.5 μm filter. For the determination of 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.

[0175] The polymers of the present invention can be non-fluorinated polymers. Specifically, the polymers of the present invention may not have perfluoroalkyl groups with 8 or more carbon atoms, perfluoroalkyl groups with 6 or more carbon atoms, perfluoroalkyl groups, fluoroalkyl groups, or fluorinated atoms.

[0176] (1) Monomer

[0177] The polymer of the present invention comprises repeating units derived from monomer (1). Monomer (1) is represented by the following formula (1-1) or formula (1-2). The following description applies independently to formulas (1-1) and (1-2), respectively.

[0178] R a -X-CY 3－α Z α (1-1)

[0179] R a -X-NY 2－β Z β (1-2)

[0180] [R] a ]

[0181] R a It is a polymerizable organic group.

[0182] Polymerizable organic groups are organic groups that possess the property of initiating polymerization reactions by reacting chemically with some molecules in response to external stimuli such as heat, light, or free radicals, resulting in cleavage or decomposition. Polymerization can be chain polymerization and / or step-polymerization. Examples of polymerizable organic groups include free radical polymerizable organic groups, cationic polymerizable organic groups, anionic polymerizable organic groups, ring-opening polymerizable organic groups, condensation polymerizable organic groups, and addition polymerizable organic groups.

[0183] R a These can be organic groups containing olefinic polymeric groups. An olefinic polymeric group is a group containing an olefinic unsaturated bond (i.e., a carbon-carbon double bond). Monomers containing organic groups containing olefinic polymeric groups can form polymers through polymerization reactions such as free radical polymerization. Such monomers are also called olefinic unsaturated monomers.

[0184] The organic group containing the olefin polymerizable group is not particularly limited and can be vinyl, vinylidene, vinylidene, acryloyl, methacryloyl or its derivatives.

[0185] R a It can be a group as shown in the following formula.

[0186] CR a1 R a2 =C(-R) a3)-R a4 -

[0187] [In the formula,

[0188] R a1 R a2 and R a3 Each can be independently a hydrogen atom, a monovalent organic group, or a halogen atom.

[0189] R a4 It can be a single bond or a divalent group.

[0190] R a1 R a2 and R a3 Each can be independently a hydrogen atom, a monovalent organic group, or a halogen atom.

[0191] R a1 R a2 and R a3 It can be independently a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. R a1 R a2 and R a3 Each can be independently a hydrogen atom, methyl group, chlorine atom, bromine atom, iodine atom, or cyano group. R a1 R a2 and R a3 Preferably, each is an independent hydrogen atom, methyl atom, or chlorine atom.

[0192] R a4 It is a single bond or a divalent group. R a4 Preferably, it has a divalent group.

[0193] R a4 It can be selected from R a41 and R a42 A group consisting of one or more of the following.

[0194] R a41 A group consisting of one or more selected from -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, and -C(OR')R'- (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms (e.g., 1 to 5, 1 to 3, or 1 carbon atoms) in each occurrence of the direct bond.

[0195] R a42 It is a direct bond or a hydrocarbon group with 1 to 22 carbon atoms.

[0196] As R a41 Examples can be listed as follows:

[0197] direct bond,

[0198] -O-、

[0199] -O-C(=O)-、

[0200] -O-C(=O)-O-、

[0201] -O-C(=O)-NR'-、

[0202] -NR'-、

[0203] -NR'-C(=O)-、

[0204] -NR'-C(=O)-O-、

[0205] -NR'-C(=O)-NR'-、

[0206] -C(=O)-、

[0207] -C(=O)-O-、

[0208] -C(=O)-NR'-、

[0209] -SO2-,

[0210] -SO2NR'-,

[0211] -C(OR')R'- etc.

[0212] (In the formula, R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears.)

[0213] R a42 It can be a hydrocarbon group with 1 to 22 carbon atoms. The number of carbon atoms in the hydrocarbon group can be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 7 or more, 9 or more, 11 or more, or 13 or more, and can be less than 22, less than 20, less than 18, less than 16, less than 14, or less than 12, less than 10, less than 8, less than 6, less than 5, less than 4, or less than 3.

[0214] As R a42 Specific examples can be listed as -(CH2). q - q is an integer from 1 to 22. q can be 1 or higher, 2 or higher, 3 or higher, 4 or higher, 5 or higher, 7 or higher, 9 or higher, 11 or higher, or 13 or higher. q can be less than 22, less than 20, less than 18, less than 16, less than 14, or less than 12, less than 10, less than 8, less than 6, less than 5, less than 4, or less than 3.

[0215] R a4The molecular weight can be above 10, above 50, above 100, above 200, above 300, above 500, or above 750. R a4 The molecular weight can be below 3000, below 2500, below 2000, below 1500, below 1000, below 750, below 500, below 300, below 200, below 100, or below 50.

[0216] From the perspective of improving water repellency, R a It can be acryloyl or methacryloyl. Specifically, R a It can be CH2=CHC(=O)- or CH2=CCH3C(=O)-.

[0217] Acryloyl or methacryloyl groups can also be derivatives. Examples of derivatives of acryloyl or methacryloyl groups include:

[0218] CH2=CHC(=O)-O-

[0219] CH2=CCH3C(=O)-O-

[0220] CH2=CHC(=O)-NR'-

[0221] CH2=CCH3C(=O)-NR'-

[0222] CH2=CHC(=O)-SR'-

[0223] CH2=CCH3C(=O)-SR'- etc.

[0224] (In the formula, R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears.)

[0225] R a Specific examples can be listed as follows: CH2=CH-, CH2=CCH3-, CH2=CHC(=O)-O-, CH2=CCH3C(=O)-O-, CH2=CHC(=O)-NH- or CH2=CCH3C(=O)-NH-.

[0226] [X]

[0227] X is a single bond or a divalent group. X is preferably a divalent group.

[0228] X is selected from X 1 and X 2 One or more divalent groups constituted,

[0229] X 1A group consisting of one or more selected from -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, and -C(OR')R'- (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms (e.g., 1 to 5, 1 to 3, or 1 carbon atoms) in each occurrence of the direct bond.

[0230] X 2 It can be a directly bonded hydrocarbon group or a divalent hydrocarbon group with 1 to 22 carbon atoms that has a substituent.

[0231] The molecular weight of X can be 10 or higher, 50 or higher, 100 or higher, 200 or higher, 300 or higher, 500 or higher, or 750 or higher. The molecular weight of X can be less than 3000, less than 2500, less than 2000, less than 1500, less than 1000, less than 750, less than 500, less than 300, less than 200, less than 100, or less than 50.

[0232] [X] 1 ]

[0233] X 1 It is a non-hydrocarbon linker.

[0234] X 1 It is a directly bonded or divalent group. X is preferred. 1 It is not only a direct bond.

[0235] X 1 The molecular weight can be below 2000, below 1500, below 1000, below 750, or below 500. X 1 The molecular weight can be above 10, above 50, above 100, above 200, above 300, or above 500.

[0236] X 1 It is composed of one or more selected from -O-, -C(=O)-, -S(=O)2-, -NR'-, and -C(OR')R'- (where R' independently consists of 1 to 30 hydrogen or carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears. As Y 1 Examples can be listed as follows:

[0237] direct bond,

[0238] -O-、

[0239] -O-C(=O)-、

[0240] -O-C(=O)-O-、

[0241] -O-C(=O)-NR'-、

[0242] -NR'-、

[0243] -NR'-C(=O)-、

[0244] -NR'-C(=O)-O-、

[0245] -NR'-C(=O)-NR'-、

[0246] -C(=O)-、

[0247] -C(=O)-O-、

[0248] -C(=O)-NR'-、

[0249] -SO2-,

[0250] -SO2NR'-,

[0251] -C(OR')R'-、

[0252] -C(OR')(-)2 etc.

[0253] (In the formula, R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears.)

[0254] [X] 2 ]

[0255] X 2 It can be a directly bonded or divalent hydrocarbon group that may have substituents.

[0256] X 2 The number of carbon atoms can be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 7 or more, 9 or more, 11 or more, or 13 or more. X 2 The number of carbon atoms can be less than 22, less than 20, less than 18, less than 16, less than 14, or less than 12, less than 10, less than 8, less than 6, less than 5, less than 4, or less than 3.

[0257] The divalent hydrocarbon group can be a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon ring. The aliphatic hydrocarbon group can be cyclic, branched, or straight-chain. The divalent aliphatic hydrocarbon group can be saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group can be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 7 or more, 9 or more, 11 or more, or 13 or more, and can be less than 22, less than 20, less than 18, less than 16, less than 14, or less than 12, less than 10, less than 8, less than 6, less than 5, less than 4, or less than 3.

[0258] X 2The hydrocarbon group in the formula may have substituents. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms each time it appears). Substituents may or may not have active hydrogen. The number of substituents can be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0.

[0259] As X 2 Specific examples can be listed as -(CH2). q - q is an integer from 1 to 22. q can be 1 or higher, 2 or higher, 3 or higher, 4 or higher, 5 or higher, 7 or higher, 9 or higher, 11 or higher, or 13 or higher. q can be less than 22, less than 20, less than 18, less than 16, less than 14, or less than 12, less than 10, less than 8, less than 6, less than 5, less than 4, or less than 3.

[0260] Specific examples of divalent aromatic hydrocarbon rings include groups from which 2 to 4 hydrogen atoms have been removed from aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, benzo[a]nephthalene, penta[a]nephthalene, pyrene, and phenanthrene. The number of ring atoms in the aromatic hydrocarbon ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the aromatic hydrocarbon ring can be 2 or more, 3 or more, or 4, and can be 4 or less, 3 or less, or 2.

[0261] The divalent aromatic ring may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms each time it appears). 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 aromatic ring having 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 be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0262] [Example X]

[0263] As an example of X, we can list -X 1 -、-X 1 -X 2 -、-X 1 -X 2 -X 1 -、-X 1 -X2 -X 1 -X 2 -、-X 2 -、-X 2 -X 1 -、-X 2 -X 1 -X 2 -、-X 2 -X 1 -X 2 -X 1 - etc. As a preferred example of X, we can list -X 1 -X 2 -、-X 2 -.

[0264] X can be a directly bonded hydrocarbon group or a hydrocarbon group with 1 to 22 carbon atoms that may have substituents. Preferably, X is a hydrocarbon group with 1 to 22 carbon atoms that may have substituents. The number of carbon atoms in the hydrocarbon group of X can be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 7 or more, 9 or more, 11 or more, or 13 or more. The number of carbon atoms in the hydrocarbon with 1 to 22 carbon atoms of X can be 22 or less, 20 or less, 18 or less, 16 or less, 14 or less, or 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0265] As a specific example of X, we can list -(CH2). q - q is an integer from 1 to 22. q can be 1 or higher, 2 or higher, 3 or higher, 4 or higher, 5 or higher, 7 or higher, 9 or higher, 11 or higher, or 13 or higher. q can be less than 22, less than 20, less than 18, less than 16, less than 14, or less than 12, less than 10, less than 8, less than 6, less than 5, less than 4, or less than 3.

[0266] As a specific example of X, it is a directly bonded or alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms.

[0267] [Y]

[0268] Y is independently a hydrocarbon group having 1 to 10 hydrogen atoms or carbon atoms. Y is preferably a branched or straight-chain (preferably a long-chain straight-chain) hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group, and especially an alkyl group. The surface free energy of the -CH3 group is lower than that of the -CH2- group, and it tends to exhibit liquid-repellent properties. Therefore, structures with many branches and many -CH3 groups are preferred. On the other hand, long-chain alkyl groups of a certain length exhibit high liquid-repellent properties due to their crystallinity. Therefore, it can be a branched hydrocarbon group (e.g., a branched alkyl group), especially tert-butyl or isopropyl, a multi-branched group, or a long-chain hydrocarbon group (or a long-chain straight-chain hydrocarbon group), such as an alkyl group.

[0269] Y can be a hydrogen atom independently.

[0270] Hydrocarbons with 1 to 10 carbon atoms in Y can have 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more carbon atoms. Hydrocarbons with 1 to 10 carbon atoms in Y can have less than 10, less than 8, less than 6, less than 5, less than 4, or less than 3 carbon atoms.

[0271] For example, Y can be -(CH2). n -CH3. n can be 0 to 9, and can be above 0, above 1, above 2, above 3, above 4 or above 6, and can be below 9, below 8, below 6, below 5, below 4 or below 3.

[0272] [α]

[0273] In equation (1-1), α refers to a number in the Z-base. α is an integer from 1 to 3. α can be 1, 2, or 3.

[0274] In one approach, α is 1.

[0275] [β]

[0276] In equation (1-2), β refers to the number of the Z-base. β is an integer of 1 or 2.

[0277] [Z]

[0278] Z is independently -Z 1 -SiZ 2 3－m Z 3 m Z represents a group with a siloxane bond.

[0279] [Z] 1 ]

[0280] In -Z 1 -SiZ 2 3－m Z 3 m In the middle, Z 1 It is a single bond or a divalent group. Z 1 Preferably, it has a divalent group.

[0281] Z 1 The source is Z. 11 and Z 12 One or more divalent groups constituted,

[0282] Z 11It can be a directly bonded group composed of one or more groups selected from -O-, -C(=O)-, -C(=NR'')-, -S-, -S(=O)2-, -NR''- and -C(OR'')R''- (where R'' is independently a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms (e.g., 1 to 5, 1 to 3 or 1 carbon atoms) each time it appears).

[0283] Z 1 The molecular weight of Y can be above 10, above 50, above 100, above 200, above 300, above 500, or above 750. The molecular weight of Y can be below 3000, below 2500, below 2000, below 1500, below 1000, below 750, below 500, below 300, below 200, below 100, or below 50.

[0284] In one approach, Z 1 It is a single key.

[0285] (Z) 11 )

[0286] Z 11 It is a non-hydrocarbon linker.

[0287] Z 11 It is a directly bonded or divalent group. Z is preferred. 11 It is not only a direct bond.

[0288] Z 11 The molecular weight can be below 2000, below 1500, below 1000, below 750, or below 500. X 1 The molecular weight can be above 10, above 50, above 100, above 200, above 300, or above 500.

[0289] Z 11 It is composed of one or more selected from -O-, -C(=O)-, -S(=O)2-, -NR'-, and -C(OR')R'- (where R' independently consists of 1 to 30 hydrogen or carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears. As Z 11 Examples can be listed as follows:

[0290] direct bond,

[0291] -O-、

[0292] -O-C(=O)-、

[0293] -O-C(=O)-O-、

[0294] -O-C(=O)-NR'-、

[0295] -NR'-、

[0296] -NR'-C(=O)-、

[0297] -NR'-C(=O)-O-、

[0298] -NR'-C(=O)-NR'-、

[0299] -C(=O)-、

[0300] -C(=O)-O-、

[0301] -C(=O)-NR'-、

[0302] -SO2-,

[0303] -SO2NR'-,

[0304] -C(OR')R'-、

[0305] -C(OR')(-)2 etc.

[0306] (In the formula, R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears.)

[0307] (Z) 12 )

[0308] Z 12 It can be a directly bonded hydrocarbon group or a hydrocarbon group that may have substituents.

[0309] Z 12 The number of carbon atoms can be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, or 8 or more. 12 The number of carbon atoms can be less than 10, less than 9, less than 8, less than 7, less than 6, or less than 5.

[0310] Z 12 The hydrocarbon group in the formula may have substituents. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms each time it appears). Substituents may or may not have active hydrogen. The number of substituents can be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0.

[0311] As Z 12 Specific examples can be listed as -(CH2). q- q is an integer from 1 to 22. q can be 1 or higher, 2 or higher, 3 or higher, 4 or higher, 5 or higher, 7 or higher, 9 or higher, 11 or higher, or 13 or higher. q can be less than 22, less than 20, less than 18, less than 16, less than 14, or less than 12, less than 10, less than 8, less than 6, less than 5, less than 4, or less than 3.

[0312] (Z) 1 (Example)

[0313] As Z 1 Examples can be listed as -Z 11 -、-Z 11 -Z 12 -、-Z 11 -Z 12 -Z 11 -、-Z 11 -Z 12 -Z 11 -Z 12 -、-Z 12 -、-Z 12 -Z 11 -、-Z 12 -Z 11 -Z 12 -、-Z 12 -Z 11 -Z 12 -Z 11 - etc. As Z 1 Preferred examples can be listed as -Z 11 -Z 12 -、-Z 12 -.

[0314] Z 1 It can be a directly bonded hydrocarbon group or a substituent group with 1 to 22 carbon atoms. Z is preferred. 1 It can be a hydrocarbon group with 1 to 10 carbon atoms that can have substituents. 1 The hydrocarbon group can have 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 7 or more, 9 or more, 11 or more, or 13 or more carbon atoms. 1 Hydrocarbons with 1 to 22 carbon atoms can have fewer than 22, 20, 18, 16, 14, 12, 10, 8, 6, 5, 4, or 3 carbon atoms.

[0315] As Z 1 Specific examples can be listed as -(CH2). s- s is an integer from 1 to 22. s can be 1 or higher, 2 or higher, 3 or higher, 4 or higher, 5 or higher, 7 or higher, 9 or higher, 11 or higher, or 13 or higher. s can be less than 22, less than 20, less than 18, less than 16, less than 14, or less than 12, less than 10, less than 8, less than 6, less than 5, less than 4, or less than 3.

[0316] [Z] 2 ]

[0317] In -Z 1 -SiZ 2 3－m Z 3 m In the middle, Z 2 Each is an independent hydrocarbon group having 1 to 10 carbon atoms. Z 2 Preferably, the hydrocarbon group is branched or straight-chain (preferably long-chain straight-chain). The hydrocarbon group is preferably aliphatic hydrocarbon group, especially saturated aliphatic hydrocarbon group, particularly alkyl group.

[0318] Z 2 Hydrocarbons with 1 to 10 carbon atoms can have more than 1, 2 or more, 3 or more, 4 or more, or 6 or more carbon atoms. 2 Hydrocarbons with 1 to 10 carbon atoms can have fewer than 10, 8, 6, 5, 4, or 3 carbon atoms. 2 It can be an alkyl group having 1 to 3 carbon atoms. 2 It can be methyl.

[0319] [m]

[0320] m is an independent integer from 1 to 3. m is 1, 2, or 3. In one mode, m is 2 or 3. In another mode, m is 1 or 2.

[0321] [Z] 3 ]

[0322] In -Z 1 -SiZ 2 3－m Z 3 m In the middle, Z 3 They are independently -(O-SiZ) 31 2) p -(CH2) q -Z 32 -SiZ 33 3.

[0323] (Z) 31 )

[0324] In -(O-SiZ) 31 2) p-(CH2) q -Z 32 -SiZ 33 In 3, Z 31 Each is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 311 3.

[0325] Z 31 Hydrocarbons with 1 to 10 carbon atoms can have more than 1, 2 or more, 3 or more, 4 or more, or 6 or more carbon atoms. 31 Hydrocarbons with 1 to 10 carbon atoms can have fewer than 10, 8, 6, 5, 4, or 3 carbon atoms. 31 It can be methyl.

[0326] The above OSiZ 31 The two Zs in 2 31 In the middle, there can be at least one Z. 31 OSiZ 311 3. The above OSiZ 31 The two Zs in 2 31 It can be -OSiZ 311 Or one of the hydrocarbon groups having 1 to 10 carbon atoms.

[0327] (Z) 311 )

[0328] Z 311 Each is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 3111 3.

[0329] Z 311 Hydrocarbons with 1 to 10 carbon atoms can have more than 1, 2 or more, 3 or more, 4 or more, or 6 or more carbon atoms. 311 Hydrocarbons with 1 to 10 carbon atoms can have fewer than 10, 8, 6, 5, 4, or 3 carbon atoms. 311 It can be methyl.

[0330] The above OSiZ 311 The three Zs in 3 311 In the middle, there can be at least one Z. 311 OSiZ 3111 3. The above OSiZ 311 The three Zs in 3 311 It can be -OSiZ 3111 One of three or one of a hydrocarbon group having 1 to 10 carbon atoms. The above OSiZ 311 The three Zs in 3 311 In the middle, there can be at least 2 Zs. 311 OSiZ 3111 3.

[0331] (Z) 3111 )

[0332] Z 3111 Each is an independent hydrocarbon group having 1 to 10 carbon atoms. Z 3111 Hydrocarbons with 1 to 10 carbon atoms can have more than 1, 2 or more, 3 or more, 4 or more, or 6 or more carbon atoms. 3111 Hydrocarbons with 1 to 10 carbon atoms can have fewer than 10, 8, 6, 5, 4, or 3 carbon atoms. 3111 It can be methyl.

[0333] (Z) 32 )

[0334] In -(O-SiZ) 31 2) p -(CH2) q -Z 32 -SiZ 33 In 3, Z 32 It can be -O- (oxygen atom) or -CH2-.

[0335] In one approach, Z 32 It is -O- (oxygen atom).

[0336] (Z) 33 )

[0337] In -(O-SiZ) 31 2) p -(CH2) q -Z 32 -SiZ 33 In 3, Z 33 Each is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 331 3. In one approach, Z 33 It can be an alkyl group with 1 to 3 carbon atoms or -OSiZ 331 3.

[0338] Z 33 Hydrocarbons with 1 to 10 carbon atoms can have more than 1, 2 or more, 3 or more, 4 or more, or 6 or more carbon atoms. 33 Hydrocarbons with 1 to 10 carbon atoms can have fewer than 10, 8, 6, 5, 4, or 3 carbon atoms. 33 It can be an alkyl group having 1 to 3 carbon atoms. 33 It can be methyl.

[0339] The above SiZ 33 The three Zs in 3 33 In the middle, there can be at least one Z. 33OSiZ 331 3. The above-mentioned SiZ 33 3 out of 3 Z 33 For OSiZ 331 One of three or one of a hydrocarbon group having 1 to 10 carbon atoms. The above-mentioned SiZ 33 The three Zs in 3 33 In the middle, there can be at least 2 Zs. 33 OSiZ 331 3.

[0340] (Z) 331 )

[0341] Z 331 Each is an independent hydrocarbon group having 1 to 10 carbon atoms.

[0342] Z 331 Hydrocarbons with 1 to 10 carbon atoms can have more than 1, 2 or more, 3 or more, 4 or more, or 6 or more carbon atoms. 331 Hydrocarbons with 1 to 10 carbon atoms can have fewer than 10, 8, 6, 5, 4, or 3 carbon atoms. 331 It can be methyl.

[0343] Z 331 Each can be an alkyl group having 1 to 3 carbon atoms, and each can be independently formed.

[0344] [p]

[0345] p is an integer from 0 to 196. p can be greater than 0, greater than 10, greater than 20, greater than 30, greater than 40, greater than 50, greater than 60, greater than 70, greater than 80, greater than 90, or greater than 100. p can be less than 196, less than 190, less than 180, less than 170, less than 160, less than 150, less than 140, less than 130, less than 120, less than 110, or less than 100.

[0346] The total value of p in equation (1-1) or (1-2) may not exceed 196.

[0347] In one mode, p is 0.

[0348] [q]

[0349] q is an integer from 0 to 10. q can be greater than 0, greater than 1, greater than 2, greater than 3, greater than 4, or greater than 5, and can be less than 10, less than 9, less than 8, less than 7, less than 6, or less than 5.

[0350] In one mode, q is 0.

[0351] The terminal portion of the monomer (1) of the present invention may contain a trialkylsiloxy group (-OSiR) bonded to a Si atom.Si 3) The structure containing trialkylsiloxy groups (R) Si (Referring to hydrocarbon groups with 1 to 10 carbon atoms as detailed below).

[0352] The Si atoms at the aforementioned terminal sites do not constitute trialkylsiloxy (-OSiR) atoms. Si 3) refers to the Si atom, but rather to the Si atom reacting with trialkylsiloxy groups (-OSiR). Si 3) Adjacent bonded Si atoms. However, this Si atom may not be bonded to an alkyl group (R... Si ) bond.

[0353] The trialkylsiloxy group (-OSiR) bonded to the Si atom at the terminal portion of the monomer (1) of the present invention Si 3) The number is an integer from 1 to 3.

[0354] Wherein, the end portion of the monomer (1) of the present invention refers to the end portion on the Z side in the above formula, which is the portion located in Z.

[0355] Specifically, the end portion of the monomer (1) of the present invention may include the structure shown in the following formula.

[0356] -Si(-OSiR) Si 3) X R Si 3－X

[0357] [In the formula,]

[0358] R Si Each is independently a hydrocarbon group having 1 to 10 carbon atoms.

[0359] x is an integer from 1 to 3.

[0360] R Si It is a hydrocarbon group with 1 to 10 carbon atoms. R Si Hydrocarbons with 1 to 10 carbon atoms can have more than 1, 2 or more, 3 or more, 4 or more, or 6 or more carbon atoms. Si Hydrocarbons with 1 to 10 carbon atoms can have fewer than 10, 8, 6, 5, 4, or 3 carbon atoms. Si It can be an alkyl group having 1 to 3 carbon atoms. R Si It can be methyl.

[0361] x is an integer from 1 to 3. x can be greater than 1 or greater than 2, and can be less than 3, less than 2, or less than 1.

[0362] Trialkylsiloxy (-OSiR) is bonded to the Si atom at the end of monomer (1). Si 3) The OSiZ mentioned above can be listed as an example.331 3.

[0363] The monomer (1) of the present invention may have a branched siloxy structure as shown in the following formula.

[0364]

[0365] [In the formula,]

[0366] X is a single bond or a divalent organic group.

[0367] R 1 and R 2 Each is independently trialkylsiloxy (-OSiR) Si 3) Alkyl, alkoxy, aryl, or aralkyl groups having 1 to 10 carbon atoms.

[0368] L 1 For i=1, the following formula represents a silyl alkyl group.

[0369]

[0370] (In the formula,

[0371] X is a single bond or a divalent organic group.

[0372] R 1 and R 2 Each is independently trialkylsiloxy (-OSiR) Si 3) Alkyl, alkoxy, aryl, or aralkyl groups having 1 to 10 carbon atoms.

[0373] i is an integer from 1 to 10, representing the total number of silyl alkyl layers, preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2.

[0374] L i＋1 The group is selected from hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups, aryl groups, aralkyl groups, and the above-mentioned silylalkyl groups, wherein,

[0375] When i = c (c is an integer from 1 to 10 representing the alkyl silane layer, preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2),

[0376] L i＋1 It consists of hydrogen atoms, alkyl, alkoxy, aryl, or aralkyl groups having 1 to 10 carbon atoms.

[0377] When i < c, it is the above-mentioned silylalkyl group.

[0378] a i The integer is between 0 and 3, preferably between 0 and 2, more preferably between 0 and 1, and even more preferably 0.

[0379] X is a single bond or a divalent group. X is preferably a divalent organic group.

[0380] As a divalent organic group, there are no particular limitations. Examples include -O- (oxygen atom), substituted or unsubstituted divalent hydrocarbon groups with 1 to 30 carbon atoms, and in a straight or branched form.

[0381] Examples of divalent hydrocarbon groups that are substituted or unsubstituted with carbon atoms from 1 to 30, and that are linear or branched, include:

[0382] Alkyl groups with 1 to 30 carbon atoms, such as methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and octamethylene;

[0383] The vinylidene group, allylidene group, butenylidene group, hexenylidene group, octeneylidene group, etc., having 2 to 30 carbon atoms;

[0384] arylene groups with 6 to 30 carbon atoms, such as phenylene and diphenylene;

[0385] Dimethylphenylene and other alkylene aryl groups having 7 to 30 carbon atoms; and

[0386] These groups are formed by replacing at least some of the hydrogen atoms bonded to the carbon atoms with halogen atoms such as fluorine, or with organic groups including methanol, epoxy, glycidyl, acyl, carboxyl, amino, methacrylate, mercapto, amide, and oxoalkylene groups.

[0387] The divalent hydrocarbon group is preferably a non-substituted divalent saturated hydrocarbon group with 1 to 30 carbon atoms, preferably a straight-chain or branched alkylene group with 1 to 6 carbon atoms, and particularly preferably a dimethylene group.

[0388] For example, a divalent organic group can be a group selected from the following groups.

[0389]

[0390] (In the formula,

[0391] R 3 The divalent hydrocarbon group described above, which has 1 to 30 carbon atoms and is either substituted or unsubstituted, and is in a straight-chain or branched form, may also have substituents, as mentioned above.

[0392] R 3’ It is a group selected from the groups shown in the following formula.

[0393] )

[0394] Preferably, it is a general formula –R that can be introduced through the reaction of hydrogen atoms bonded to silicon atoms and alkenyl groups. 3 - or -R 3 -R 3’ - The divalent organic group shown. Similarly, the general formula -R can be introduced through the reaction of hydrogen atoms bonded to silicon atoms and unsaturated carboxylic acid functional groups. 3 -COO-R 3 - or -R 3 -COO-R 3’ The divalent organic group shown is also suitable.

[0395] In particular, it is preferred that the above-mentioned X is a straight-chain or branched alkylene group with -O- (oxygen atom) and 1 to 30 carbon atoms, and especially preferred that it is -O- (oxygen atom) or dimethylene (ethylene).

[0396] Examples of alkyl, alkoxy, aryl, or aralkyl groups having 1 to 10 carbon atoms include:

[0397] Alkyl groups with 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl;

[0398] Cyclopentyl, cyclohexyl, and other cyclic alkyl groups with 3 to 10 carbon atoms;

[0399] Alkoxy groups, such as methoxy, ethoxy, and butoxy, are straight-chain or branched alkoxy groups with 1 to 10 carbon atoms.

[0400] Aryl groups with 6 to 10 carbon atoms, such as phenyl, tolyl, and xylyl;

[0401] Aryl groups with 7 to 10 carbon atoms, such as benzyl; and

[0402] These groups are formed by replacing at least some of the hydrogen atoms bonded to the carbon atoms with halogen atoms such as fluorine, or with organic groups including methanol, epoxy, glycidyl, acyl, carboxyl, amino, methacrylate, mercapto, amide, and oxoalkylene groups.

[0403] Alkyl, alkoxy, aryl, or aralkyl are preferably unsubstituted alkyl, alkoxy, aryl, or aralkyl with 1 to 10 carbon atoms, more preferably unsubstituted alkyl or aryl with 1 to 6 carbon atoms, and particularly preferably methyl, ethyl, or phenyl.

[0404] Trialkylsiloxy (-OSiR) Si 3) As described above.

[0405] The aforementioned branched siloxy structure can be a highly branched chemical structure that radiates from a single silicon atom, and i represents the degree of branching as the total number of silyl alkyl layers mentioned above.

[0406] The following structure is particularly preferred as a branched siloxy structure.

[0407]

[0408] (where X and R are in the formula) 2 Same as above.

[0409]

[0410] (where X and R are in the formula) 2 Same as above.

[0411] A monomer (1) having a branched siloxy structure is represented, for example, by the following formula.

[0412] .

[0413] (In the formula,

[0414] R a It is a polymerizable organic group, as mentioned above.

[0415] X, R 1 R 2 L 1 and a i Same as above.

[0416] The monomer (1) having a branched siloxy group structure preferably has a group selected from CH2=C(-R) b )-C(=O)-O-R c - (where R is the formula) b R is a hydrogen atom or a methyl group. c (Alkylene group having 1 to 10 carbon atoms) or CH2=C(-R) b )-C(=O)-NH-R c - (where R is the formula) b and R c Organic groups containing acrylic acid or methacrylic acid groups as shown above, organic groups containing alkenyl aryl groups as shown in the following general formula, and groups in alkenyl groups having 2 to 10 carbon atoms.

[0417]

[0418] (where R) 6 R is a hydrogen atom or a methyl group. 7 R is an alkyl group having 1 to 10 carbon atoms. 8 (where b is an alkylene group with 1 to 10 carbon atoms, b is an integer from 0 to 4, and c is 0 or 1.)

[0419] Monomers (1) having a branched siloxane structure can be manufactured, for example, according to the method for manufacturing branched siloxane-silanealkylene copolymers described in Japanese Patent Application Publication No. 11-1530 (Japanese Patent Application Publication No. 9-171154). For example, it can be manufactured by using the general formula: R a -Si-(OSiR) 2 2H)3 (where R) a and R 2 The product is manufactured by a hydrosilylation reaction of a silicon compound containing silicon atoms bonded to hydrogen atoms (as shown above) with an alkenyl-containing organosilicon compound. Examples of silicon compounds shown in the above formula include 3-methacryloyloxypropyltris(dimethylsiloxy)silane, 3-acryloyloxypropyltris(dimethylsiloxy)silane, and 4-vinylphenyltris(dimethylsiloxy)silane. Examples of alkenyl-containing organosilicon compounds include vinyltris(trimethylsiloxy)silane, vinyltris(dimethylphenylsiloxy)silane, and 5-hexenyltris(trimethylsiloxy)silane. The hydrosilylation reaction is preferably carried out in the presence of a transition metal catalyst such as chloroplatinic acid or a vinylsiloxane platinum coordination compound.

[0420] [(1) Examples of monomers]

[0421] Monomer (1) can be expressed as CH2=C(-R) a5 )-C(=O)-R a6 -X-CY 3－α Z α Or CH2=C(-R) a5 )-C(=O)-R a6 -X-NY 2－β Z β The monomer shown.

[0422] [In the formula,]

[0423] R a5 Each is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0424] R a6 They are independently -O- or -NH-.

[0425] X is independently -(CH2) q -,

[0426] q are independent integers from 1 to 10.

[0427] Y can be independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0428] Z is -Z 1 -SiZ 2 3－m Z3 m ,

[0429] Z 1 It is a single bond or -(CH2). s -,

[0430] s is an integer from 1 to 3.

[0431] Z 2 Each is independently an alkyl group having 1 to 10 carbon atoms.

[0432] m is an integer from 1 to 3.

[0433] Z 3 They are independently -(O-SiZ) 31 2) p -(CH2) q -Z 32 -SiZ 33 3,

[0434] p can be 0 or 1 independently.

[0435] q can be 0 or 1 independently.

[0436] Z 31 Each is independently an alkyl group having 1 to 3 carbon atoms.

[0437] Z 32 It is -O- or -CH2-.

[0438] Z 33 Each is independently an alkyl group having 1 to 10 carbon atoms or -OSiZ 331 3,

[0439] Z 331 Each is an alkyl group having 1 to 10 carbon atoms.

[0440] R a5 It is an alkyl group having 1 to 3 carbon atoms or hydrogen atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.

[0441] R a6 It can be -O- or -NH-, preferably -O-.

[0442] X is -(CH2) q -.

[0443] q is an integer from 1 to 10. q can be greater than 1, greater than 2, greater than 3, greater than 4, or greater than 5, and can be less than 10, less than 9, less than 8, less than 6, or less than 5.

[0444] Y is independently either a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.

[0445] Z is -Z 1 -SiZ 2 3－m Z 3 m .

[0446] m is an integer from 1 to 3, and can be 1, 2, or 3.

[0447] Z 1 It is a single bond or -(CH2). s -,

[0448] s is an integer from 1 to 3.

[0449] Z 2 Each of the components is an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.

[0450] Z 3 Each independently is -O-SiZ 33 3.

[0451] Z 31 Each is independently an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.

[0452] Z 32 It can be -O- or -CH2-.

[0453] Z 33 Each is independently an alkyl group having 1 to 10 carbon atoms or -OSiZ 331 3. Z 33 The hydrocarbon having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.

[0454] Z 331 Each of the components is an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.

[0455] [(1) Examples of monomers]

[0456] Examples of monomers (1) can be listed, but are not limited to, compounds represented by the following formulas. In the following formulas, TMS represents -Si(CH3)3.

[0457] Formula (A)

[0458]

[0459] Formula (B)

[0460]

[0461] Formula (C)

[0462]

[0463] Equation (D)

[0464]

[0465] Equation (E)

[0466]

[0467] Formula (F)

[0468]

[0469] Formula (G)

[0470]

[0471] Formula (H)

[0472]

[0473] Formula (I)

[0474]

[0475] Formula (J)

[0476]

[0477] Formula (K)

[0478]

[0479] Formula (L)

[0480]

[0481] Among the above formulas (A) to (L), the preferred formulas are (A), (B), (C), (D), (E), (F), (G), and (H).

[0482] Monomer (1) can be polymerized using known synthetic methods or can be a product that is commercially available. Monomer (1) can be synthesized, for example, as described below.

[0483] Prepare the precursor compound shown in formula (1-1a) or (1-2a) below.

[0484] Q-X-CY 3－α (-Z 1 -SiZ 2 3－m R Si m ) α(1-1a)

[0485] Q-X-NY 2－β (-Z 1 -SiZ 2 3－m R Si m ) β (1-2a)

[0486] [In the formula,]

[0487] Q can be F, Cl, Br, or I independently.

[0488] R Si -OR 1Si ,

[0489] R 1Si It is a hydrocarbon group with 1 to 10 carbon atoms.

[0490] The meanings of all other symbols are the same as above.

[0491] In the above formula, -Si-R becomes Si m The group is equivalent to a hydrolyzable silyl group.

[0492] Next, the aforementioned precursor compound is reacted with a Si-H-based organosilicon compound. Specifically, the hydrolyzable silyl group of formula (1-1a) or (1-2a) is reacted with the Si-H group of the Si-H-based organosilicon compound. During the reaction, the reaction can be promoted by using a Lewis acid such as tris(pentafluorophenyl)borane.

[0493] Examples of precursor compounds represented by formula (1-1a) or (1-2a) include silane compounds such as (3-chloropropyl)diethoxy(methyl)silane and (3-chloropropyl)trimethoxysilane.

[0494] As a Si-H-based organosilicon compound, it contains the above-mentioned Z 3 Examples of siloxane compounds include: hydrosilanes such as trimethoxysilane, triethoxysilane, and triethylsilane; dimethyl polysiloxanes with a single-terminal Si-H group such as 1,1,3,3,3-pentamethyldisiloxane and 1,1,1,3,3,5,5-heptamethyltrisiloxane; and dimethyl polysiloxanes with a side chain containing Si-H groups such as 1,1,1,3,5,5,5-heptamethyltrisiloxane.

[0495] By reacting the above precursor compound with a Si-H-based organosilicon compound, a hydrolyzable silyl group of the above precursor compound can be obtained. Si "Contains Si-H group-based organosilicon compounds including "Z" 3The group "" replaces the compound shown in formula (1-1b) or (1-2b) below.

[0496] Q-X-CY 3－α (-Z 1 -SiZ 2 3－m Z 3 m ) α (1-1b)

[0497] Q-X-NY 2－β (-Z 1 -SiZ 2 3－m Z 3 m ) β (1-2b)

[0498] [In the formula,]

[0499] Q can be F, Cl, Br, or I independently.

[0500] The meanings of all symbols except Q are the same as above.

[0501] By reacting the compound shown in formula (1-1b) or (1-2b) with an organic group R having polymerizable properties... a The reaction of the compound can yield the monomer (1) shown in formula (1-1) or (1-2).

[0502] R a -X-CY 3－α Z α (1-1)

[0503] R a -X-NY 2－β Z β (1-2)

[0504] Having polymerizable organic groups R a The compound preferably has a functional group capable of reacting with Q, and preferably has, for example, a carboxylic acid, an amine, or a derivative thereof. It has a polymerizable organic group R. a Examples of compounds that can be listed include (meth)acrylic acid, (meth)acrylamide, etc.

[0505] The monomer (1) of the present invention can be manufactured, for example, according to the contents described in WO2020 / 142474, WO2020 / 142441, Japanese Patent Application Publication No. 2019-89715, WO2020 / 142388, etc.

[0506] (2) Hydrophobic monomers

[0507] The polymer of the present invention may also contain repeating units derived from hydrophobic monomers (2) having 2 to 40 carbon atoms.

[0508] The hydrocarbon group in monomer (2) can be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group (alkyl). The hydrocarbon group can be branched or linear, more preferably linear. The hydrocarbon group can be saturated or unsaturated. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl). 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, 14 or more, or 16 or more. The number of carbon atoms in the hydrocarbon group 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.

[0509] Monomer (2) may contain an amide group, a urea group, or a urethane group. The hydrocarbon monomer may also be a combination of a hydrocarbon monomer having an amide group, a urea group, or a urethane group and a hydrocarbon monomer not having an amide group, a urea group, or a urethane group. By including such groups in monomer (2), the effects of the present invention can be well obtained.

[0510] The hydrophobic monomer (2) is the monomer shown in the following formula.

[0511] CH2=C(-R b )-C(=O)-R c -(R) d ) k (2)

[0512] [In the formula,]

[0513] R b It can be a hydrogen atom, a monovalent organic group, or a halogen atom.

[0514] R c It is a direct bond, a hydrocarbon group with 1 carbon atom in the 2-4 valence, and composed of -C6H4-, -O-, -S-, -C(=O)-, -S(=O)2- and -NR-. C1 - (R) C1 A divalent to tetravalent group consisting of at least one of a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

[0515] k is 1 to 3

[0516] R d It consists of hydrocarbon groups with 2 to 40 carbon atoms.

[0517] [R] b ]

[0518] R bIt can be a hydrogen atom, a monovalent organic group, or a halogen atom.

[0519] R b It can be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. R 12 Examples include hydrogen atoms, methyl groups, chlorine atoms, bromine atoms, iodine atoms, and cyano groups. R 12 Preferably, it contains hydrogen atoms, methyl groups, or chlorine atoms. R 12 More preferably, it is methyl. (Through R) 12 As a methyl group, it provides higher liquid-repellent properties. Especially from a reactivity standpoint, R... 12 It can be a hydrogen atom.

[0520] [R] c ]

[0521] R c It is a direct bond, a hydrocarbon group with 1 carbon atom in the 2-4 valence, and composed of -C6H4-, -O-, -S-, -C(=O)-, -S(=O)2- and -NR-. C1 - (R) C1 A divalent to tetravalent group consisting of at least one of a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

[0522] k is between 1 and 3.

[0523] R c Preferably, it is a divalent group. Examples of hydrocarbon groups with 1 carbon atom in the divalent to tetravalent range include -CH2-, -CH= with a branched structure, and -C≡ with a branched structure.

[0524] R c It can be -R Y -、-R Y -R Y -、-R Y -C(=O)-, -C(=O)-R Y -、-R Y -C(=O)-R Y -、-R Y -R X -、-R Y -R Y -R Y -、-R Y -R X -R Y -C(=O)-, -R Y -R X -C(=O)-R Y -、-R Y -R X -R Y -C(=O)-R Y- or -R Y -R X -R Y -R X -.

[0525] [In the formula, R] Y Independently for direct bonding, -O-, and -NR respectively. C11 - (R) C11 (A hydrocarbon group consisting of 1 to 4 hydrogen atoms or carbon atoms) or -S(=O)2-,

[0526] R X For -(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 represents an independent integer from 0 to 5, and -C6H4- represents phenylene).

[0527] Preferred R c It is not only a divalent hydrocarbon group.

[0528] R c Specific examples include -O-, -NH-, -O-C(=O)-, -NH-C(=O)-, -O-C(=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 -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 -NH-S(=O)2-, -NH-(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- or -NH-(CH2) m -NH-C6H4- [where m is an integer from 1 to 5, especially 2 or 4].

[0529] R c Preferably, it is -O-, -NH-, or -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- or -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -O-C(=O)-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -O-C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -NH-C(=O)-NH- [where m is an integer from 1 to 5, especially 2 or 4]. R c More preferably, it is -O- or -O-(CH2). m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O- or -O-(CH2) m -NH-C(=O)-, -O-(CH2) m-NH-S(=O)2- or -O-(CH2) m -S(=O)2-NH-, particularly preferred to be -O-(CH2). m -NH-C(=O)-.

[0530] [R] d ]

[0531] R d It consists of hydrocarbon groups with 2 to 40 carbon atoms.

[0532] R d The hydrocarbon group is preferably branched or straight-chain (preferably long-chain straight-chain) in shape. The hydrocarbon group is preferably aliphatic, especially saturated aliphatic, and particularly alkyl. The surface free energy of the -CH3 group is lower than that of the -CH2- group, making it more prone to liquid repellency. Therefore, structures with many branches and many -CH3 groups are preferred. On the other hand, long-chain alkyl groups of a certain length exhibit high liquid repellency due to their crystallinity. Therefore, it can be a branched hydrocarbon group (e.g., a branched alkyl group), especially tert-butyl or isopropyl, a multi-branched group, or a long-chain hydrocarbon group (or a long-chain straight-chain hydrocarbon group), such as an alkyl group. d The number of carbon atoms can be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 11 or more, 12 or more, 14 or more, 16 or more, or 18 or more, preferably 10 or more. d The number of carbon atoms can be less than 40, less than 30, less than 25, less than 20, less than 15, or less than 12.

[0533] [k]

[0534] k is 1, 2, or 3. In R c In the case of hydrocarbon groups with one carbon atom in the tetravalent state, k = 3. In R... c In the case of hydrocarbon groups with 1 carbon atom in the trivalent state, k = 2. In R... c Cases without a hydrocarbon group having 1 carbon atom in either trivalent or tetravalent form (e.g., R) c In the case of a hydrocarbon group (-CH2-) with 1 carbon atom in divalent form (e.g., 1 to 6), k = 1.

[0535] Examples of monomer (2) include the monomer shown in formula (a1) and the monomer shown in formula (a2).

[0536] (a1) Equation: CH2=C(-X) a1 )-C(=O)-Y a1 -R a1

[0537] [In the formula, R] a1 It consists of hydrocarbon groups with 6 to 40 carbon atoms.

[0538] X a1 It can be a hydrogen atom, a monovalent organic group, or a halogen atom.

[0539] Y a1 It can be -O- or -NH-.

[0540] (a2) Equation: CH2=C(-X) a2 )-C(=O)-Y a21 -Z(-Y) a22 -R a2 ) n

[0541] [In the formula, R] a2 Each is independently a hydrocarbon group with 6 to 40 carbon atoms.

[0542] X a2 It can be a hydrogen atom, a monovalent organic group, or a halogen atom.

[0543] Y a21 It is -O- or -NH-.

[0544] Y a22 Each group is independently directly bonded or consists of at least one group selected from -O-, -C(=O)-, -S(=O)2-, -NH-, or -CH2-.

[0545] Z is a hydrocarbon group with direct bonding, or with 1 to 5 carbon atoms in di or trivalent form.

[0546] n is 1 or 2.

[0547] (a1) Monomer

[0548] The monomer (a1) is a compound represented by the following formula.

[0549] CH2=C(-X a1 )-C(=O)-Y a1 -R a1

[0550] [In the formula, R] a1 It consists of hydrocarbon groups with 6 to 40 carbon atoms.

[0551] X a1 It can be a hydrogen atom, a monovalent organic group, or a halogen atom.

[0552] Y a1 It can be -O- or -NH-.

[0553] Monomer (a1) is Y a1 It is a long-chain acrylate monomer of -O- or Y- a1 It is a long-chain acrylamide monomer with -NH-.

[0554] R a1 Preferably, it is an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group, particularly an alkyl group. In R a1 In this process, the number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example 16 to 26, and especially 18 to 22.

[0555] 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.

[0556] Preferred examples of long-chain acrylate monomers include lauryl (meth)acrylate, stearyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, stearyl-α-chloroacrylate, eicosyl-α-chloroacrylate, and behenyl-α-chloroacrylate.

[0557] Preferred examples of long-chain acrylamide monomers include stearyl (meth)acrylamide, eicosyl (meth)acrylamide, and behenyl (meth)acrylamide.

[0558] (a2) monomer

[0559] Monomer (a2) is a monomer different from monomer (a1). Monomer (a2) is a (meth)acrylate or (meth)acrylamide having a group consisting of at least one group selected from -O-, -C(=O)-, -S(=O)2-, -NH- or -CH2-.

[0560] The monomer (a2) can be a compound as shown in the following formula.

[0561] CH2=C(-X a2 )-C(=O)-Y a21 -Z(-Y) a22 -R a2 ) n

[0562] [In the formula, R] a2 Each is independently a hydrocarbon group with 6 to 40 carbon atoms.

[0563] X a2 It can be a hydrogen atom, a monovalent organic group, or a halogen atom.

[0564] Y a21 It is -O- or -NH-.

[0565] Y a22 Each group is independently directly bonded or consists of at least one group selected from -O-, -C(=O)-, -S(=O)2-, -NH-, or -CH2-.

[0566] Z is a hydrocarbon group with direct bonding, or with 1 to 5 carbon atoms in di or trivalent form.

[0567] n is 1 or 2.

[0568] Y a22 And / or Z may not be a direct bond. Y a22 Z and Z can not be direct bonds at the same time.

[0569] R a2 Preferably, it is an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group, particularly an alkyl group. In R a2 In the hydrocarbon group, the number of carbon atoms is preferably 12 to 30, for example 16 to 26 or 15 to 26, especially 18 to 22 or 17 to 22.

[0570] 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.

[0571] Y a22 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'-.

[0572] [In the formula, Y' can be a direct bond, -O-, -NH-, or -S(=O)2-, respectively.]

[0573] 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, and -C6H4- is a phenylene oxide).

[0574] Y a22 Specific examples include direct bonds, -O-, -NH-, -O-C(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O)2-, -S(=O)2-NH-, -O-C(=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 -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-, -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- [where m is an integer from 1 to 5].

[0575] Y a22 Preferred are -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O)2-, -S(=O)2-NH-, -O-C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-. Y a22 More preferably, it is -NH-C(=O)-, -C(=O)-NH-, -O-C(=O)-NH-, -NH-C(=O)-O-, or -NH-C(=O)-NH-. a22 It does not have to be a direct bond.

[0576] Z is a directly bonded hydrocarbon group, 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, especially 2. Specific examples of Z include directly bonded, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH= with a branched structure, -CH2(CH-)CH2- with a branched structure, -CH2CH2CH= with a branched structure, -CH2CH2CH2CH2CH= with a branched structure, -CH2CH2(CH-)CH2- with a branched structure, and -CH2CH2CH2CH= with a branched structure. Z may not be directly bonded.

[0577] The monomer (a2) is preferably CH2=C(-X) a2 )-C(=O)-O-(CH2) m -NH-C(=O)-R a2 CH2=C(-X) a2 )-C(=O)-O-(CH2) m -O-C(=O)-NH-R a2 CH2=C(-X) a2 )-C(=O)-O-(CH2) m -NH-C(=O)-O-R a2 CH2=C(-X) a2 )-C(=O)-O-(CH2) m -NH-C(=O)-NH-R a2 [Here, R] 3 and X a2 [The meaning is the same as above].

[0578] The monomer (a2) is particularly preferred to be CH2=C(-X) a2 )-C(=O)-O-(CH2) m -NH-C(=O)-R a2 .

[0579] The monomer (a2) 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, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, behenyl isocyanate, etc.

[0580] Alternatively, monomer (a2) can also be produced by reacting a (meth)acrylate, such as methacrylate-2-methacryloyloxyethyl ester with isocyanate groups on its side chain, with a long-chain alkylamine or a long-chain alkyl alcohol. Examples of long-chain alkylamines include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine. Examples of long-chain alkyl alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

[0581] Preferred examples of monomer (2) are as follows.

[0582] Stearyl (meth)acrylate, behenyl (meth)acrylate, stearyl-α-chloroacrylate, behenyl-α-chloroacrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, eicosyl (meth)acrylate, eicosyl-α-chloroacrylate, stearamide ethyl (meth)acrylate, 2-stearamide ethyl acrylate, CH2=CHC(=O)OC2H4NHSO2C 18 H 37 ;

[0583] Stearyl (meth)acrylamide, behenyl (meth)acrylamide;

[0584]

[0585]

[0586]

[0587]

[0588]

[0589]

[0590]

[0591]

[0592]

[0593]

[0594]

[0595]

[0596]

[0597] [In the above formula, n is a number from 6 to 40, and m is a number from 1 to 5.]

[0598] The compounds with the above chemical formula are acrylic acid compounds with a hydrogen atom at the α-position, but specific examples could also be methacrylic acid compounds with a methyl atom at the α-position and α-chloroacrylic acid compounds with a chlorine atom at the α-position.

[0599] In monomer (2), 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, preferably 30% or more by weight.

[0600] The polymer of the present invention may further comprise repeating units derived from one or more monomers selected from the monomers (3) to (8) below.

[0601] (3) Monomers containing hydrophilic groups

[0602] The polymer of the present invention may contain a monomer (3) having a hydrophilic group. The monomer (3) may be a monomer other than the monomer (1), and is a monomer having a hydrophilic group. The hydrophilic group is preferably an oxoalkylene group (the alkylene group has 2 to 6 carbon atoms), especially an oxoethylene group. The monomer (3) is particularly preferred to be an oxoalkylene (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.

[0603] The monomer (3) is preferably an oxane (meth) acrylate as shown in the following formula.

[0604] CH2=CX b C(=O)-Y b -(R) b O) n -A b

[0605] [In the formula,]

[0606] X b It can be a hydrogen atom or a methyl group.

[0607] Y b It is -O- or -NH-.

[0608] R b Each is independently an alkylene group having 2 to 6 carbon atoms.

[0609] A bIt consists of hydrogen atoms, unsaturated or saturated hydrocarbon groups with 1 to 22 carbon atoms, or CH2=CX. b C(=O)-,

[0610] n is an integer from 1 to 90.

[0611] Examples of monomer (3) are preferably compounds represented by formulas (b1), (b2), and (b3).

[0612] CH2=CX b C(=O)-O-(R b O) n -A bi (b1)

[0613] CH2=CX b C(=O)-O-(R b O) n -C(=O)CX b =CH2 (b2)

[0614] CH2=CX b C(=O)-NH-(R b O) n -A bi (b3)

[0615] [In the formula,]

[0616] X b Each can be independently a hydrogen atom or a methyl group.

[0617] A bi Each group consists independently of a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms.

[0618] R b Each is independently an alkylene group having 2 to 6 carbon atoms.

[0619] n is an integer from 1 to 90.

[0620] n can be, for example, 1 to 50, especially 1 to 30, especially 1 to 15 or 2 to 15. Or, n can be, for example, 1.

[0621] 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 — [In the formula, 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)) x2The order of - is not limited to the recorded formula, and can also be random groups as shown in the diagram.

[0622] In -(R) b O) n In the given text, R can be two or more types (e.g., 2 to 4 types, especially 2 types), -(R b O) n For example, it could be -(R) 1 O) n1 - and - (R) 2 O) n2 — [where R is the formula] 1 With R 2 They are different from each other, and are 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.

[0623] R in equations (b1), (b2) and (b3) b Particularly preferred are ethylene, propylene, or butylene, especially butylene. R in formulas (b1), (b2), and (b3) b It can also 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 ethylidene / propylene, ethylidene / butylidene, and propylene / butylidene. Monomer (3) can also be a mixture of two or more. In this case, it is preferable that at least one of the monomers (3) contains R from formula (b1), (b2), or (b3). b It is ethylene, propylene, or butylene. Furthermore, when using the polyalkylene glycol di(meth)acrylate shown in formula (b2), it is not preferred to use it alone as monomer (3), but rather in combination with monomer (b1). In this case, the compound shown in formula (b2) is preferably controlled to be less than 30% by weight in the monomer (3) used.

[0624] Specific examples of monomer (3) may be listed below, but are not limited to these.

[0625] CH2=CHCOO-CH2CH2O-H

[0626] CH2=CHCOO-CH2CH2CH2O-H

[0627] CH2=CHCOO-CH2CH(CH3)O-H

[0628] CH2=CHCOO-CH(CH3)CH2O-H

[0629] CH2=CHCOO-CH2CH2CH2CH2O-H

[0630] CH2=CHCOO-CH2CH2CH(CH3)O-H

[0631] CH2=CHCOO-CH2CH(CH3)CH2O-H

[0632] CH2=CHCOO-CH(CH3)CH2CH2O-H

[0633] CH2=CHCOO-CH2CH(CH2CH3)O-H

[0634] CH2=CHCOO-CH2C(CH3)2O-H

[0635] CH2=CHCOO-CH(CH2CH3)CH2O-H

[0636] CH2=CHCOO-C(CH3)2CH2O-H

[0637] CH2=CHCOO-CH(CH3)CH(CH3)O-H

[0638] CH2=CHCOO-C(CH3)(CH2CH3)O-H

[0639] CH2=CHCOO-(CH2CH2O)2-H

[0640] CH2=CHCOO-(CH2CH2O)4-H

[0641] CH2=CHCOO-(CH2CH2O)5-H

[0642] CH2=CHCOO-(CH2CH2O)6-H

[0643] CH2=CHCOO-(CH2CH2O)5-CH3

[0644] CH2=CHCOO-(CH2CH2O)9-CH3

[0645] CH2=CHCOO-(CH2CH2O) 23 CH3

[0646] CH2=CHCOO-(CH2CH2O) 90 CH3

[0647] CH2=CHCOO-(CH2CH(CH3)O)9-H

[0648] CH2=CHCOO-(CH2CH(CH3)O)9-CH3

[0649] CH2=CHCOO-(CH2CH(CH3)O) 12 -CH3

[0650] CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)2-H

[0651] CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3

[0652] CH2=CHCOO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0653] CH2=CHCOO-(CH2CH2O) 23 -OOC(CH3)C=CH2

[0654] CH2=CHCOO-(CH2CH2O) 20 -(CH2CH(CH3)O)5-CH2-CH=CH2

[0655] CH2=CHCOO-(CH2CH2O)9-H

[0656] CH2=C(CH3)COO-CH2CH2O-H

[0657] CH2=C(CH3)COO-CH2CH2CH2O-H

[0658] CH2=C(CH3)COO-CH2CH(CH3)O-H

[0659] CH2=C(CH3)COO-CH(CH3)CH2O-H

[0660] CH2=C(CH3)COO-CH2CH2CH2CH2O-H

[0661] CH2=C(CH3)COO-CH2CH2CH(CH3)O-H

[0662] CH2=C(CH3)COO-CH2CH(CH3)CH2O-H

[0663] CH2=C(CH3)COO-CH(CH3)CH2CH2O-H

[0664] CH2=C(CH3)COO-CH2CH(CH2CH3)O-H

[0665] CH2=C(CH3)COO-CH2C(CH3)2O-H

[0666] CH2=C(CH3)COO-CH(CH2CH3)CH2O-H

[0667] CH2=C(CH3)COO-C(CH3)2CH2O-H

[0668] CH2=C(CH3)COO-CH(CH3)CH(CH3)O-H

[0669] CH2=C(CH3)COO-C(CH3)(CH2CH3)O-H

[0670] CH2=C(CH3)COO-(CH2CH2O)2-H

[0671] CH2=C(CH3)COO-(CH2CH2O)4-H

[0672] CH2=C(CH3)COO-(CH2CH2O)5-H

[0673] CH2=C(CH3)COO-(CH2CH2O)6-H

[0674] CH2=C(CH3)COO-(CH2CH2O)9-H

[0675] CH2=C(CH3)COO-(CH2CH2O)5-CH3

[0676] CH2=C(CH3)COO-(CH2CH2O)9-CH3

[0677] CH2=C(CH3)COO-(CH2CH2O) 23 -CH3

[0678] CH2=C(CH3)COO-(CH2CH2O) 90 -CH3

[0679] CH2=C(CH3)COO-(CH2CH(CH3)O)9-H

[0680] CH2=C(CH3)COO-(CH2CH(CH3)O)9-CH3

[0681] CH2=C(CH3)COO-(CH2CH(CH3)O) 12 -CH3

[0682] CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)2-H

[0683] CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3

[0684] CH2=C(CH3)COO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0685] CH2=C(CH3)COO-(CH2CH2O) 23 -OOC(CH3)C=CH2

[0686] CH2=C(CH3)COO-(CH2CH2O) 20 -(CH2CH(CH3)O)5-CH2-CH=CH2

[0687] CH2=CH-C(=O)-NH-CH2CH2O-H

[0688] CH2=CH-C(=O)-NH-CH2CH2CH2O-H

[0689] CH2=CH-C(=O)-NH-CH2CH(CH3)O-H

[0690] CH2=CH-C(=O)-NH-CH(CH3)CH2O-H

[0691] CH2=CH-C(=O)-NH-CH2CH2CH2CH2O-H

[0692] CH2=CH-C(=O)-NH-CH2CH2CH(CH3)O-H

[0693] CH2=CH-C(=O)-NH-CH2CH(CH3)CH2O-H

[0694] CH2=CH-C(=O)-NH-CH(CH3)CH2CH2O-H

[0695] CH2=CH-C(=O)-NH-CH2CH(CH2CH3)O-H

[0696] CH2=CH-C(=O)-NH-CH2C(CH3)2O-H

[0697] CH2=CH-C(=O)-NH-CH(CH2CH3)CH2O-H

[0698] CH2=CH-C(=O)-NH-C(CH3)2CH2O-H

[0699] CH2=CH-C(=O)-NH-CH(CH3)CH(CH3)O-H

[0700] CH2=CH-C(=O)-NH-C(CH3)(CH2CH3)O-H

[0701] CH2=CH-C(=O)-NH-(CH2CH2O)2-H

[0702] CH2=CH-C(=O)-NH-(CH2CH2O)4-H

[0703] CH2=CH-C(=O)-NH-(CH2CH2O)5-H

[0704] CH2=CH-C(=O)-NH-(CH2CH2O)6-H

[0705] CH2=CH-C(=O)-NH-(CH2CH2O)9-H

[0706] CH2=CH-C(=O)-NH-(CH2CH2O)5-CH3

[0707] CH2=CH-C(=O)-NH-(CH2CH2O)9-CH3

[0708] CH2=CH-C(=O)-NH-(CH2CH2O) 23 -CH3

[0709] CH2=CH-C(=O)-NH-(CH2CH2O) 90 -CH3

[0710] CH2=CH-C(=O)-NH-(CH2CH(CH3)O)9-H

[0711] CH2=CH-C(=O)-NH-(CH2CH(CH3)O)9-CH3

[0712] CH2=CH-C(=O)-NH-(CH2CH(CH3)O) 12 -CH3

[0713] CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H

[0714] CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3

[0715] CH2=CH-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0716] CH2=C(CH3)-C(=O)-NH-CH2CH2O-H

[0717] CH2=C(CH3)-C(=O)-NH-CH2CH2CH2O-H

[0718] CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)O-H

[0719] CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2O-H

[0720] CH2=C(CH3)-C(=O)-NH-CH2CH2CH2CH2O-H

[0721] CH2=C(CH3)-C(=O)-NH-CH2CH2CH(CH3)O-H

[0722] CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)CH2O-H

[0723] CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2CH2O-H

[0724] CH2=C(CH3)-C(=O)-NH-CH2CH(CH2CH3)O-H

[0725] CH2=C(CH3)-C(=O)-NH-CH2C(CH3)2O-H

[0726] CH2=C(CH3)-C(=O)-NH-CH(CH2CH3)CH2O-H

[0727] CH2=C(CH3)-C(=O)-NH-C(CH3)2CH2O-H

[0728] CH2=C(CH3)-C(=O)-NH-CH(CH3)CH(CH3)O-H

[0729] CH2=C(CH3)-C(=O)-NH-C(CH3)(CH2CH3)O-H

[0730] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)2-H

[0731] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)4-H

[0732] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-H

[0733] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)6-H

[0734] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-H

[0735] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-CH3

[0736] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-CH3

[0737] CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 23 -CH3

[0738] CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 90 -CH3

[0739] CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)9-H

[0740] CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)9-CH3

[0741] CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O) 12 -CH3

[0742] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H

[0743] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3

[0744] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0745] As monomer (3), preferably X 2Acrylates or acrylamides containing hydrogen atoms. Monomer (3) is particularly preferred to be hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate or hydroxyethyl acrylamide.

[0746] (4) Monomers containing ion-donating groups

[0747] The polymer of the present invention may contain a monomer (4) containing an ion-donating group. The monomer (4) is preferably a monomer having an olefinic carbon-carbon double bond and an ion-donating group (especially an acrylic monomer). The ion-donating group is an anion-donating group and / or a cation-donating group.

[0748] Monomers having anion-donating groups can include those having carboxyl, sulfonic acid, or phosphate groups. Specific examples of monomers having anion-donating groups include (meth)acrylic acid, crotonic 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.

[0749] Salts that can donate anionic groups include alkali metal salts, alkaline earth metal salts, or ammonium salts, such as methyl ammonium salts, ethanol ammonium salts, and triethanolammonium salts.

[0750] Among monomers having a cationic donor group, examples of cationic donor groups include amino groups, preferably tertiary amino and quaternary amino groups. In tertiary amino groups, the two groups bonded to the nitrogen atom may be the same or different, preferably an aliphatic group (especially alkyl) with 1 to 5 carbon atoms, an aromatic group (aryl) with 6 to 20 carbon atoms, or an aromatic aliphatic group (especially aralkyl, e.g., benzyl (C6H5-CH2-)) with 7 to 25 carbon atoms. In quaternary amino groups, the three groups bonded to the nitrogen atom may be the same or different, preferably an aliphatic group (especially alkyl) with 1 to 5 carbon atoms, an aromatic group (aryl) with 6 to 20 carbon atoms, or an aromatic aliphatic group (especially aralkyl, e.g., benzyl (C6H5-CH2-)) with 7 to 25 carbon atoms. In tertiary and quaternary amino groups, the remaining group bonded to the nitrogen atom may have a carbon-carbon double bond. The cationic donor group may also be in the form of a salt.

[0751] The cation-donating 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.

[0752] Specific examples of monomers having cationic groups are as follows.

[0753] CH2=CHCOO-CH2CH2-N(CH3)2 and its salts (e.g., acetates)

[0754] CH2=CHCOO-CH2CH2-N(CH2CH3)2 and its salts (e.g., acetates)

[0755] CH2=C(CH3)COO-CH2CH2-N(CH3)2 and its salts (e.g., acetates)

[0756] CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2 and its salts (e.g., acetates)

[0757] CH2=CHC(O)N(H)-CH2CH2CH2-N(CH3)2 and its salts (e.g., acetates)

[0758] CH2=CHCOO-CH2CH2-N(-CH3)(-CH2-C6H5) and its salts (e.g., acetates)

[0759] CH2=C(CH3)COO-CH2CH2-N(-CH2CH3)(-CH2-C6H5) and its salts (e.g., acetates).

[0760] CH2=CHCOO-CH2CH2-N + (CH3)3Cl －

[0761] CH2=CHCOO-CH2CH2-N + (-CH3)2(-CH2-C6H5)Cl －

[0762] CH2=C(CH3)COO-CH2CH2-N + (CH3)3Cl －

[0763] CH2=CHCOO-CH2CH(OH)CH2-N + (CH3)3Cl －

[0764] CH2=C(CH3)COO-CH2CH(OH)CH2-N + (CH3)3Cl －

[0765] CH2=C(CH3)COO-CH2CH(OH)CH2-N + (-CH2CH3)2(-CH2-C6H5)Cl －

[0766] CH2=C(CH3)COO-CH2CH2-N + (CH3)3Br －

[0767] CH2=C(CH3)COO-CH2CH2-N + (CH3)3I －

[0768] CH2=C(CH3)COO-CH2CH2-N + (CH3)3O － SO3CH3

[0769] CH2=C(CH3)COO-CH2CH2-N + (CH3)(-CH2-C6H5)2Br －

[0770] As a monomer containing an ion-donating group (4), methacrylic acid, acrylic acid or dimethylaminoethyl methacrylate is preferred, and methacrylic acid or dimethylaminoethyl methacrylate is more preferred.

[0771] (5) Halogenated olefin monomers

[0772] The polymer of the present invention may have repeating units derived from a halogenated olefin monomer (5). The halogenated olefin monomer (5) may not have fluorine atoms. The halogenated olefin monomer (5) is preferably an olefin with 2 to 20 carbon atoms substituted with 1 to 10 chlorine, bromine, or iodine atoms. The halogenated olefin monomer (5) 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 halogenated olefin monomer (5) are: vinyl halogenates, such as vinyl chloride, vinyl bromide, vinyl iodide; vinylidene halide, such as vinylidene chloride, vinylidene bromine, vinylidene iodide. Vinyl chloride or vinylidene chloride is preferred due to improved water repellency (especially water repellency durability). By having repeating units derived from the halogenated olefin monomer (5), the polymer of the present invention provides improved wash durability.

[0773] (6) Crosslinking monomers

[0774] The polymer of the present invention may have a crosslinking monomer (6). The crosslinking monomer has at least two reactive groups and / or an olefinic unsaturated double bond (preferably a (meth)acrylate group), and the crosslinking monomer (6) may be a fluorine-free monomer. It may be a fluorine-free compound. The crosslinking monomer (6) may be a compound having at least two olefinic unsaturated double bonds (preferably a (meth)acrylate group), or a compound having at least one olefinic unsaturated double bond and at least one reactive group. Examples of reactive groups include hydroxyl, epoxy, chloromethyl, terminal isocyanate, amino, carboxyl, etc.

[0775] The crosslinking monomer can be a mono(meth)acrylate, di(meth)acrylate, or di(meth)acrylamide with a reactive group.

[0776] An example of a crosslinking monomer is a vinyl monomer having a reactive group.

[0777] Examples of crosslinking monomers include, for example, 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.

[0778] (7) Monomers containing cyclic hydrocarbon groups

[0779] The polymer of the present invention may have repeating units derived from a monomer (7) containing a cyclic hydrocarbon group. The monomer (7) containing a cyclic hydrocarbon group is a monomer having a cyclic hydrocarbon group, which may be a monomer having an olefinic unsaturated double bond and a cyclic hydrocarbon group.

[0780] The monomer (7) containing a cyclic hydrocarbon group preferably has a (meth)acrylic acid group as an olefinic unsaturated double bond. For example, as an olefinic unsaturated double bond, it may have a (meth)acrylate group or a (meth)acrylamide group.

[0781] The cyclic hydrocarbon group can be alicyclic or aromatic, preferably alicyclic. The cyclic hydrocarbon group can be saturated or unsaturated, preferably saturated. The cyclic hydrocarbon group can be monocyclic, polycyclic, or bridged, preferably bridged. The cyclic hydrocarbon group can have chain-like groups (e.g., straight-chain or branched hydrocarbon groups).

[0782] The number of carbon atoms in a cyclic hydrocarbon group can be 4 or more, 6 or more, or 8 or more, and can be less than 30, 26 or less, 22 or less, 18 or less, or 14 or less.

[0783] 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, adamantylene, phenylene, naphthylene, etc.), and groups that are substitutes for them.

[0784] Specific examples of monomers containing cyclic hydrocarbon groups include cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentoxyethyl (meth)acrylate, tricyclopentyl (meth)acrylate, adamantyl (meth)acrylate, methyl-2-meth-2-adamantyl (meth)acrylate, ethyl-2-adamantyl (meth)acrylate, and compounds in which these acrylates are replaced with acrylamide. They can be used alone or in combination of two or more.

[0785] (8) Other monomers

[0786] Other monomers include acrylonitrile, (meth)acrylates containing organosiloxanes, short-chain alkyl (meth)acrylates, vinyl acetate, styrene, α-methylstyrene, p-methylstyrene, vinyl alkyl ethers, etc., but are not limited to these examples. Other monomers (8) may be used alone or in combination of two or more.

[0787] <Polymer Composition>

[0788] Regarding the combination of monomers (1) to (8) that constitute the repeating unit of the polymer, as long as (1) is included, there is no particular limitation, for example as described below (parentheses omitted). (1)

[0790] (1) + (2)

[0791] (1) + (2) + (3)

[0792] (1) + (3)

[0793] (1) + (4)

[0794] (1) + (2) + (3) + (4)

[0795] (1) + (2) + (3) + (4) + (5)

[0796] (1) + (2) + (3) + (4) + (5) + (6)

[0797] (1) + (2) + (3) + (4) + (5) + (6) + (7)

[0798] Other monomers (8) can also be used in combination with the above combination. In the case of fiber products, it is preferable to use monomers (1) and (2) together.

[0799] [(1) Amount of monomers]

[0800] The amount of repeating units derived from monomer (1) relative to the polymer can be 0.1% by mass or more, 0.5% by mass or more, 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more.

[0801] The amount of repeating units derived from monomer (1) relative to the polymer can be less than 95% by weight, less than 85% by weight, less than 75% by weight, less than 65% by weight, less than 55% by weight, less than 50% by weight, less than 45% by weight, less than 35% by weight, less than 33% by weight, less than 30% by weight, less than 27% by weight, less than 25% by weight, less than 20% by weight, less than 17% by weight, less than 15% by weight, less than 10% by weight, or less than 5% by weight.

[0802] The amount of repeating units derived from monomer (1) relative to the polymer can also be 100% by weight. That is, the polymer of the present invention can be a polymer of monomer (1).

[0803] [(2) Amount of hydrophobic monomers]

[0804] The amount of repeating units derived from monomer (2) relative to the polymer can be more than 1% by weight, more than 5% by weight, more than 10% by weight, more than 20% by weight, more than 30% by weight, more than 40% by weight, more than 50% by weight, more than 60% by weight, more than 70% by weight, more than 80% by weight, or more than 90% by weight.

[0805] The amount of repeating units derived from monomer (2) relative to the polymer can be less than 95% by weight, less than 85% by weight, 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, less than 15% by weight, or less than 5% by weight.

[0806] The amount of repeating units derived from monomer (2) may be 0.01 parts or more, 0.1 parts or more, 1 part or more, 3 parts or more, 5 parts or more, 10 parts or more, 15 parts or more, 20 parts or more, 50 parts or more, 75 parts or more, 100 parts or more, 300 parts or more, 500 parts or more, or 1000 parts or more, relative to 100 parts by weight of repeating units derived from monomer (1).

[0807] The amount of repeating units derived from monomer (1) is 100 parts by weight, and the amount of repeating units derived from monomer (2) may be 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.

[0808] In one approach, the amount of repeating units derived from monomer (2) may be less than the amount of repeating units derived from monomer (1).

[0809] [(3) Amount of monomers containing hydrophilic groups]

[0810] The amount of repeating units derived from monomer (3) relative to the polymer can be more than 1% by weight, more than 5% by weight, more than 10% by weight, more than 20% by weight, more than 30% by weight, more than 40% by weight, more than 50% by weight, more than 60% by weight, more than 70% by weight, more than 80% by weight, or more than 90% by weight.

[0811] The amount of repeating units derived from monomer (3) relative to the polymer can be less than 95% by weight, less than 85% by weight, 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, less than 15% by weight, or less than 5% by weight.

[0812] The amount of repeating units derived from monomer (3) may be 0.01 parts or more, 0.1 parts or more, 1 part or more, 3 parts or more, 5 parts or more, 10 parts or more, 15 parts or more, 20 parts or more, 50 parts or more, 75 parts or more, 100 parts or more, 300 parts or more, 500 parts or more, or 1000 parts or more, relative to 100 parts by weight of repeating units derived from monomer (1).

[0813] The amount of repeating units derived from monomer (1) is 100 parts by weight, and the amount of repeating units derived from monomer (3) may be 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.

[0814] [(4) Amount of monomers containing ion-donating groups]

[0815] The amount of repeating units derived from monomer (4) relative to the polymer can be more than 1% by weight, more than 5% by weight, more than 10% by weight, more than 20% by weight, more than 30% by weight, more than 40% by weight, more than 50% by weight, more than 60% by weight, more than 70% by weight, more than 80% by weight, or more than 90% by weight.

[0816] The amount of repeating units derived from monomer (4) relative to the polymer can be less than 95% by weight, less than 85% by weight, 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, less than 15% by weight, or less than 5% by weight.

[0817] The amount of repeating units derived from monomer (4) 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, more than 100 parts by weight, more than 300 parts by weight, more than 500 parts by weight, or more than 1000 parts by weight, relative to the amount of repeating units derived from monomer (1) being 100 parts by weight.

[0818] The amount of repeating units derived from monomer (1) is 100 parts by weight, and the amount of repeating units derived from monomer (4) may be 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.

[0819] [(5) Amount of haloolefin monomers]

[0820] The amount of repeating units derived from monomer (5) relative to the polymer can be more than 1% by weight, more than 5% by weight, more than 10% by weight, more than 20% by weight, more than 30% by weight, more than 40% by weight, more than 50% by weight, more than 60% by weight, more than 70% by weight, more than 80% by weight, or more than 90% by weight.

[0821] The amount of repeating units derived from monomer (5) relative to the polymer can be less than 95% by weight, less than 85% by weight, 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, less than 15% by weight, or less than 5% by weight.

[0822] The amount of repeating units derived from monomer (5) can be 0.01 parts or more, 0.1 parts or more, 1 part or more, 3 parts or more, 5 parts or more, 10 parts or more, 15 parts or more, 20 parts or more, 50 parts or more, 75 parts or more, 100 parts or more, 300 parts or more, 500 parts or more, or 1000 parts or more, relative to the amount of 100 parts by weight of repeating units derived from monomer (1).

[0823] The amount of repeating units derived from monomer (1) is 100 parts by weight, and the amount of repeating units derived from monomer (5) may be 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.

[0824] [(6) Amount of cross-linking monomers]

[0825] The amount of repeating units derived from monomer (6) relative to the polymer can be more than 1% by weight, more than 5% by weight, more than 10% by weight, more than 20% by weight, more than 30% by weight, more than 40% by weight, more than 50% by weight, more than 60% by weight, more than 70% by weight, more than 80% by weight, or more than 90% by weight.

[0826] The amount of repeating units derived from monomer (6) relative to the polymer can be less than 95% by weight, less than 85% by weight, 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, less than 15% by weight, or less than 5% by weight.

[0827] The amount of repeating units derived from monomer (6) 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, more than 100 parts by weight, more than 300 parts by weight, more than 500 parts by weight, or more than 1000 parts by weight, relative to the amount of repeating units derived from monomer (1) of 100 parts by weight.

[0828] The amount of repeating units derived from monomer (1) is 100 parts by weight, and the amount of repeating units derived from monomer (6) may be 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.

[0829] [(7) Amount of monomers containing cyclic hydrocarbon groups]

[0830] The amount of repeating units derived from monomers (7) relative to the polymer 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.

[0831] The amount of repeating units derived from monomer (7) relative to the polymer can be less than 95% by weight, less than 85% by weight, 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, less than 15% by weight, or less than 5% by weight.

[0832] The amount of repeating units derived from monomer (7) can be 0.01 parts or more, 0.1 parts or more, 1 part or more, 3 parts or more, 5 parts or more, 10 parts or more, 15 parts or more, 20 parts or more, 50 parts or more, 75 parts or more, 100 parts or more, 300 parts or more, 500 parts or more, or 1000 parts or more, relative to 100 parts by weight of repeating units derived from monomer (1).

[0833] The amount of repeating units derived from monomer (1) is 100 parts by weight, and the amount of repeating units derived from monomer (7) may be 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.

[0834] [(8) Amount of other monomers]

[0835] The amount of repeating units derived from monomer (8) relative to the polymer can be more than 1% by weight, more than 5% by weight, more than 10% by weight, more than 20% by weight, more than 30% by weight, more than 40% by weight, more than 50% by weight, more than 60% by weight, more than 70% by weight, more than 80% by weight, or more than 90% by weight.

[0836] The amount of repeating units derived from monomer (8) relative to the polymer can be less than 95% by weight, less than 85% by weight, 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, less than 15% by weight, or less than 5% by weight.

[0837] The amount of repeating units derived from monomer (8) can be 0.01 parts or more, 0.1 parts or more, 1 part or more, 3 parts or more, 5 parts or more, 10 parts or more, 15 parts or more, 20 parts or more, 50 parts or more, 75 parts or more, 100 parts or more, 300 parts or more, 500 parts or more, or 1000 parts or more, relative to the amount of 100 parts by weight of repeating units derived from monomer (1).

[0838] The amount of repeating units derived from monomer (1) is 100 parts by weight, and the amount of repeating units derived from monomer (8) may be 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.

[0839] <Methods for manufacturing polymers>

[0840] The polymer of the present invention can be manufactured using any conventional polymerization method, and the conditions of the polymerization reaction can be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.

[0841] In solution polymerization, the monomer can be dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen replacement, the mixture can be heated and stirred at 30–120°C for 30 minutes to 48 hours, for example, 3 to 24 hours. Examples of polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxypentanoate, and diisopropyl peroxydicarbonate. The amount of polymerization initiator used relative to 100 parts by weight of monomer is 0.01–20 parts by weight, for example, 0.01–10 parts by weight.

[0842] Organic solvents are substances whose monomers are inactive and which can dissolve them. Examples include esters (e.g., esters with 2 to 30 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2 to 30 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), and alcohols (e.g., alcohols with 1 to 30 carbon atoms, specifically isopropanol). Specific examples of organic solvents include acetone, chloroform, HCHC225, isopropanol, pentane, hexane, heptane, octane, 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 amount of organic solvent used is in the range of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight, relative to a total of 100 parts by weight of monomers.

[0843] In emulsion polymerization, the monomer can be emulsified in water in the presence of a polymerization initiator and an emulsifier. After nitrogen replacement, polymerization is carried out by stirring at 50–80°C for 30 minutes to 48 hours, for example, 3–24 hours. Polymerization initiators can be water-soluble substances such as benzoyl peroxide, lauroyl peroxide, tert-butyl peroxide, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutyronitrile dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, and ammonium persulfate; and oil-soluble substances such as azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxypentanoate, and diisopropyl peroxide dicarbonate. The amount of polymerization initiator used is in the range of 0.01–10 parts by weight relative to 100 parts by weight of monomer.

[0844] To obtain a polymer aqueous dispersion with excellent storage stability, it is preferable to use an emulsification device that provides strong abrasive energy, such as a high-pressure homogenizer or an ultrasonic homogenizer, to micronize and polymerize the monomers in water. Furthermore, various anionic, cationic, or nonionic emulsifiers can be used as emulsifiers, in an amount ranging from 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 compatible, it is preferable to add a compatibilizer to ensure adequate compatibility, such as a water-soluble organic solvent or a low molecular weight monomer. Adding a compatibilizer can improve emulsification and copolymerization properties.

[0845] Examples of water-soluble organic solvents include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol, with an amount relative to water ranging from 1 to 50 parts by weight, for example, 10 to 40 parts by weight per 100 parts by weight. Additionally, examples of low molecular weight monomers include methyl methacrylate, glycidyl methacrylate, and methyl methacrylate-2,2,2-trifluoroethyl methacrylate, with an amount relative to the total monomer amount ranging from 1 to 50 parts by weight, for example, 10 to 40 parts by weight per 100 parts by weight.

[0846] Chain transfer agents can be used during polymerization. The molecular weight of the polymer can be varied according to the amount of chain transfer agent used. Examples of chain transfer agents include compounds containing thiol groups such as lauryl thiols, thioglycols, and thioglycerols (especially alkyl thiols, e.g., those with 1 to 30 carbon atoms), and inorganic salts such as sodium hypophosphite and sodium bisulfite. The amount of chain transfer agent used is 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.

[0847] Polymers are preferably manufactured using emulsion polymerization or solution polymerization. Water (or an aqueous medium) is preferably added after the polymer is manufactured by polymerization to disperse the polymer in water. Water (or an aqueous medium) may also be added after the polymer is manufactured by polymerization. For example, after polymerizing monomers in the presence of an organic solvent to manufacture a polymer, water can be added to the polymer mixture, and the organic solvent can be removed by distillation to disperse the polymer in water. The organic solvent may also not be removed by distillation. Surfactants may be added before or after polymerization, or they may not be added at all. A good aqueous dispersion can be obtained without adding surfactants.

[0848] <Composition>

[0849] The compositions of the present invention contain the polymer of the present invention. The compositions of the present invention can be obtained by combining the polymer of the present invention with additional components (e.g., emulsifiers, liquid media, waxes, etc.). The compositions of the present invention can be obtained by polymerizing monomer (1), or monomer (1) and hydrophobic monomer (2), in the presence of additional components of the present invention (e.g., surfactants, liquid media, waxes, etc.).

[0850] The composition contains the polymer, emulsifier, and water of the present invention, and can yield an emulsion composition.

[0851] [surfactants]

[0852] The compositions of the present invention may contain surfactants as additional components. The surfactants in the compositions may include nonionic surfactants. Furthermore, the surfactants may also include one or more surfactants selected from cationic surfactants, anionic surfactants, and amphoteric surfactants. A combination of nonionic and cationic surfactants is preferred.

[0853] (Nonionic surfactant)

[0854] Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides.

[0855] Examples of ethers include compounds having oxyalkylene groups (preferably polyoxyethylene groups).

[0856] Examples of esters include esters of alcohols and fatty acids. Examples of alcohols are alcohols with 1 to 6 hydroxyl groups (especially 2 to 5 hydroxyl groups) and 1 to 50 carbon atoms (especially 10 to 30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0857] Examples of ester ethers include compounds formed by the addition of alkyl epoxides (especially ethylene oxide) to the esters of alcohols and fatty acids. Examples of alcohols are alcohols with 1 to 6 hydroxyl groups (especially 2 to 5 hydroxyl groups) and 1 to 50 carbon atoms (especially 3 to 30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0858] 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.

[0859] Polyols can be alcohols with 2 to 5 hydroxyl groups and 10 to 30 carbon atoms.

[0860] The amine oxide can be an oxide of an amine (secondary amine or preferably tertiary amine) (e.g., having 5 to 50 carbon atoms).

[0861] The nonionic surfactant is preferably a nonionic surfactant having an oxoalkylene group (preferably polyoxoethylene). The number of carbon atoms in the oxoalkylene group is preferably 2 to 10. The number of oxoalkylene groups in the molecule of the nonionic surfactant is generally preferably 2 to 100.

[0862] The nonionic surfactant is selected from ethers, esters, ester ethers, alkanolamides, polyols and amine oxides, and is preferably a nonionic surfactant with oxyalkylene oxides.

[0863] Nonionic surfactants can be alkylene oxide 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), polyoxyethylene (POE) / polyoxypropylene (POP) copolymers (random copolymers or block copolymers), alkylene glycol alkylene oxide adducts, etc. Among these, it is preferred that the structure of the alkylene oxide adduct and the polyalkylene glycol portion is polyoxyethylene (POE), polyoxypropylene (POP), or POE / POP copolymer (which can be a random copolymer or a block copolymer).

[0864] In addition, considering environmental issues (biodegradability, endocrine disruptors, etc.), nonionic surfactants are preferably those without aromatic groups.

[0865] Nonionic surfactants can be compounds represented by the following formula.

[0866] R 1 O-(CH2CH2O) p -(R) 2 O) q -R 3

[0867] [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.

[0868] Each R 2 Independent, can be the same or different, and is an alkylene group with 3 or more carbon atoms (e.g., 3 to 10).

[0869] R 3 It consists of hydrogen atoms, alkyl groups having 1 to 22 carbon atoms, or alkenyl groups having 2 to 22 carbon atoms.

[0870] p is a number greater than or equal to 2.

[0871] q is a number that is 0 or greater than 1.

[0872] R 1 Preferably, the number of carbon atoms is 8–20, particularly 10–18. As R… 1 Preferred specific examples may include lauryl, tridecyl, and oleyl.

[0873] R 2 Examples include propylidene and butylidene.

[0874] In nonionic surfactants, 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.

[0875] Nonionic surfactants can be polyoxyethylene alkylene ethers with a central hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (especially a polyoxyalkylene chain). Examples of hydrophobic oxyalkylene chains include oxypropylene chains, oxybutylene chains, and styrene chains, with oxypropylene chains being preferred.

[0876] Specific examples of nonionic surfactants include ethylene oxide with hexylphenol, isooctylphenol, hexadecyl alcohol, oleic acid, and alkanes (C... 12 -C 16 Thiols, sorbitol monofatty acids (C7-C5) 19 ) or alkyl (C 12 -C 18 Condensation products of amines, etc.

[0877] The proportion of polyoxyethylene blocks relative to the molecular weight of the nonionic surfactant (polymer) can be 5 to 80% by weight, for example 30 to 75% by weight, and particularly 40 to 70% by weight.

[0878] The average molecular weight of nonionic surfactants is typically 300–5000, for example, 500–3000.

[0879] Nonionic surfactants can be mixtures of compounds with an HLB (hydrophilicity-hydrophobicity balance) of less than 15 (especially less than 5) and compounds with an HLB of 15 or more. Examples of compounds with an HLB of less than 15 include sorbitan fatty acid esters. Examples of compounds with an HLB of 15 or more include polyoxyethylene alkyl ethers. The weight ratio of compounds with an HLB of less than 15 to compounds with an HLB of 15 or more can be 90:10 to 20:80, for example, 85:15 to 55:45.

[0880] Nonionic surfactants can be a single type or a mixture of two or more types.

[0881] (Catonic surfactants)

[0882] Cationic surfactants are preferably compounds that do not have amide groups.

[0883] Cationic surfactants can be amine salts, quaternary ammonium salts, or ethylene oxide addition ammonium salts. Specific examples of cationic surfactants are not particularly limited, but can include: amine salt type surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazoline; and quaternary ammonium salt type surfactants such as alkyl trimethylammonium salts, dialkyl dimethylammonium salts, alkyl dimethyl benzylammonium salts, pyridinium salts, alkyl isoquinoline onion salts, and benzyl chloride.

[0884] Preferred examples of cationic surfactants include compound R. 21 -N + (-R 22 (-R) 23 (-R) 24 )X － .

[0885] [In the formula, R] 21 R 22 R 23 and R 24 It consists of hydrocarbon groups with 1 to 40 carbon atoms.

[0886] X is an anionic group.

[0887] R 21 R 22 R 23 and -R 24 Specific examples of X include alkyl groups (e.g., methyl, butyl, stearyl, palmityl). Specific examples of X include halogens (e.g., chlorine) and acids (e.g., hydrochloric acid, acetic acid).

[0888] Cationic surfactants are particularly preferred monoalkyltrimethylammonium salts (alkyl groups have 4 to 40 carbon atoms).

[0889] The cationic surfactant is preferably an ammonium salt. The cationic surfactant can be an ammonium salt as shown in the following formula.

[0890] R 1 p -N + R 2 q X －

[0891] [In the formula, R] 1 For C12 and above (e.g., C 12 ~C 50 Straight-chain and / or branched aliphatic (saturated and / or unsaturated) groups,

[0892] R 2It is an alkyl group, benzyl group, or polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (especially 2, especially 3) to 50) of H or C1 to 4 (particularly preferred CH3, C2H5).

[0893] X is a halogen atom (e.g., ), or a C1-C4 fatty acid salt.

[0894] p is 1 or 2, q is 2 or 3, and p + q = 4.

[0895] R 1 The number of carbon atoms can be 12 to 50, for example 12 to 30.

[0896] Specific examples of cationic surfactants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyl di(hydroxypolyoxyethylene)ammonium chloride, benzyldodecyl di(hydroxypolyoxyethylene)ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0897] (Anionic surfactants)

[0898] Examples of anionic surfactants 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 surfactants, phosphate monoester or diester type surfactants, and sulfosuccinates.

[0899] (Amphoteric surfactants)

[0900] Examples of amphoteric surfactants include alanine-based surfactants, imidazoline betaines, amide betaines, and acetate betaines. More specifically, examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazoline betaine, lauryl dimethyl aminoacetic acid betaine, and fatty acid amide propyl dimethyl aminoacetic acid betaine.

[0901] Among surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants can each be one type or a combination of two or more types.

[0902] (Amount of surfactant)

[0903] The amount of surfactant relative to 100 parts by weight of the polymer 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. The amount of surfactant relative to 100 parts by weight of the polymer can be 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.

[0904] The surfactants exemplified in this invention can also be used as emulsifiers. That is, the nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants exemplified in this invention can be used as nonionic emulsifiers, cationic emulsifiers, anionic emulsifiers, and amphoteric emulsifiers.

[0905] [Liquid medium]

[0906] The compositions of the present invention may contain a liquid medium as an additional component. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. A mixture of water and an organic solvent is preferred.

[0907] 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)). They can be used alone or in combination of two or more.

[0908] (Amount of liquid medium)

[0909] The amount of liquid medium relative to the composition can be 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, or 97% by weight or more. The amount of liquid medium relative to the composition can be 99.9% by weight or less, 99% by weight or less, 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, or 50% by weight or less.

[0910] The amount of organic solvent relative to the composition may be 0.5% by weight or more, 1% by weight or more, 2% by weight or more, 3% by weight or more, 5% by weight or more, 7.5% by weight or more, 10% by weight or more, 12.5% ​​by weight or more, 15% by weight or more, or 20% by weight or more. The amount of organic solvent relative to the composition may be 75% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, or 5% by weight or less.

[0911] The amount of organic solvent relative to the liquid medium can be 1% or more by weight, 3% or more by weight, 5% or more by weight, 10% or more by weight, 20% or more by weight, 30% or more by weight, or 40% or more by weight. The amount of organic solvent relative to the liquid medium can be less than 55% by weight, less than 45% by weight, less than 35% by weight, less than 25% by weight, less than 15% by weight, less than 12.5% ​​by weight, less than 7.5% by weight, or less than 5.0% by weight.

[0912] The amount of organic solvent relative to 100 parts by weight of the polymer can be 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 20 parts by weight, more than 30 parts by weight, more than 40 parts by weight, or more than 50 parts by weight. The amount of organic solvent relative to 100 parts by weight of the polymer can be 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.

[0913] The amount of organic solvent relative to 100 parts by weight of water can be 0.5 parts by weight or more, 1 part by weight or more, 1.5 parts 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, 30 parts by weight or more, or 40 parts by weight or more. The amount of organic solvent relative to 100 parts by weight of water can be less than 100 parts by weight, less than 75 parts by weight, less than 50 parts by weight, less than 25 parts by weight, less than 10 parts by weight, or less than 5 parts by weight.

[0914] [Organosilicon]

[0915] The compositions of the present invention may also contain organosilicon in addition to the monomer (1) and the hydrophobic monomer (2).

[0916] Organosilicon can be a polymer as shown in formula (S1).

[0917] (R 53 )3Si-O-[-Si(R 51 )2-O-] a -[-Si(R)51 )2-O-] b -Si(R) 53 )3 (S1)

[0918] [In the formula, each R] 51 Independently representing a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, or an alkoxy group having 1 to 40 carbon atoms.

[0919] Each R 53 Independently representing a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a saturated hydrocarbon group having 1 to 40 carbon atoms.

[0920] 'a' represents an integer greater than or equal to 0, 'b' represents an integer greater than or equal to 1, and (a + b) ranges from 5 to 200.

[0921] In R 51 and R 53 In this context, alkyl groups with 1 to 40 carbon atoms and aryl groups with 6 to 40 carbon atoms can be unsubstituted or substituted.

[0922] R 51 and R 53 Specific examples include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl; cyclopentyl, cyclohexyl, cycloheptyl; phenyl, tolyl, naphthyl, or groups in which some or all of the hydrogen atoms bonded to these groups are replaced by halogen atoms, amino groups, cyano groups, etc. 51 and R 53 Methyl or ethyl is preferred.

[0923] In R 51 and R 53 In alkoxy groups, those with 1 to 40 carbon atoms can be either straight-chain or branched. Examples of alkoxy groups with 1 to 40 carbon atoms include methoxy, ethoxy, propoxy, and butoxy.

[0924] Organosilicones can have at least one long-chain hydrocarbon group. For example, R in formula (S1) 51 At least one of them, R 53 At least one of, or R 51 and R 53 At least one of each can be a long-chain hydrocarbon group, R 51At least one (e.g., one) may be a long-chain hydrocarbon group. Here, the long-chain hydrocarbon group may be a saturated hydrocarbon group with 6 or more, 10 or more, 15 or more, or 20 or more, preferably 10 or more or 23 or more. Here, the hydrocarbon group may be straight-chain or branched, preferably alkyl. Specific examples of hydrocarbon groups include hexyl (6 carbon atoms), octyl (8 carbon atoms), lauryl (12 carbon atoms), myristyl (14 carbon atoms), stearyl (18 carbon atoms), behenyl (22 carbon atoms), trialkyl (23 carbon atoms), creosyl (tetraalkyl, 24 carbon atoms), waxyl (hexadecyl, 26 carbon atoms), montanyl (octadecyl, 28 carbon atoms), betaine (triadecyl, 30 carbon atoms), and tris(dodecyl) (32 carbon atoms).

[0925] From the perspective of ease of industrial manufacture and availability, R is preferred as a long-chain hydrocarbon group. 51 and R 53 Other than R 51 and R 53 It can be a hydrogen atom or a methyl group, more preferably a methyl group.

[0926] a is an integer greater than or equal to 0. From the viewpoint of ease of industrial manufacture and availability, a can be less than 40, less than 30, less than 20, and preferably less than 30.

[0927] The sum of a and b is 5 to 200. From the viewpoint of ease of industrial manufacture, availability, and operation, the sum of a and b is preferably 10 to 100, more preferably 40 to 60. a can be 0 to 150, for example 1 to 100. The lower limit of b can be 1, 2, or 3, and the upper limit of b can be 150, 10, or 5.

[0928] When a or b is 2 or more, there are multiple R's. 51 and R 52 They can be the same or different.

[0929] Preferred R 51 and R 53 The base (for example, R in the case shown in equation (S2) below) 51 R 52 base and R 53 The total percentage of methyl groups is more than 50 mol%.

[0930] The order of repeating units enclosed in a or b is not limited to the order shown in the chemical formula and is arbitrary. That is, organosilicon can be a random polymer or a block polymer.

[0931] For example, organosilicon can also be a polymer as shown in formula (S2).

[0932] (R53 )3Si-O-[-Si(R 51 )2-O-] a -[-Si(R) 51 (R) 52 )-O-] b -Si(R) 53 )3 (S2)

[0933] [In the formula, each R] 51 Independently representing a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a long-chain hydrocarbon group.

[0934] Each R 52 Independently representing long-chain hydrocarbon groups,

[0935] Each R 53 Independently representing a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a long-chain hydrocarbon group.

[0936] 'a' represents an integer greater than or equal to 0, 'b' represents an integer greater than or equal to 1, and (a + b) ranges from 5 to 200.

[0937] In equation (S2), R 51 and R 53 It may have alkyl groups with 3 to 40 carbon atoms or unsaturated hydrocarbon groups with 6 to 40 carbon atoms (e.g., hydrocarbon groups with aromatic rings), but preferably does not have these groups.

[0938] Examples of organosilicon are as follows.

[0939]

[0940] [In the formula, a represents an integer from 0 to 150,]

[0941] b represents an integer from 1 to 150.

[0942] (a+b) ranges from 5 to 200.

[0943] n is an integer from 1 to 36 (preferably n is a long-chain hydrocarbon group).

[0944] Organosilicones can be synthesized using existing, well-known methods. For example, organosilicones can be obtained by hydrosilylation of an α-olefin with an organosilicon having a SiH group.

[0945] Examples of organosilicones with SiH groups include methylhydrosiloxanes with a degree of polymerization of 10 to 200, or copolymers of dimethylsiloxanes and methylhydrosiloxanes. Among these, methylhydrosiloxanes are preferred from the viewpoint of ease of industrial manufacture and availability. Hydrogen organosilicones (e.g., methylhydrosiloxanes) refer to compounds in which a portion of the side chain of a polydiorganosiloxane is replaced by hydrogen, and the hydrogen atom is directly bonded to the silicon atom. When using hydrogen organosilicones, a catalyst can be used to improve reactivity. For example, zinc, tin, manganese, cobalt, iron, and amine-based catalysts can be used. As these catalysts, organic acid metal salts are preferred, and as organic acids, fatty acids are preferred. From the viewpoint of excellent operability, zinc stearate, etc., can be used. Catalysts that readily exert their effect when used at 10 to 40% relative to methylhydrosiloxanes are preferred. Two or more types of amino-modified, epoxy-modified, carboxyl-modified, and methylhydrosiloxanes can be mixed. These are all organosilicones with reactive groups, and organosilicones with film-forming properties are preferred. The term "film-forming property" refers to the fact that after the organosilicon is applied to the fiber surface in an emulsion state, it does not form an oily or gel-like substance, but rather a solid film.

[0946] α-Alkenes are compounds that are the source of long-chain hydrocarbon groups in organosilicon. Specific examples of α-alkenes include 1-tridecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-tridecene, and 1-tridodecene.

[0947] The hydrosilylation reaction can be carried out stepwise or in one step with the organosilicon having the SiH group in the presence of a catalyst, depending on the need.

[0948] The amounts of SiH-based organosilicon and α-olefin used in the hydrosilylation reaction can be appropriately selected based on the SiH equivalent or number-average molecular weight of the SiH-based organosilicon.

[0949] Catalysts used in the hydrosilylation reaction include, for example, compounds of platinum, palladium, etc., with platinum compounds being preferred. Examples of platinum compounds include platinum(IV) chloride.

[0950] The reaction conditions for the hydrosilylation reaction are not particularly limited and can be adjusted appropriately. The reaction temperature is, for example, 10–200°C, preferably 50–150°C. At a reaction temperature of 50–150°C, the reaction time is, for example, 3–12 hours.

[0951] The hydrosilylation reaction is preferably carried out under a non-reactive gas atmosphere. Examples of non-reactive gases include nitrogen and argon. The reaction can also be carried out under solvent-free conditions, but solvents can also be used. Examples of solvents include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

[0952] (Reactive organosilicon)

[0953] Organosilicones can include reactive organosilicones. Reactive organosilicones can be listed as polysiloxanes with reactive groups on side chains, at single ends, at both ends, or on both side chains and at both ends. However, from the viewpoint of excellent slip resistance and excellent water repellency, it can be a polysiloxane with reactive groups on side chains and / or at both ends. There are no particular limitations on reactive organosilicones as long as they have reactive groups within the molecule; examples include amino-modified organosilicones, epoxy-modified organosilicones, carboxyl-modified organosilicones, hydrogen-modified organosilicones, etc. Reactive organosilicones can also be substances in which one or more substituents of formula (S1) or formula (S2) above are replaced by reactive groups.

[0954] Examples of amino-modified organosilicones include substances having an amino group bonded to an organic group directly bonded to a silicon atom. The organic group can be any of an alkylene group or a divalent aromatic group. As an alkylene group, it is preferred that it has 2 or more carbon atoms. As a divalent aromatic group, it is preferred that it has 6 or more carbon atoms. The amino group can be any of a primary amino group, a secondary amino group, or a tertiary amino group. Examples of organic groups bonded with amino groups include: 2-aminoethyl, N-methyl-2-aminoethyl, N,N-dimethyl-2-aminoethyl, N-ethyl-2-aminoethyl, N,N-diethyl-2-aminoethyl, N,N-methylethyl-2-aminoethyl, N,N-methylethyl-2-aminoethyl, 3-aminopropyl, N-methyl-3-aminopropyl, N,N-dimethyl-3-aminopropyl, N-ethyl-3-aminopropyl, N,N-diethyl-3-aminopropyl, and N,N-methylethyl-3-aminopropyl. These functional groups can be present on the side chains of polysiloxanes or at the ends.

[0955] Examples of epoxy-modified organosilicones include substances having an epoxy group bonded to an organic group directly bonded to a silicon atom. The organic group can be any of an alkylene group or a divalent aromatic group. In this form, it is typically bonded to the aforementioned organic group in the form of a glycidyl ether. Examples of such functional groups include 3-epoxypropoxypropyl and 2-epoxypropoxyethyl. These functional groups can be present on the side chains of the polysiloxane or at the ends.

[0956] Examples of carboxyl-modified organosilicones include substances having a structure in which a carboxyl group is bonded to an organic group directly bonded to a silicon atom. The organic group can be either an alkylene group or a divalent aromatic group. As an alkylene group, it is preferred that it has 2 or more carbon atoms. As a divalent aromatic group, it is preferred that it has 6 or more carbon atoms. Examples of such functional groups include 3-carboxypropyl and 2-carboxyethyl. These functional groups can be present in the side chain or at the end of the polysiloxane.

[0957] (Organosilicon resin)

[0958] Organosilicon can include organosilicon resins. Organosilicon resins are derived from R3SiO2. 1／2 Unit (M unit), RSiO 3／2 Unit (T unit) and SiO 4／2 The silicone resin is composed of at least one of the units (Q unit), where R is a monovalent alkyl group with 1 to 18 carbon atoms in a straight or branched chain, and does not include silicone resins composed only of M units or only of Q units. From the viewpoint of achieving the effects of the present invention, it is preferred that the silicone resin (3) does not contain R2SiO. 2／2 Unit (D unit).

[0959] The silicone resin is preferably in a sol state. Examples of R include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, 2-ethylhexyl, decyl, cetyl, stearyl, etc. However, considering the stability of silicone resin (3) in the sol state, the availability of raw materials, and the price, R is preferably methyl, and it is particularly preferred that more than 90% of all R is methyl. However, R can also contain different types of groups.

[0960] In organosilicon resin containing R2SiO 2／2 When D-units are used, the low slippage properties of the composition may be compromised. Additionally, silicone resins composed solely of Q-units may hinder the water-repellent properties of the composition.

[0961] The structure of the silicone resin can be exemplified as (i) composed of M units and Q units, (ii) composed of M units, T units and Q units, (iii) composed of M units and T units, (iv) composed of T units and Q units, and (v) composed only of T units. Preferably, it is the silicone resin composed of (i) M units and Q units and (v) composed only of T units. In the silicone resin composed of (i) M units and Q units, the molar ratio (M / Q) of the M units to the Q units is preferably M / Q = 0.6 to 1.3, more preferably M / Q = 0.8 to 1.1. However, two or more of these silicone resins can also be used together.

[0962] In addition, the organosilicon resin (3) may contain structural units having hydroxyl groups bonded to silicon atoms. Specifically, (HO)RSiO can be listed as an example. 2／2 Unit or (HO)2RSiO 1／2 Unit, (HO)SiO 3／2 Unit, (HO)2SiO 2／2 Unit, (HO)3SiO 1／2 The unit, a portion of the hydroxyl group, can be an alkoxy group as shown by the RO group.

[0963] Sol containing organosilicon resin can be manufactured as described in Japanese Patent 3852921 by the following manufacturing methods: a manufacturing method in which an organodisiloxane and a tetraalkoxysilane and their partially hydrolyzed condensates are uniformly dispersed and polymerized in water containing a surfactant, or a manufacturing method in which the silane compounds shown below are hydrolyzed in water.

[0964] A detailed description is provided of a method for manufacturing silane compounds by hydrolyzing them in water. The raw materials used in this manufacturing process are chlorinated or alkoxy groups, and may contain one, three, or four hydrolyzable groups. Any silane compound with an alkyl group satisfying the above conditions can be used. Examples of usable silane compounds include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrichlorosilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrichlorosilane, isopropyltrimethoxysilane, and isopropyltriethoxysilane. Silane, Butyltrichlorosilane, Butyltrimethoxysilane, Butyltriethoxysilane, Isobutyltrichlorosilane, Isobutyltrimethoxysilane, Isobutyltriethoxysilane, Hexyltrichlorosilane, Hexyltrimethoxysilane, Hexyltriethoxysilane, 2-Ethylhexyltrichlorosilane, 2-Ethylhexyltrimethoxysilane, 2-Ethylhexyltriethoxysilane, Decyltrichlorosilane, Decyltrimethoxysilane, Decyltriethoxysilane, Cetyltrichlorosilane, Cetyltrimethoxysilane, Cetyltrichlorosilane, Cetyltrimethoxysilane, Cetyltrichlorosilane Wax-based triethoxysilane, stearyl trichlorosilane, stearyl trimethoxysilane, stearyl triethoxysilane, trimethylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, dimethylethylchlorosilane, dimethylethylmethoxysilane, dimethylethylethoxysilane, dimethylpropylchlorosilane, dimethylpropylmethoxysilane, dimethylpropylethoxysilane, dimethylisopropylchlorosilane, dimethylisopropylmethoxysilane, dimethylisopropylethyl... Silanes that can be used include oxysilanes, dimethylhexylchlorosilane, dimethylhexylmethoxysilane, dimethylhexylethoxysilane, dimethyldecylchlorosilane, dimethyldecylmethoxysilane, dimethyldecylethoxysilane, dimethylcetylchlorosilane, dimethylcetylmethoxysilane, dimethylcetylethoxysilane, dimethylstearylchlorosilane, dimethylstearylmethoxysilane, dimethylstearylethoxysilane, and their partial hydrolysates, but are not limited to these. From the perspectives of operability, ease of distillation removal of byproducts, and ease of access to raw materials, methoxysilanes or ethoxysilanes are preferred. One or a mixture of two or more of these silane compounds can be used.

[0965] As a method for hydrolyzing silane compounds in water, conventional methods that are generally known can be used. That is, the method of adding the silane compound dropwise into the water while carrying out the hydrolysis reaction, or the method of mixing the water and the silane compound together before carrying out the hydrolysis reaction.

[0966] A hydrolysis catalyst can be used when carrying out the hydrolysis reaction. Existing known catalysts can be used, and both acidic and basic catalysts can be employed. In the case of an acidic catalyst, solid acids such as hydrogen halides, carboxylic acids, sulfonic acids, acidic or weakly acidic inorganic salts, and ion exchange resins are preferred. In the case of a basic catalyst, alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate, alkali metal silanodes such as sodium siloxide and potassium silanodes, amines such as triethylamine, diethylamine, and aniline, and ammonia water can be used. Regarding the amount of catalyst, it is preferable to adjust the amount added in a way that adjusts the pH of the aqueous solution to 2-7 or 7-12. Furthermore, after the reaction is complete, a neutralizing agent can be added as needed to neutralize the acidic or basic catalyst.

[0967] A surfactant can be added to the aqueous solution to disperse the silane compound and the hydrolysis products in the water. There are no particular limitations on the surfactant; anionic surfactants such as alkyl sulfates, alkylbenzene sulfonates, and alkyl phosphates; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene propylene alkyl ethers, polyoxyethylene alkylphenyl ethers, and polyoxyethylene fatty acid esters; cationic surfactants such as quaternary ammonium salts and alkylamine acetates; and amphoteric surfactants such as alkyl betaines and alkyl imidazolines can be used alone or in combination of two or more. Additionally, substances exhibiting acidity or alkalinity can also serve as hydrolysis catalysts. There are no particular limitations on the amount of surfactant added, but 1 to 50 parts by weight relative to 100 parts by weight of the silane compound is preferred. Less than 1 part by weight will not provide sufficient surfactant effect, while more than 50 parts by weight may impair the water-repellent properties of the surfactant.

[0968] Hydrolysis catalysts and surfactants can be added to a mixture of water and silane compounds as needed, and the hydrolysis reaction can be carried out at 0–90°C for 10 minutes to 24 hours. Afterwards, a neutralization reaction is performed as needed, thereby obtaining an organosilicon resin. Furthermore, alcohols and neutralizing salts generated as byproducts of the hydrolysis reaction can be removed by vacuum distillation or filtration. Various additives can be incorporated into this organosilicon resin. For example, preservatives, thickeners, etc., can be added depending on the purpose.

[0969] (Amount of organosilicon)

[0970] The amount of organosilicon relative to 100 parts by weight of the polymer 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. The amount of organosilicon relative to 100 parts by weight of the polymer can be 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.

[0971] [wax]

[0972] The composition of the present invention preferably contains wax in addition to monomer (1) and hydrophobic monomer (2). By containing wax, it can possess good water-repellent properties. The composition of the present invention may contain both organosilicon and wax, or either organosilicon or wax.

[0973] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, animal and plant waxes, and mineral waxes, with paraffin wax being preferred. Specific examples of compounds constituting waxes include n-alkanes (e.g., tris(2-), tetras(2-), pentas(2-), hexas(2-), heptadecane, octadecane, nonadecane, triadecane, triadecane, dodecane, tris(2-), tetradecane, pentadecane, hexadecane, and hexadecane), and n-olefins (e.g., 1-eicosene, 1-diecane, 1-trisene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, nonadecene, triadecene, octadecene, dodecanene, trisene, tetradecene, pentadecene, and hexadecene). The compounds constituting the wax preferably have 20 to 60 carbon atoms, for example, 25 to 45. The molecular weight of the wax can be 200 to 2000, for example, 250 to 1500, or 300 to 1000. They can be used alone or in combination of two or more.

[0974] The melting point of the wax can be above 50°C, above 55°C, above 60°C, above 65°C, or above 70°C, preferably above 55°C, and more preferably above 60°C. The melting point of the wax is determined according to JIS K 2235-1991.

[0975] (Amount of wax)

[0976] The amount of wax relative to 100 parts by weight of the polymer 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. The amount of wax relative to 100 parts by weight of the polymer can be 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.

[0977] [Organic acids]

[0978] The compositions of the present invention may contain an organic acid as an additional component. Known substances can be used as the organic acid. Carboxylic acids, sulfonic acids, sulfinic acids, etc., are preferred examples of organic acids, with carboxylic acids being particularly preferred. Examples of such carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., with formic acid or acetic acid being particularly preferred. In the present invention, one or more organic acids may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0979] (Amount of organic acids)

[0980] The amount of organic acid relative to 100 parts by weight of the polymer 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. The amount of organic acid relative to 100 parts by weight of the polymer can be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of organic acid can be adjusted so that the pH of the composition reaches 3 to 10, for example 5 to 9, particularly 6 to 8. The composition can be acidic (pH 7 or less, for example 6 or less).

[0981] [Curing agent]

[0982] The composition may contain a curing agent (an active hydrogen reactive compound or a compound containing active hydrogen). The curing agent may be added to the composition after polymerization to obtain the polymer.

[0983] The curing agent (crosslinking agent) in the composition enables the polymer to cure well. The curing agent can be an active hydrogen reactive compound or a compound containing active hydrogen that reacts with the active hydrogen or active hydrogen reactive groups present in the polymer. Examples of active hydrogen reactive compounds include polyisocyanate 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, and melamine compounds.

[0984] The curing agent can be a polyisocyanate compound. A polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. Polyisocyanate compounds act as crosslinking agents. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, and their derivatives.

[0985] 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, 1,03-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanate. Aliphatic diisocyanates such as methylhexanoate; and aliphatic triisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanate octyl ester, 1,6,11-triisocyanate undecyl ester, 1,8-diisocyanate-4-isocyanate methyl octyl ester, 1,3,6-triisocyanate hexyl ester, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyl octyl ester, etc. They can be used alone or in combination of two or more.

[0986] 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), and 1,3,5-triisocyanate cyclohexyl ester. They can be used alone or in combination of two or more.

[0987] Examples of aromatic aliphatic polyisocyanates include aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of aromatic aliphatic polyisocyanates include 1,3- or 1,4-phenylenedimethylene diisocyanate or mixtures thereof, 1,3- or 1,4-bis(1-isocyanate-1-methylethyl)benzene (tetramethylphenylenedimethylene diisocyanate) or mixtures thereof, and 1,3,5-triisocyanate-methylbenzene. They can be used alone or in combination of two or more.

[0988] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include isophenylene diisocyanate, terephthalene 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. They can be used alone or in combination of two or more.

[0989] Derivatives of polyisocyanates include, for example, dimers, trimers, biurets, urethanes, carbodiimides, urea diketones, urea ketimides, isocyanurates, iminooxadiazine diketones, and various other derivatives of the aforementioned polyisocyanate compounds. They can be used alone or in combination of two or more.

[0990] These polyisocyanates can be used in one or in combination of two or more.

[0991] As a polyisocyanate compound, it is preferable to use a compound in which the isocyanate group of the polyisocyanate compound is capped by a capping agent, i.e., a capped polyisocyanate compound (capped isocyanate). Capped polyisocyanate compounds are preferred because they are relatively stable even in aqueous solutions and can be used in the same aqueous solution as the composition.

[0992] End-capping agents are used to seal free isocyanate groups. End-capped polyisocyanate compounds can be regenerated by heating to, for example, above 100°C or above 130°C, thereby readily reacting with hydroxyl groups. Examples of end-capping agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. Polyisocyanate compounds can be used alone or in combination of two or more.

[0993] Epoxides are compounds that have epoxy groups. Examples of epoxy compounds include those with polyoxyalkylene groups, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether, etc.

[0994] Chloromethyl compounds are compounds containing a chloromethyl group. Examples of chloromethyl compounds include chloromethyl polystyrene.

[0995] Carboxyl-containing compounds are compounds that contain a carboxyl group. Examples of carboxyl-containing compounds include (poly)acrylic acid and (poly)methacrylic acid.

[0996] Specific examples of ketone-containing compounds include (poly)diacetone acrylamide and diacetone alcohol.

[0997] Specific examples of acylhydrazide compounds include hydrazine, carbazide, and adipic hydrazide.

[0998] Specific examples of melamine compounds include melamine resins and methylated melamine resins.

[0999] (Amount of curing agent)

[1000] The amount of curing agent relative to 100 parts by weight of the polymer 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. The amount of curing agent relative to 100 parts by weight of the polymer is 50 parts by weight or less and 40 parts by weight or less.

[1001] [Hydrophilic particles]

[1002] The compositions of the present invention may contain hydrophilic particles as an additional component. Here, hydrophilicity refers to the property that the particles readily disperse in an aqueous solvent without agglomeration. For example, adding 1.0% by weight of the particle powder and any dispersant relative to the aqueous solvent, stirring at 700 rpm for 10 minutes using a homogenizer, and then allowing it to stand for 1 hour, in this case, hydrophilicity is considered to be present when no precipitation or agglomeration of the particles can be visually observed. Furthermore, regarding aqueous dispersions of particles sold in a state where the particles are dispersed in an aqueous solvent, the particles contained therein are considered to be hydrophilic.

[1003] Hydrophilic particles can have hydrophilic groups on their surface. Examples of hydrophilic groups include cationic groups, anionic groups, amino groups, and hydroxyl groups. The surface of hydrophilic particles can be hydrophilized, but generally not hydrophobicated.

[1004] There are no particular limitations on hydrophilic particles as long as they possess hydrophilicity. Examples include inorganic particles (e.g., inorganic oxide particles) such as alumina, silica, and titanium dioxide, as well as organic particles such as latex, acrylic fiber, and nylon. Among these, inorganic particles are preferred from the perspective of ease of handling, and at least one of silica and alumina is particularly preferred. Commercially available examples include silicon oxide particles such as "SNOWTEX ST-OYL," "SNOWTEX ST-AK-L," and "SNOWTEX ST-AK-YL" (all manufactured by Nissan Chemical Co., Ltd.); titanium oxide particles such as "TA300" and "TA300D" (all manufactured by FUJI TITANIUM INDUSTRY CO., LTD.); and aluminum oxide particles such as "TM-5D" (manufactured by Daimei Chemical Industry Co., Ltd.). These particles can be used alone or in combination of two or more.

[1005] (Average primary particle size)

[1006] The average primary particle size of the hydrophilic particles can be 5 nm or more, 10 nm or more, 15 nm or more, 20 nm or more, 25 nm or more, or 30 nm or more. The average primary particle size can be 600 nm or less, 400 nm or less, 200 nm or less, 100 nm or less, 40 nm or less, 37.5 nm or less, 35 nm or less, 32.5 nm or less, 30 nm or less, 27.5 nm or less, 25 nm or less, or 22.5 nm or less, preferably 40 nm or less. Within these ranges, good water-repellent properties are achieved. The average primary particle size can be measured using a microscope (scanning electron microscope or transmission electron microscope). Specifically, the raw material is observed from above at any magnification using a microscope. Then, when the particle shape is spherical, its diameter is considered as the particle size; when it is non-spherical, the average of its longest and shortest diameters is considered as the particle size (particle size). Repeat the process of measuring the particle size of all particles present in the field of view, then moving the field of view and measuring the particle size again, so as to measure the particle size at more than 10 locations, and take the average value as the average primary particle size.

[1007] (Turbidity)

[1008] The turbidity of an aqueous dispersion obtained by dispersing hydrophilic particles in water at a concentration of 10 g / L and adjusting the pH to 7 can be 0.1 ppm or higher, 1 ppm or higher, 5 ppm or higher, or 10 ppm or higher. The turbidity of an aqueous dispersion obtained by dispersing hydrophilic particles in water at a concentration of 10 g / L and adjusting the pH to 7 can be 200 ppm or lower, 100 ppm or lower, 50 ppm or lower, 20 ppm or lower, 10 ppm or lower, 5 ppm or lower, or 2.5 ppm or lower, preferably 20 ppm or lower. Within these ranges, good balance between water repellency, slip resistance, and storage stability can be achieved. Turbidity can be measured using an integrating sphere turbidimeter PT200 manufactured by Nittoseiko Analytech Co., Ltd., according to JIS K0101, water supply test method, by plotting a standard curve (range 0–1000 ppm) using the turbidity of a standard kaolin (pigment) sample, and calculations are performed based on this standard curve.

[1009] (Zeta potential)

[1010] The zeta potential of an aqueous dispersion obtained by dispersing hydrophilic particles in water at a concentration of 10 g / L and adjusting the pH to 7 can be -20 mV or higher, -10 mV or higher, 0 mV or higher, +5 mV or higher, +10 mV or higher, or +20 mV or higher, preferably 0 mV or higher or +10 mV or higher. The zeta potential of an aqueous dispersion obtained by dispersing hydrophilic particles in water at a concentration of 10 g / L and adjusting the pH to 7 can be +200 mV or lower, +150 mV or lower, +100 mV or lower, +50 mV or lower, +30 mV or lower, +100 mV or lower, +10 mV or lower, or +5 mV or lower, preferably +100 mV or lower. By maintaining turbidity within the above range, good balance between water repellency, slip resistance, and storage stability can be achieved. The zeta potential can be measured, for example, using a commercially available zeta potential measuring device.

[1011] (Amount of hydrophilic particles)

[1012] The amount of hydrophilic particles, relative to the total amount of polymer and hydrophilic particles, can be 0.01% by weight or more, 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 1% by weight or more, 2% by weight or more, 3% by weight or more, or 5% by weight or more, preferably 0.5% by weight or more, and particularly preferably 2% by weight or more. The amount of hydrophilic particles, relative to the total amount of polymer and hydrophilic particles, can be 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 3% by weight or less, or 2% by weight or less, preferably 12% by weight or less. With the amount of hydrophilic particles within the above ranges, good water-repellent properties can be achieved.

[1013] The organosilicones, waxes, hydrophilic particles, liquid media, dispersants, surfactants, or curing agents listed above can be added after the polymer is manufactured, or the polymer monomers can be polymerized in the presence of the organosilicones, waxes, hydrophilic particles, liquid media, dispersants, surfactants, or curing agents listed above to manufacture the polymer.

[1014] [Other ingredients]

[1015] The composition may contain other components besides those listed above. Other components may be added after the polymer is manufactured. Examples of other components include water-repellent and / or oil-repellent agents, anti-slip agents, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorants, fragrances, etc. They may be used alone or in combination of two or more. In addition to the components listed above, other components include texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, anti-wrinkle agents, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, anti-shrinkage agents, washing anti-wrinkle agents, shape-retaining agents, drape-retaining agents, ironing improvers, whitening agents, bleaching agents, fabric softening clay, anti-dye migration agents such as polyvinylpyrrolidone, polymeric dispersants, stain removers, scum dispersants, and disodium 4,4-bis(2-sulfostylenyl)biphenyl (CIBA SPECIALTY). Fluorescent whitening agents such as TINOPALCBS-X (manufactured by CHEMICALS), dye fixatives, anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine, detergents, enzymes such as cellulase, amylase, protease, lipase, and keratinase used as fiber surface modifiers, antifoaming agents, silk protein powder that imparts the feel and function of silk such as moisture absorption and release, their surface modifiers, and emulsion dispersions. Specifically, these can be combined with K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk solution (for upholstery), SILKGEN G Soluble S (ICHIMARU PHARCOS), nonionic polymers composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units, such as FR627 manufactured by Muyo Chemical Industry and SRC-1 manufactured by Clariant Japan, etc., as anti-fouling agents. They can be used individually or in combination of two or more.

[1016] (Antistatic agent)

[1017] Examples of antistatic agents include: quaternary ammonium salts, pyridinium salts, and cationic antistatic agents with cationic functional groups such as primary, secondary, and tertiary amino groups; anionic antistatic agents with anionic functional groups such as sulfonates or 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 also be obtained by polymerization or copolymerization of monomers with cationic, anionic, or amphoteric ionic conductive groups. They can be used alone or in combination of two or more.

[1018] (preservative)

[1019] Preservatives are mainly used to increase preservative and bactericidal properties, ensuring preservation during long-term storage. Examples of preservatives include isothiazolino-based organosulfur compounds, benzisothiazoline-based organosulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propylene glycol. The amount of preservative relative to the total weight of the composition is preferably 0.0001 to 1% by weight. When the amount of preservative is above the lower limit of the above range, the effect of adding preservative is sufficiently obtained; when it is below the upper limit, the composition exhibits good storage stability.

[1020] (UV absorber)

[1021] Ultraviolet (UV) absorbers are agents that protect against ultraviolet radiation. They absorb UV rays and convert them into infrared or visible light, which are then released. Examples of UV absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, and 4-tert-butyl-4'-methoxybenzoylmethane.

[1022] (Antibacterial agent)

[1023] Antimicrobial agents are ingredients that inhibit the proliferation of bacteria on fibers, thereby suppressing the production of unpleasant odors caused by 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-hydroxyquinoline, and polylysine.

[1024] (Deodorant)

[1025] Examples of deodorants include clustered dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyl dimethylamine oxide, and aminocarboxylic acid metal complexes (such as the zinc complex of trisodium methylglycine diacetate described in International Publication No. 2012 / 090580).

[1026] (spices)

[1027] As a spice, there are no particular limitations, and a list of spice ingredients that can be used can be found in various literature, such as: "Perfume and Flavor Chemicals", Vol. I and II, Steffen Arctander, Allured Pub.Co. (1994). (“Synthetic Fragrance Chemistry and Commercial Knowledge”, by Motokazu Into, Chemical Industry Daily (1996)); “Perfume and Flavor Materials of Natural Origin”, by Steffen Arctander, Allured Pub. Co. (1994). (“Encyclopedia of Fragrance”, edited by the Japan Fragrance Association, Asakura Shoten (1989)); “Perfumery Material Performance V.3.3”, Boelens Aroma Chemical Information Service (1996); and “Flower oils and Floral Compounds In Perfumery”, Danute Lajaujis Anonis, Allured Pub. Co. (1993), etc., may be cited as part of the invention described herein.

[1028] (Amount of other ingredients)

[1029] The amount of other components relative to 100 parts by weight of the polymer 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. The amount of other components relative to 100 parts by weight of the polymer can be 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.

[1030] (Amount of polymer)

[1031] In the composition, the amount of polymer can be 0.01% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, or 30% by weight or more. In the composition, the amount of polymer can be 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight or less.

[1032] <Uses of the Composition>

[1033] Examples of uses of the compositions of the present 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, stain removers, release agents, and mold release agents (external or internal mold release agents). Alternatively, the compositions of the present invention can be used as 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, stain removers, release agents, and mold release agents (external or internal mold release agents).

[1034] <Method for manufacturing the composition>

[1035] The method of manufacturing the composition may include a process of reacting (polymerizing) the monomer (1) in a medium (e.g., a liquid medium) containing the monomer (1) and the additional components listed above (e.g., emulsifiers, liquid media, waxes, etc.) to obtain the polymer.

[1036] Alternatively, the method of manufacturing the composition may include the steps of adding an additional component (e.g., an emulsifier, a liquid medium, a wax, etc.) to a solution or dispersion of the polymer, or the steps of mixing a solution or dispersion of the polymer with a solution or dispersion of an additional component (e.g., an emulsifier, a liquid medium, a wax, etc.).

[1037] To ensure the composition exhibits high water repellency, it is preferable to subject the composition to ultrasound (ultrasound treatment). Ultrasound treatment is preferably performed just before application to the object being treated. For example, the composition is applied to the object 1 minute to 1 hour after ultrasound treatment. Ultrasound treatment can be performed by applying ultrasound to the composition. There are no particular limitations on the ultrasound generator, but a power of 500W or more, for example, 500 to 2000W, is preferred for efficient mixing. The treatment time for ultrasound treatment can be from 0.5 minutes to 60 minutes. For example, a homogeneous composition can be obtained by treating the composition for 10 minutes using a 500W ultrasound generator.

[1038] Examples of polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization.

[1039] In solution polymerization, the monomer can be dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen replacement, the mixture can be 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 amount of polymerization initiator used relative to 100 parts by weight of monomer is 0.01–20 parts by weight, for example, 0.01–10 parts by weight.

[1040] Organic solvents are substances whose monomers are inactive and which can dissolve them. Examples include esters (e.g., esters with 2-40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2-40 carbon atoms, specifically methyl ethyl ketone, diisobutyl ketone, and methyl isobutyl ketone), and alcohols (e.g., alcohols with 1-40 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 amount of organic solvent used is 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.

[1041] In emulsion polymerization, the monomer can be emulsified in water in the presence of a polymerization initiator and an emulsifier. After nitrogen replacement, polymerization is carried out by stirring at 50–80°C for 1–20 hours. Polymerization initiators 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; and oil-soluble substances such as azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxypentanoate, and diisopropyl peroxide dicarbonate. The amount of polymerization initiator used is in the range of 0.01–10 parts by weight relative to 100 parts by weight of monomer.

[1042] To obtain a polymer aqueous dispersion with excellent storage stability, it is preferable to use an emulsification device that provides strong abrasive energy, such as a high-pressure homogenizer or an ultrasonic homogenizer, to micronize and polymerize the monomers in water. Furthermore, various anionic, cationic, or nonionic emulsifiers can be used as emulsifiers, in an amount ranging from 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 compatible, it is preferable to add a compatibilizer to ensure adequate compatibility, such as a water-soluble organic solvent or a low molecular weight monomer. Adding a compatibilizer can improve emulsification and copolymerization properties.

[1043] 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, etc., used in amounts ranging from 1 to 50 parts by weight, 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, etc., used in amounts ranging from 1 to 50 parts by weight, for example, 10 to 40 parts by weight, relative to 100 parts by weight of the total monomer.

[1044] Chain transfer agents can be used during polymerization, allowing the molecular weight of the polymer to vary depending on the amount of chain transfer agent used. Examples of chain transfer agents include compounds containing thiol groups such as lauryl thiols, thioglycols, and thioglycerols (especially alkyl thiols, e.g., those with 1 to 40 carbon atoms), and inorganic salts such as sodium hypophosphite and sodium bisulfite. The amount of chain transfer agent used relative to 100 parts by weight of the total monomer is in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight.

[1045] The composition can be in the form of a solution, emulsion (especially an aqueous dispersion) or aerosol.

[1046] <Water-repellent agent>

[1047] The water-repellent agent of the present invention contains the polymer of the present invention. The water-repellent agent of the present invention can be the composition of the present invention. That is, the composition of the present invention can be used directly as a water-repellent agent. In addition to the polymer of the present invention, the water-repellent agent of the present invention can also be prepared using various materials and conditions used to prepare the composition of the present invention.

[1048] The water-repellent agent of the present invention may not contain any one of the following: compounds having 8 or more fluoroalkyl groups, compounds having 8 or more perfluoroalkyl groups, compounds having 4 or more fluoroalkyl groups, compounds having 4 or more perfluoroalkyl groups, compounds having perfluoroalkyl groups, compounds having fluoroalkyl groups, and compounds having fluorine atoms. Even without these fluorine compounds, the water-repellent agent of the present invention can impart liquid-repellent properties to the substrate.

[1049] <Uses of water-repellent agent>

[1050] Examples of uses of the water-repellent agent of the present 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, stain removers, release agents, mold release agents (external mold release agents or internal mold release agents), etc.

[1051] <Method for manufacturing processed products>

[1052] The method for manufacturing the treated article of the present invention includes the step of applying the water-repellent agent of the present invention to a substrate.

[1053] [Processed Products]

[1054] Examples of substrates treated with the water-repellent agent of the present invention include fiber substrates, 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, kiln products, plastics, coatings, and plaster. Various examples of fiber products can be listed. 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 cellulose 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 agent, a woven fabric will be described in detail.

[1055] (woven fabric)

[1056] • Manufacturing methods of woven fabrics

[1057] The woven fabric can be obtained by weaving a base fabric from yarns composed of long and short fibers, as described above, followed by post-processing and water-repellent finishing. Weaving can be done using known looms or knitting machines, and the preparatory processes prior to weaving can also utilize known equipment.

[1058] After weaving, the fabric can be further processed using known scouring and dyeing methods and equipment corresponding to the fiber raw materials of the fabric.

[1059] After post-processing, the woven fabric can be subjected to a water-repellent treatment. In this treatment, an aqueous solution containing a water-repellent agent (which can be the water-repellent agent or composition of this invention) is first 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. Depending on the requirements, the aqueous solution may also contain crosslinking agents, softeners, antistatic agents, etc. After the water-repellent treatment, the woven fabric can be further calendered to improve its water-repellent properties.

[1060] Woven fabrics are suitable for clothing applications requiring water repellency, especially for outdoor or sportswear such as skiing, snowboarding, and golf, as well as uniforms.

[1061] •Laminated fabric

[1062] The fabric can also be provided as a laminated fabric in which a moisture-permeable and waterproof layer is provided on one side of the woven fabric of the present invention. The moisture-permeable and waterproof layer can be directly laminated onto the woven fabric, or it can be laminated onto the woven fabric using an adhesive layer. In the case where the laminated fabric of the present invention is used for clothing or the like, it is configured such that the woven side is exposed to rainwater or the like.

[1063] • Breathable waterproof layer

[1064] 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.

[1065] 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 using the adhesive described later.

[1066] There are no particular limitations on the resin used to form the breathable and waterproof layer, but non-porous resins and porous resins are preferred. Non-porous resins can be polyurethane resins or polyester elastomer resins that have hydrophilic components to achieve breathability. In addition, porous resins can be polyurethane resins that form wet porous membranes or polyurethane resins that achieve pores through electrospinning, as well as porous membranes of PTFE, PE, or PP.

[1067] As a polyurethane resin, a known resin obtained by reacting a polyisocyanate component with a polyol component can be used.

[1068] A breathable and waterproof membrane with a microporous structure can be obtained by wet coagulation of a DMF solution of polyurethane resin containing inorganic micropowders. Examples of inorganic micropowders include those composed of silica, alumina, or titanium dioxide. Furthermore, the average primary particle size of the inorganic micropowder is preferably around 7 to 40 nm. The amount of 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.

[1069] The thickness of the breathable waterproof layer is preferably 5 μm or more, more preferably 10 to 30 μm. When the thickness is within the above range, the balance between waterproofness and breathability is excellent, and it also has advantages in terms of feel.

[1070] • Adhesive layer

[1071] The laminated fabric preferably includes an adhesive layer. That is, the woven fabric and the breathable waterproof layer are preferably laminated using an adhesive layer. Furthermore, in terms of breathability, the adhesive layer is preferably a discontinuous layer such as a dotted or grid pattern.

[1072] There are no particular limitations on the type of adhesive used to form the adhesive layer, but an adhesive with excellent compatibility with the breathable and waterproof layer is preferred. For example, if a resin with polyurethane resin as the main component is selected as the resin for forming the breathable and waterproof layer, an adhesive layer composed of a polyurethane-based adhesive is preferred. Polyurethane-based adhesives can be adhesives of any structure, such as ether-based, ester-based, or polycarbonate-based adhesives.

[1073] The adhesive layer can be formed on the entire surface of one side of the woven fabric, or it can be patterned from the viewpoint of moisture permeability or hand feel. There are no particular limitations on the form of the pattern, and examples include dotted, linear, grid, checkered, and tortoise shell patterns, all of which are preferably uniformly distributed.

[1074] The thickness of the adhesive layer is preferably about 10 to 100 μm, and more preferably 20 to 80 μm.

[1075] • Lining made of fiber fabric

[1076] In the laminated fabric of the present invention, a lining fiber fabric may also be laminated on the surface of the breathable waterproof layer (the surface of the breathable waterproof layer opposite to the surface of the woven fabric on which the present invention is laminated). The lining fiber fabric can protect the breathable waterproof layer and can make the waterproof performance (water pressure resistance) and strength even better.

[1077] Various woven fabrics and knitted fabrics can be listed as lining textiles. Among them, compared with woven fabrics, the structural lines of knitted fabrics tend to stand out on the surface and do not form a flat surface. From the viewpoint of further enhancing the anchoring effect and preventing peeling from the breathable and waterproof layer, knitted fabrics are preferred. In addition, warp-knitted fabrics can produce a long base fabric during weaving and have fewer seams, which allows them to be evenly layered on the breathable and waterproof layer, making them also preferred in this respect.

[1078] The material of the fibers constituting the lining fabric is not particularly limited and can be appropriately selected, but nylon fibers are preferred. This is because nylon fibers typically use acid dyes, making them less prone to the problem of disperse dye migration and sublimation into the breathable and waterproof layer, which is common in polyester fibers using disperse dyes. The morphology (long fibers, short fibers, or yarns) or fineness of the constituent fibers of the lining fabric is not particularly limited and can be appropriately selected without compromising the effectiveness of the invention.

[1079] • Characteristics of laminated fabrics

[1080] The laminated fabric has excellent water resistance. As a preferred example of the water resistance of the laminated fabric of the present invention, the water level measured according to the water resistance test specified in JIS L 1092:2009 Method A (low water pressure method) is, for example, 10,000 mm or more, preferably 15,000 mm or more, more preferably 16,000 mm or more, and particularly preferably 20,000 mm or more.

[1081] The laminated fabric exhibits excellent moisture permeability. As a preferred example of the moisture permeability of the laminated fabric of the present invention, a moisture permeability measured according to the JIS L 1099:2021 B-1 method (potassium acetate method) is, for example, 10000 g / m². 2 • 24 hours or more, preferably 15000g / m 2 • 24 hours or more, preferably 20000g / m 2 • More than 24 hours. There is no specific upper limit for this moisture permeability; for example, 40,000 g / m² could be listed. 2 • 24h or 35000g / m 2 •24h•mm. Additionally, according to JIS L 1099:2021 A-1 method (calcium chloride method), the permeability can be, for example, 4000 g / m³. 2 • 24 hours or more, preferably 8000g / m 2 • 24 hours or more, preferably 10000g / m 2 • More than 24 hours. Regarding the upper limit of this moisture permeability, as the limit of the measurement method, it is 13000–15000 g / m³. 2 • Approximately 24 hours.

[1082] For laminated fabrics, in the laminated fabrics of the present invention, when the peel strength between the woven fabric and the breathable waterproof layer is measured according to the method of JIS K 6404-2, for example, it is suitable for clothing use if it is 2.55 N / 2.54 cm or more, and in some applications it is preferred to be 5 N / 2.54 cm or more.

[1083] • Manufacturing method of laminated fabric

[1084] There are no particular restrictions on the manufacturing method of the laminated fabric. For example, the first manufacturing method and the second manufacturing method shown below can be listed.

[1085] First manufacturing method: including a process of coating the surface of a woven fabric with a resin constituting the above-mentioned breathable and waterproof layer, thereby forming the above-mentioned breathable and waterproof layer.

[1086] 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 to the breathable waterproof layer using the adhesive layer.

[1087] In the first manufacturing method, a coating method can be used as a method for applying a resin constituting a breathable and waterproof layer to the surface of the woven fabric. In the coating method, a doctor blade coater or a comma coater can be used. Furthermore, from the viewpoint of possessing excellent breathability, a wet method is preferred for obtaining the breathable and waterproof layer.

[1088] In the second manufacturing method, lamination is an example of a method for forming an adhesive layer on a woven fabric or a breathable waterproof layer. In lamination, the adhesive layer can be formed using a resin solution or a hot-melt method. First, gaps are made on the surface of a release material (release paper, release cloth, or release film, etc.), and while adjusting the thickness, a breathable waterproof layer is formed and then dried and heat-treated, thereby forming a film by completely reacting the breathable waterproof layer with a resin composition (e.g., a resin composition containing resin and an organic solvent). The release material can be appropriately removed after lamination or curing. Alternatively, in the case of lamination using a hot-melt method, the release material can be peeled off, and the film can be laminated separately.

[1089] In addition, breathable and waterproof membranes can be laminated to membranes made by extrusion methods such as T-die method and blow molding under solvent-free conditions, or porous membranes made by electrospinning, such as PTFE, PE, PP, etc.

[1090] Then, an adhesive layer is formed on the woven fabric or the breathable waterproof layer. For example, in the method using a resin solution, a two-component curing polyurethane resin solution with a viscosity adjusted to the range of 500–5000 mPa•s can be applied to the entire surface or in a pattern. After drying, the adhesive layer is formed, and the woven fabric and the breathable waterproof layer are bonded together using the adhesive layer by pressing or heat-pressing, thereby performing the second manufacturing method.

[1091] On the other hand, in the case of hot melting, a moisture-curing resin that reacts with moisture in the air is preferred, and in practical terms, a resin that melts in a temperature range of approximately 80–150°C is more preferable. In this case, firstly, considering the resin's melting point and viscosity during melting, the hot-melt resin is melted. Then, while coating the molten resin onto the woven fabric or the breathable waterproof layer and cooling it at room temperature, it is allowed to cure, forming an adhesive layer. Afterward, the woven fabric and the breathable waterproof layer are bonded and pressed together using the adhesive layer, thereby performing the second manufacturing method. Alternatively, if a good feel is desired, the pattern can be applied to the breathable waterproof membrane before bonding it to the woven fabric.

[1092] Then, using appropriate methods known to the public, a lining of fibrous fabric is layered on top of the breathable and waterproof layer.

[1093] • Applications of laminated fabrics

[1094] The laminated fabric has excellent water repellency and moisture permeability, and the moisture permeability and waterproof layer will not peel off even in harsh environments. Therefore, it is preferred for use in uniforms, sportswear, outdoor products and other fields used outdoors.

[1095] [Handling Method]

[1096] The water-repellent agent of the present invention can be applied to a substrate (especially a fiber substrate) as a treatment agent (particularly a surface treatment agent) using existing known methods. This can be achieved by dispersing the water-repellent agent of the present invention in an organic solvent or water for dilution, applying it to the surface of the substrate using known methods such as dip coating, spray coating, or foam coating, and then drying it. After drying, a fiber article with the solid components of the water-repellent agent adhering to it can be obtained. Alternatively, if desired, it can be applied together with a suitable crosslinking agent and cured. Furthermore, the water-repellent agent of the present invention can be used in combination with various additives such as water-repellent and / or oil-repellent agents, antislip agents, antistatic agents, hand feel modifiers, softeners, antibacterial agents, flame retardants, coating fixatives, antiwrinkle agents, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, and defoamers. Examples of various additives are the same as those described in the "Other Components" section of the above-described composition. The concentration of the polymer in the treatment agent that comes into contact with the substrate can be varied appropriately depending on the application, and can be 0.01 to 10% by weight, for example 0.05 to 5% by weight.

[1097] [Fiber Products]

[1098] Various examples can be listed for fiber products used as a base material, such as cloth or paper products. Fiber products used as a base material are also called fiber-based materials.

[1099] 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 cellulose acetate; inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber; and blends thereof. Textile products include woven fabrics, knitted fabrics, and non-woven fabrics; clothing-like cloths and carpets; but they can also be made from fibers, yarns, and intermediate fiber products (such as cotton slivers or rovings) that were not yet cloth.

[1100] Examples of paper products include paper made from bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp, high-yield pulps 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 of paper, and molded objects made of 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, 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).

[1101] The water-repellent agent can be applied to the fiber substrate (e.g., fabric) using any known method for treating the fiber substrate with a liquid. The fiber substrate can be impregnated with the water-repellent agent, or the solution can be adhered to or sprayed onto the fiber substrate. To exhibit water repellency, the treated fiber substrate is preferably dried and cured by heating. The heating temperature can be, for example, 80°C to 250°C, 100°C to 170°C, or 100°C to 120°C. The heating temperature is preferably 100°C to 170°C. In this invention, good performance can be obtained even with low-temperature heating (e.g., 100°C to 140°C). In this invention, the heating time can be from 5 seconds to 60 minutes, for example, from 30 seconds to 3 minutes.

[1102] Alternatively, the water-repellent agent can also be applied to the fiber substrate by washing, for example, by washing or by dry cleaning.

[1103] The treated fiber substrate can be fabric, including woven fabrics, knitted fabrics, nonwoven fabrics, clothing-like fabrics, and carpets, but can also be fibers, yarns, or intermediate fiber products (e.g., slivers or rovings). The water-repellent agent of the present invention is particularly effective in making fiber products (e.g., synthetic fibers) water-repellent.

[1104] The fibers constituting the fiber substrate 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 types can be used together.

[1105] Examples of natural fibers include cellulose fibers such as cotton, flax, and pulp, as well as chitin, chitosan, wool, and silk. Specific examples of wood pulp include mechanical pulps such as groundwood pulp (GP), pressurized groundwood pulp (PGW), and thermomechanical pulp (TMP); chemical pulps such as high-content unbleached coniferous kraft pulp (HNKP, N material), bleached coniferous kraft pulp (NBKP, N material, NB material), unbleached hardwood kraft pulp (LUKP, L material), and bleached hardwood kraft pulp (LBKP, L material); waste paper pulps such as deinked pulp (DIP); and semi-chemical pulps such as waste paper pulp (WP) or semi-chemical pulp (CP).

[1106] 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; and polyvinyl alcohol, polyurethane, and polyvinyl chloride.

[1107] Examples of semi-synthetic fibers include acetate and triacetate. Examples of regenerated fibers include rayon, cupro, high wet modulus viscose, lyocell, and Tencel. Examples of inorganic fibers include glass fiber and carbon fiber.

[1108] Alternatively, the fiber substrate can also be leather. To make the leather hydrophobic and oleophobic, the manufacturing polymer can be applied to the leather as an aqueous solution or aqueous emulsion at various stages of leather processing, such as during the wetting process or the final processing of the leather.

[1109] Alternatively, the fiber substrate can also be paper. The manufacturing polymer can be applied to pre-formed paper, or it can be applied at various stages of papermaking, such as during the paper drying process.

[1110] "Treatment" refers to applying the water-repellent agent to a substrate through impregnation, spraying, coating, or other methods. Through treatment, the polymer of the water-repellent agent, as the active ingredient, penetrates into the interior of the substrate and / or adheres to its surface. In other words, through treatment, a substrate (e.g., a fiber product) can be obtained with the polymer in the water-repellent agent of this invention adhering to it. This substrate is a water-repellent fiber product, i.e., a water-repellent fiber product.

[1111] [Pretreatment of fiber substrate]

[1112] The fiber substrate can be pretreated before being treated with the water-repellent agent of the present invention. By pretreating the fiber substrate, the water-repellent agent can impart excellent strength to the treated fiber substrate.

[1113] Examples of pretreatment for fiber substrates include cationization treatment based on reactions 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.

[1114] There are no limitations on the method for pretreating the fiber substrate; any existing known method can be used. Alternatively, the pretreatment solution can be dispersed and diluted in an organic solvent or water as needed, and then applied to the surface of the fiber substrate using known methods such as dip coating, spray coating, or foam coating, followed by drying. The pH and temperature of the pretreatment solution can also be adjusted according to the desired level of treatment. As an example of a method for pretreating the fiber substrate, a method using a hydrocarbon-based water-repellent agent will be described in detail.

[1115] Pretreatment methods for fiber substrates may include imparting a coating of fibers with a material selected from SO3M. 1 (where M) 1 The monovalent group (representing a monovalent cation) and -COOM are indicated by the 1-valent group. 2 (where M) 2 The monovalent group (representing a monovalent cation) and -O-P(O)(OX) are shown. 1 (OX) 2 (where X) 1 and X 2 A process of taking 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).

[1116] 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 alkyl, it is preferred to be an alkyl group with 1 to 22 carbon atoms, and more preferably an alkyl group with 4 to 12 carbon atoms.

[1117] Fibers containing the aforementioned specific functional groups (hereinafter sometimes referred to as "fibers containing functional groups") can be prepared by, for example, the following methods.

[1118] (i) To attach a compound having the specific functional group described above to a fibrous material. The attachment of the compound may be a state in which a portion of the compound and a portion of the fiber are chemically bonded within a range where the specific functional group remains in sufficient quantity.

[1119] (ii) A fiber in which the aforementioned specific functional groups are directly introduced into the material constituting the fiber.

[1120] In case (i), for example, a functional group-containing fiber can be obtained 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.

[1121] As raw materials for fiber materials, there are no particular limitations. Examples include natural fibers such as cotton, linen, silk, and wool; semi-synthetic fibers such as rayon and cellulose 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, such as fibers (tows, slivers, etc.), yarns, woven fabrics (including cross-knitted fabrics), woven fabrics (including interwoven fabrics), non-woven fabrics, and paper.

[1122] In this embodiment, from the viewpoint of obtaining a fiber product with good water repellency, 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), polyterephthalate trimethyl terephthalate, polylactic acid and other polyesters, as well as blended fibers containing them.

[1123] As mentioned above, it has -SO3M 1 For compounds, phenolic polymers can be used. Examples of such phenolic polymers include materials containing at least one compound represented by the following general formula.

[1124]

[1125] [In formula (2), X] 2 Indicates - SO3M 3 (where M) 3 [A group representing a monovalent cation or a group represented by the following general formula, where n is an integer from 20 to 3000.]

[1126]

[1127] [In the formula, M] 4 This indicates a monovalent cation.

[1128] As for the above M 3 Examples include H, K, Na, or ammonium ions that may have substituents.

[1129] As for the above M 4 Examples include H, K, Na, or ammonium ions that may have substituents.

[1130] The compounds represented by the above general formula can be, for example, formaldehyde condensates of phenol sulfonic acid or methyl acetal condensates of sulfonated bisphenol S.

[1131] As mentioned above, it has -COOM 2 Compounds that can be listed include polycarboxylic acid polymers.

[1132] As a polycarboxylic acid polymer, for example, polymers synthesized by using acrylic acid, methacrylic acid, maleic acid, etc. as monomers according to existing known free radical polymerization methods or commercially available polymers can be used.

[1133] As a method for manufacturing polycarboxylate polymers, one example is adding a free radical polymerization initiator to an aqueous solution of the aforementioned monomers and / or their salts, and reacting at 30–150°C for 2–5 hours. Alternatively, an alcohol such as methanol, ethanol, or isopropanol, or an aqueous solvent such as acetone, can be added to the aqueous solution of the aforementioned monomers and / or their salts. Examples of free radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; redox polymerization initiators combining 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 mercaptoacetate) can be added to adjust the degree of polymerization.

[1134] In free radical polymerization, in addition to the monomers mentioned above, copolymerizable monomers can also be used. 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.

[1135] In polycarboxylate polymers, the carboxyl groups can be free or neutralized by alkali metals or amine compounds. Examples of alkali metals include sodium, potassium, and lithium; examples of amine compounds include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[1136] 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.

[1137] Polycarboxylate polymers can be commercially available products such as "NEOCRYSTAL 770" (manufactured by Nichika Chemical Co., Ltd., trade name) and "SELOPOL PC-300" (manufactured by Sanyo Chemical Co., Ltd., trade name).

[1138] As mentioned above, having -O-P(O)(OX) 1 (OX) 2 Compounds of which, for example, can be listed as phosphate ester compounds represented by the following general formula.

[1139]

[1140] [In the formula, X] 1 or X 2 The meaning is the same as above, X 3 [Represents alkyl groups with 1 to 22 carbon atoms.]

[1141] 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.

[1142] From the viewpoint of obtaining fiber products with good water repellency, lauryl phosphate and decyl phosphate are preferred.

[1143] Phosphate compounds can be commercially available products such as "PHOSPHANOL ML-200" (manufactured by Toho Chemical Industry Co., Ltd., trade name).

[1144] A pretreatment solution containing one or more of the compounds having the specific functional groups described above can be prepared as an aqueous solution of, for example, the compounds described above. Additionally, the pretreatment solution may also contain acids, bases, surfactants, chelating agents, etc.

[1145] Methods for treating fibrous materials using the aforementioned pretreatment solution include, for example, padding, impregnation, spraying, and coating. As for padding, for example, using... (From pages 396-397 of the Dictionary of Fiber Dyeing and Processing (published by Nikkan Kogyo Shimbun in 1949)) The method of the padding apparatus described on pages 256-260 of (Coloring Chemicals III (published by Jikkyo Publishing Co., Ltd. in 1975)). As a coating treatment, examples include using... The coating machine method is described on pages 473-477 of "An Overview of Dyeing and Finishing Equipment (Published by Textile Company, 1956)". As an impregnation treatment, examples include using... The batch dyeing machine method described on pages 196-247 of "Overview of Dyeing and Finishing Equipment (Published by Textile Company, 1956)" can utilize liquid flow dyeing machines, airflow dyeing machines, roller dyeing machines, skein dyeing machines, washing dyeing machines, and package dyeing machines. For spray treatment, examples include gas spraying using compressed air to form a mist of the treatment liquid before spraying, and gas spraying using hydraulic atomization. The concentration of the treatment liquid and subsequent heat treatment conditions can be appropriately adjusted considering the purpose and performance. Furthermore, if the pretreatment liquid contains water, it is preferable to dry it after it is applied to the fiber material to remove the water. There are no particular limitations on the drying method; either dry heat or wet heat methods are acceptable. There are also no particular limitations on the drying temperature; for example, drying can be done at room temperature to 200°C for 10 seconds to several days. If necessary, a heat treatment at 100-180°C for approximately 10 seconds to 5 minutes can be performed after drying.

[1146] In addition, when the fiber material is a dyed product, the pretreatment with the pretreatment solution can be carried out before dyeing or in the same bath as dyeing. However, when performing reduction soaping, there is a risk that the adsorbed compounds with the above-mentioned specific functional groups (such as phenolic polymers) may be shed during the process. Therefore, it is preferable to perform the treatment after reduction soaping after dyeing.

[1147] The treatment temperature for immersion can be set to 60–130℃. The treatment time can be set to 5–60 minutes.

[1148] In the functional group introduction process using a pretreatment solution, it is preferable to treat the material with an amount of the compound having the aforementioned specific functional groups in a quantity 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.

[1149] 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.

[1150] In the pretreatment solution, salts can also be used to more effectively adsorb compounds with the aforementioned specific functional groups onto the fiber material through the salting-out effect. Examples of usable salts include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate.

[1151] In the functional group introduction process using a pretreatment solution, it is preferable to remove excess compounds containing the aforementioned specific functional groups after treatment. Washing with water is an example of such removal methods. By ensuring thorough removal, the obstruction of water-repellent properties during subsequent water-repellent processing can be prevented, and the resulting fiber product has a better hand feel. Furthermore, it is preferable that the obtained functional group-containing fibers are thoroughly dried before contacting with the hydrocarbon-based water-repellent agent.

[1152] (ii) As a fiber in which the above-mentioned specific functional groups are directly introduced into the material constituting the fiber, cationic dyeable polyester (CD-PET) can be listed as an example.

[1153] From the viewpoint of improving the water repellency of the resulting fiber product, the surface zeta potential of functional group-containing fibers 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.).

[1154] As a method for treating pulp substrates, internal treatment methods can be employed, such as adding a dispersant to the pulp before papermaking (e.g., pulp stock), or external treatment methods, such as applying a dispersant to the pulp after papermaking (e.g., pulp products). Examples of internal treatment methods include mixing and impregnation, which may involve adding a dispersant to the pulp stock and then mixing it. Examples of external treatment methods include spraying and coating, specifically including sizing presses with glue tanks, gate rolls, and metering rods. The treatment can be either internal or external. For example, when the pulp substrate is paper, the solution can be coated onto the paper, applied to the paper, sprayed onto the paper, or mixed with the pulp stock before papermaking.

[1155] The implementation methods have been described above, but it should be understood that various changes can be made to the methods and details as long as they do not depart from the spirit and scope of the claimed protection.

[1156] Example

[1157] The following describes specific embodiments of the present invention, but the embodiments are not intended to limit the present invention.

[1158] <Experimental Methods>

[1159] The steps of the experiment are as follows.

[1160] [Molecular weight distribution]

[1161] Average molecular weight:

[1162] The average molecular weight of the copolymer was determined using GPC (gel permeation chromatography) (converted from polystyrene).

[1163] For gel permeation chromatography, an HLC-8420GPC EcoSEC Elite-WS (manufactured by Tosoh Corporation) was used. For the column, a column consisting of two TSKgel SuperMultipore HZ-M columns connected together was used. For the detector, an RI detector was used. For the reference material, standard polystyrene (SRM706a NIST) was used.

[1164] The analytical sample was prepared by dissolving the copolymer in tetrahydrofuran to prepare a 0.1% by weight solution, which was then passed through a 0.5 μm filter. For the determination of the average molecular weight, the column was maintained at 40 °C, tetrahydrofuran was used as the eluent, and the flow rate was set to 0.35 mL / min, with 10 μL of the analytical sample injected.

[1165] [Adhesion]

[1166] The product obtained by drying the polymer-containing solution at 50–60°C for 2 hours, or the product obtained by extracting the polymer-containing solution with ethanol, is placed on a metal sample stage with a diameter of 80 mm and heated at 40°C for 3 minutes. The product is then evaluated using a probe with a diameter of 50 mm. The viscosity is calculated as the average of three measurements, or, if the measured value fluctuates, five measurements are taken, discarding the upper and lower limits, and the average of the remaining values ​​is used.

[1167] Machine Name: RHESCA Viscosity Testing Machine TAC-II

[1168] Test conditions:

[1169] constant load

[1170] (1) Immersion speed: 120 mm / min.

[1171] (2) Test speed 600 mm / min.

[1172] (3) Preload 500gf

[1173] (4) Holding time 10 seconds

[1174] (5) Distance 5mm

[1175] The higher the measured value, the greater the adhesion.

[1176] [Water-repellent properties]

[1177] The water repellency of the test-treated fabric was evaluated using the spray method according to JIS-L-1092 (AATCC-22).

[1178] Evaluate water repellency based on the benchmarks shown below. A higher score indicates better water repellency. Set intermediate values ​​(95, 85, 75, 65, 55) according to the condition.

[1179] 100: No moisture or water droplets were observed on the surface.

[1180] 90: The surface was not wet, but small water droplets were observed adhering to it.

[1181] 80: Small, individual water droplet-like wetting is observed on the surface.

[1182] 70: More than half of the surface is wet, and the condition of the small, individually wetted permeable fabrics can be observed.

[1183] 50: The surface appears wet overall.

[1184] 0: Moisture was observed on both the surface and the back.

[1185] [Lightly remove oil]

[1186] For the test-treated fabric, an oil made by blending oleic acid and PEG at a ratio of 1:9 was used, and the oil-repelling performance was evaluated according to the following four grades. Intermediate values ​​(B+, B-, C+, C-) were set according to the condition.

[1187] A: The droplet is transparent (unwetted) and round.

[1188] B: The edges or bottom of the droplet are slightly dark and rounded.

[1189] C: Droplets are visible seeping into the greige fabric.

[1190] D: The droplet has completely penetrated.

[1191] [Chalk resistance]

[1192] Place each test cloth on a flat surface, gently scratch the surface of the test cloth with your fingernail, and visually evaluate the trace left by the fingernail scratch, which resembles chalk residue.

[1193] ◎○: The trajectory is almost invisible

[1194] ○: The trajectory is basically invisible

[1195] 〇△: The trajectory is faintly visible

[1196] △: Trajectory visible

[1197] △×: The trajectory appears quite dark.

[1198] Si-based monomers (A)

[1199] The SILAPLANE TM-0701T manufactured by JNC Corporation shown below is used as the Si-based monomer (A).

[1200]

[1201] Si-based monomers (B)

[1202] [Preparation of monomers]

[1203] (Synthesis of intermediate 1)

[1204] A thermometer, dropping funnel, and nitrogen line were fitted to a four-necked flask, which was then immersed in an ice bath. Next, 14.74 g of 1,1,1,3,3-pentamethyldisiloxane (a siloxane compound), 0.04 g of tris(pentafluorophenyl)borane, and 30 mL of toluene were added to the flask, and the solution was stirred. After creating a nitrogen atmosphere in the flask, 5.1 mL of (3-chloropropyl)diethoxy(methyl)silane (a silane compound) and 10 mL of toluene were added to the dropping funnel, and the solution was slowly added to the flask. After the addition was complete, the flask was removed from the ice bath and stirred at room temperature for 6 hours. After confirming the Si-OEt conversion by 1H-NMR, neutral alumina was added to the flask and stirred for 30 minutes. The stirred alumina mixture was filtered through a 0.45 μm filter to obtain a solution. The solvent was removed from the obtained solution by rotary evaporation to obtain a transparent liquid intermediate 1. Intermediate 1 was evaluated using 1H-NMR and GC.

[1205] (Synthesis of Si-based monomers (B))

[1206] A thermometer, dropping funnel, and nitrogen line were fitted to a four-necked flask, which was then immersed in an ice bath. Next, 0.01 g of butylated hydroxytoluene, 0.36 g of potassium iodide, 0.98 g of sodium acrylate, 40 mL of dimethylformamide, and 5 g of intermediate 1 were added to the flask to obtain a mixture. After creating a nitrogen atmosphere in the flask, it was heated to 120 °C and the mixture was stirred for 5 hours. The flask was then cooled to 50 °C, and the mixture was washed with water using a separatory funnel to obtain a yellow liquid. This liquid was dried with sodium sulfate, and the resulting mixture was filtered to obtain a Si-based monomer (B) as a clear liquid. The Si-based monomer (B) was evaluated using 1H-NMR and GC.

[1207]

[1208] Si-based monomers (C)

[1209] The following Si-based monomer (C) was obtained according to WO2020 / 142474.

[1210]

[1211] Si-based monomers (D)

[1212] The following Si-based monomer (D) was obtained according to Japanese Patent Application Publication No. 2019-89715.

[1213]

[1214] Si-based monomers (E)

[1215] [Preparation of monomers]

[1216] (Synthesis of intermediate 2)

[1217] Perform the same steps as in the synthesis of intermediate 1, using (3-chloropropyl)trimethoxysilane as the silane compound.

[1218] (Synthesis of Si-based monomers (E))

[1219] The same steps as those for the synthesis of Si-based monomer (B) were performed, using intermediate 2, to obtain Si-based monomer (E) in the form of a transparent liquid.

[1220]

[1221] Si-based monomers (F)

[1222] [Preparation of monomers]

[1223] (Synthesis of intermediate 3)

[1224] Perform the same steps as in (the synthesis of intermediate 1), using 1,1,1,3,5,5,5-heptamethyltrisiloxane as the siloxane compound and (3-chloropropyl)trimethoxysilane as the silane compound.

[1225] (Synthesis of Si-based monomers (F))

[1226] The same steps as those for the synthesis of Si-based monomer (B) were performed, using intermediate 3, to obtain Si-based monomer (F) in the form of a transparent liquid.

[1227]

[1228] Si-based monomers (G)

[1229] The following Si-based monomer (G) was obtained according to WO2020 / 142388.

[1230]

[1231] Si-based monomers (H)

[1232] The following Si-based monomer (H) was obtained according to WO2020 / 142441.

[1233]

[1234] [Preparation of raw materials]

[1235] (Example of manufacturing an aqueous dispersion containing organosilicon polymer)

[1236] Manufacturing Example 1

[1237] Add 15g of water-soluble glycol solvent as organic solvent, 100g of pure water as liquid medium, 100g of Si monomer (A), 4g of dehydrated sorbitol fatty acid ester as surfactant, 4g of cationic emulsifier and 3g of polyoxyethylene alkyl ether to a 500ml plastic container. Heat to 80℃, stir at 2000rpm for 1 minute using a homogenizer, and then emulsify and disperse using ultrasound for 15 minutes.

[1238] Next, the mixture was transferred to a 500 ml four-necked separable flask, and after purging with nitrogen, 0.1 g of lauryl thiol was added as a chain transfer agent. Then, 0.3 g of an azo-containing water-soluble initiator was added as a polymerization initiator, the mixture was heated to 60 °C and reacted for 4 hours to obtain an aqueous dispersion of the organosilicon polymer (water-repellent resin). This dispersion was further diluted with pure water to prepare an aqueous dispersion containing the organosilicon polymer with a non-volatile component concentration of 30% (specifically, an aqueous dispersion containing the organosilicon polymer, surfactant, and liquid medium).

[1239] Manufacturing Examples 2-8

[1240] Except for changing the formulation according to Table 1-1, the same procedure as in Manufacturing Example 1 was followed to prepare an aqueous dispersion containing an organosilicon polymer, a surfactant, and a liquid medium.

[1241] Manufacturing Example 9

[1242] Add 15g of water-soluble glycol solvent as an organic solvent, 100g of pure water as a liquid medium, 75g of Si monomer (A), 25g of stearyl acrylate (meth) acrylate containing long-chain aliphatic hydrocarbon groups, 4g of dehydrated sorbitol fatty acid ester as a surfactant, 4g of cationic emulsifier and 3g of polyoxyethylene alkyl ether to a 500ml plastic container. Heat to 80℃, stir at 2000rpm for 1 minute using a homogenizer, and then emulsify and disperse using ultrasound for 15 minutes.

[1243] Next, the mixture was transferred to a 500 ml four-necked separable flask. After purging with nitrogen, 0.1 g of lauryl thiol was added as a chain transfer agent. Then, 0.3 g of an azo-containing water-soluble initiator was added as a polymerization initiator. The mixture was heated to 60 °C and reacted for 4 hours to obtain an aqueous dispersion of organosilicon-acrylic polymer (water-repellent resin). This dispersion was further diluted with pure water to prepare an aqueous dispersion containing organosilicon-acrylic polymer with a non-volatile component concentration of 30% (specifically, an aqueous dispersion containing organosilicon-acrylic polymer, surfactant, and liquid medium).

[1244] Manufacturing Examples 10, 11, 16-22

[1245] Except for changing the formulation according to Tables 1-1 and 1-2, the same procedure as in Manufacturing Example 1 was followed to prepare an aqueous dispersion containing an organosilicon-acrylic polymer, a surfactant, and a liquid medium.

[1246] Manufacturing Example 12

[1247] Add 15g of water-soluble glycol solvent as an organic solvent, 100g of pure water as a liquid medium, 30g of Si monomer (A), 56g of stearyl acrylate (meth)acrylate containing long-chain aliphatic hydrocarbon groups, 4g of dehydrated sorbitol fatty acid ester as a surfactant, 4g of cationic emulsifier, and 3g of polyoxyethylene alkyl ether to a 500ml plastic container. Heat to 80℃, stir at 2000rpm for 1 minute using a homogenizer, and then emulsify and disperse using ultrasound for 15 minutes.

[1248] Next, the mixture was transferred to a 500 ml autoclave. After purging with nitrogen, 0.1 g of lauryl mercaptan and 14 g of vinyl chloride were added as chain transfer agents. Then, 0.3 g of an azo-containing water-soluble initiator was added as a polymerization initiator. The mixture was heated to 60 °C and reacted for 4 hours to obtain an aqueous dispersion of the organosilicon-acrylic acid polymer. This dispersion was further diluted with pure water to obtain an aqueous dispersion with a non-volatile component concentration of 30%.

[1249] Manufacturing Examples 13-15

[1250] Except for changing the formulation according to Table 1-2, the same procedure as in Manufacturing Example 12 was followed to prepare an aqueous dispersion containing an organosilicon-acrylic polymer, a surfactant, and a liquid medium.

[1251] Comparative Manufacturing Examples 1-2

[1252] Except for changing the formulation according to Table 1-2, the comparative aqueous dispersion was prepared in the same manner as in Manufacturing Example 1.

[1253] The aqueous dispersion of the above-mentioned organosilicon polymer or organosilicon-acrylic polymer (water-repellent resin) was centrifuged at 14,000 rpm for 1 hour, the supernatant was discarded, isopropanol was added, and the mixture was centrifuged again at 14,000 rpm for 30 minutes to separate the polymer. The average molecular weight and adhesiveness of the separated polymer were evaluated. The results are recorded in Tables 1-1 and 1-2.

[1254] [Table 1-1]

[1255]

[1256] The numbers in the table represent the amount of feed added (g).

[1257] [Table 1-2]

[1258]

[1259] The numbers in the table represent the amount of feed added (g).

[1260] Example 1

[1261] The aqueous dispersion with a non-volatile component concentration of 30% obtained in Manufacturing Example 1 was diluted with tap water to prepare a treatment solution with a non-volatile component concentration of 0.9%. Polyester fabric, nylon fabric, and polyester / spandex fabric were immersed in this treatment solution and then extruded using a rolling mill. The treated fabric was then passed through a pin-plate tenter frame at 170°C for 1 minute for drying and curing. The water repellency, light oil repellency, and chalk stain resistance of the test fabrics obtained through this process were evaluated. The evaluation results are shown in Table 2.

[1262] Examples 2-22

[1263] Except for the changes in the formulation as shown in Table 2, the same procedure as in Example 1 was followed to prepare a treatment solution with a non-volatile component concentration of 0.9%. Using this treatment solution, the fabric was treated in the same manner as in Example 1, and its water repellency, light oil repellency, and chalk stain resistance were evaluated. The results are shown in Table 2.

[1264] Comparative Examples 1-2

[1265] Except for the changes in the formulation as shown in Table 2, the same procedure as in Example 1 was followed to prepare a treatment solution with a non-volatile component concentration of 0.9%. Using this treatment solution, the fabric was treated in the same manner as in Example 1, and its water repellency, light oil repellency, and chalk stain resistance were evaluated. The results are shown in Table 2.

[1266] [Table 2]

[1267]

[1268] Industrial availability

[1269] The polymer of the present invention has low viscosity and can be used to impart water-repellent and oil-repellent properties to various products (e.g., paper, fiber products, etc.).

Claims

1. A polymer, characterized in that: The polymer comprises repeating units derived from monomer 1 as shown in formula (1-1) or formula (1-2) below, and the polymer has an adhesion of 800 gf or less. R a -X-CY 3－α Z α (1-1) R a -X-NY 2－β Z β (1-2) Among the various types, R a It is a polymerizable organic group. X is a single bond or a divalent group. Y can be independently a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms. α is an integer from 1 to 3. β is an integer of 1 or 2. Z is independently -Z 1 -SiZ 2 3－m Z 3 m , Z 1 It is a single bond or a divalent group. Z 2 Each is independently a hydrocarbon group having 1 to 10 carbon atoms. m is an integer from 1 to 3. Z 3 They are independently -(O-SiZ) 31 2) p -(CH2) q -Z 32 -SiZ 33 3, Z 31 Each is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 311 3, Z 311 Each is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 3111 3, Z 3111 Each is independently a hydrocarbon group having 1 to 10 carbon atoms. Z 32 It is O or CH2. Z 33 Each is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 331 3, Z 331 Each is independently a hydrocarbon group having 1 to 10 carbon atoms. p is an integer from 0 to 196. q is an integer from 0 to 10.

2. The polymer according to claim 1, characterized in that: The adhesion is below 600gf.

3. The polymer according to claim 1, characterized in that: The adhesion is below 300gf.

4. The polymer according to any one of claims 1 to 3, characterized in that: X is selected from X 1 and X 2 One or more divalent groups constituted, X 1 It is a directly bonded group composed of one or more groups selected from -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, and -C(OR')R'-, wherein R' is independently a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms each time it appears. X 2 It is a direct bond, and can have a hydrocarbon group with 1 to 22 carbon atoms or a divalent aromatic hydrocarbon ring with substituents.

5. The polymer according to any one of claims 1 to 4, characterized in that: X is a hydrocarbon group with 1 to 22 carbon atoms that is directly bonded or may have substituents.

6. The polymer according to any one of claims 1 to 5, characterized in that: Z 1 The source is Z. 11 and Z 12 One or more divalent groups constituted, Z 11 It is a directly bonded group composed of one or more groups selected from -O-, -C(=O)-, -C(=NR'')-, -S-, -S(=O)2-, -NR''-, and -C(OR'')R''-, wherein R'' is independently a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms each time it appears. Z 12 It can be a hydrocarbon group with 1 to 22 carbon atoms that is directly bonded or can have substituents.

7. The polymer according to any one of claims 1 to 6, characterized in that: Z 1 It can be a hydrocarbon group with 1 to 22 carbon atoms that is directly bonded or can have substituents.

8. The polymer according to any one of claims 1 to 7, characterized in that: R a It is an organic group containing an olefinic polymeric group.

9. The polymer according to any one of claims 1 to 8, characterized in that: R a It is acryloyl or methacryloyl.

10. The polymer according to any one of claims 1 to 9, characterized in that: It also contains repeating units derived from hydrophobic monomer 2 having 2 to 40 carbon atoms.

11. The polymer according to claim 10, characterized in that: The hydrophobic monomer 2 is the monomer shown in the following formula (2), CH2=C(-R b )-C(=O)-R c -(R d ) k (2) In the formula, R b It can be a hydrogen atom, a monovalent organic group, or a halogen atom. R c It is a direct bond, a hydrocarbon group with 1 carbon atom in the 2-4 valence, and composed of -C6H4-, -O-, -S-, -C(=O)-, -S(=O)2- and -NR-. C1 - at least one of the 2 to 4 valent groups constituted by R C1 It consists of a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. k is 1 to 3 R d It consists of hydrocarbon groups with 2 to 40 carbon atoms.

12. The polymer as claimed in claim 10 or 11, characterized in that: The amount of repeating units derived from the hydrophobic monomer 2 is 20% by weight or more relative to the polymer.

13. The polymer according to claim 12, characterized in that: The amount of repeating units derived from the monomer unit 1 relative to the polymer is 0.5% by weight or more.

14. The polymer according to any one of claims 1 to 13, characterized in that: It is a non-fluorinated polymer.

15. The polymer according to claim 1, characterized in that: R a It can be CH2=CHC(=O)-O- or CH2=CCH3C(=O)-O-. X is a directly bonded or alkylene group having 1 to 5 carbon atoms. Y can be an alkyl chain with 1 to 3 carbon atoms, or either a hydrogen atom or a carbon atom.

16. The polymer according to claim 1, characterized in that: α is 1, β is 1, Z is independently -Z 1 -SiZ 2 3－m Z 3 m , Z 1 It is a single bond or -(CH2) s -, s is an integer from 1 to 3. Z 2 Each is independently an alkyl group having 1 to 3 carbon atoms. m is an integer from 1 to 3. Z 3 They are independently -(O-SiZ) 31 2) p -(CH2) q -Z 32 -SiZ 33 3, p can be 0 or 1 independently. q can be 0 or 1 independently. Z 31 Each is independently an alkyl group having 1 to 3 carbon atoms. Z 32 It is -O- or -CH2-. Z 33 Each is independently an alkyl group having 1 to 3 carbon atoms or -OSiZ 331 3, Z 331 Each is independently an alkyl group having 1 to 3 carbon atoms. The viscosity of the polymer is below 300 gf.

17. The polymer according to claim 1, characterized in that: R a It can be CH2=CHC(=O)-O- or CH2=CCH3C(=O)-O-. X is a directly bonded or alkylene group having 1 to 5 carbon atoms. Y is either a hydrogen atom or an alkyl chain with 1 to 3 carbon atoms. α is 1, β is 1, Z is independently -Z 1 -SiZ 2 3－m Z 3 m , Z 1 It is a single bond or -(CH2) s -, s is an integer from 1 to 3. Z 2 Each is independently an alkyl group having 1 to 3 carbon atoms. m is an integer from 1 to 3. Z 3 They are independently -(O-SiZ) 31 2) p -(CH2) q -Z 32 -SiZ 33 3, p can be 0 or 1 independently. q can be 0 or 1 independently. Z 31 Each is independently an alkyl group having 1 to 3 carbon atoms. Z 32 It is -O- or -CH2-. Z 33 Each is independently an alkyl group having 1 to 3 carbon atoms or -OSiZ 331 3, Z 331 Each is independently an alkyl group having 1 to 3 carbon atoms. The viscosity of the polymer is below 300 gf.

18. A composition, characterized in that: It contains the polymer and emulsifier as described in any one of claims 1 to 17.

19. The composition of claim 18, characterized in that: It contains water.

20. A water-repellent agent, characterized in that: It contains the polymer of any one of claims 1 to 17, or is the composition of claim 18 or 19.

21. A water-repellent fiber product, characterized in that: The polymer of any one of claims 1 to 17 is attached to the fiber substrate.

22. The water-repellent fiber product as described in claim 21, characterized in that: An ingredient selected from SO3M is attached to the fiber substrate. 1 The monovalent group shown, -COOM 2 The monovalent groups shown and -O-P(O)(OX) 1 (OX) 2 Compounds with one or more functional groups in the monovalent group shown in the figure. In the formula, M 1 M represents a monovalent cation. 2 X represents a monovalent cation. 1 and X 2 Alkyl groups, each representing a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, can be used independently.

23. A method for manufacturing a water-repellent fiber product, characterized in that: The step includes applying the water-repellent agent of claim 20 to the fiber substrate.

24. The method for manufacturing a water-repellent fiber product as described in claim 23, characterized in that: Before applying the water-repellent agent to the fiber substrate, the fiber substrate is given a coating selected from SO3M. 1 The monovalent group shown, -COOM 2 The monovalent groups shown and -O-P(O)(OX) 1 (OX) 2 The process of having one or more functional groups in the monovalent group shown in the figure. In the formula, M 1 M represents a monovalent cation. 2 X represents a monovalent cation. 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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