Polymer, water repellent, textile product, and method for manufacturing textile product

Abstract

To provide a polymer which has low tackiness and can impart superior water repellency and oil repellency to a substrate.SOLUTION: Disclosed is a polymer which includes a repeating unit that is derived from a monomer (1) represented by formula (1-1) or formula (1-2), and which has a tackiness of 800 gf or less. Ra-X-CY3-αZα (1-1), Ra-X-NY2-βZβ (1-2). [In each formula: Ra represents a polymerizable organic group, X represents a single bond or a divalent group, each Y independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, α represents an integer of 1 to 3, β represents an integer of 1 or 2, each Z independently represents -Z1-SiZ23-mZ3m, Z1 represents a single bond or a divalent group, each Z2 independently represents a hydrocarbon group having 1 to 10 carbon atoms, m represents an integer of 1 to 3, each Z3 independently represents -(O-SiZ312)p-(CH2)q-Z32-SiZ333].SELECTED DRAWING: None

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE The present disclosure relates to polymers, water repellents, textiles, and methods for making textiles. [Background technology]

[0002] Non-fluorine-based water repellents have been developed to impart water repellency to substrates (especially textile products). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2023 / 086692 [Patent Document 2] International Publication No. 2023 / 019044 [Patent Document 3] International Publication No. 2023 / 197350 [Patent Document 4] Japanese Patent Publication No. 2017 / 218713 Summary of the Invention [Problem to be solved by the invention]

[0004] Patent Document 1 discloses that good chalk mark resistance can be imparted by treating a textile or other object with a composition prepared by dissolving in a solvent a silicone-containing copolymer containing structural units derived from a (meth)acrylic acid alkyl ester monomer. However, the resulting composition does not have sufficient water and oil repellency. Another requirement for water repellents is tackiness. Materials with a high tackiness tend to be highly adhesive, which can contaminate equipment during textile processing. Therefore, a water repellent with a low tackiness is desirable.

[0005] An object of the present disclosure is to provide a polymer that has low tack and can impart excellent water and oil repellency to a substrate. [Means for solving the problem]

[0006] The present disclosure includes the following aspects: [Item 1] A polymer containing a repeating unit derived from a monomer (1) represented by the following formula (1-1) or formula (1-2), and having a tackiness 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) [In each formula: R a is a polymerizable organic group, X is a single bond or a divalent group; Y's each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; α is an integer from 1 to 3, β is an integer of 1 or 2, Each Z is independently -Z 1 -SiZ 2 3-m Z 3 m and Z 1 is a single bond or a divalent group Z 2 are each independently a hydrocarbon group having 1 to 10 carbon atoms, m is an integer from 1 to 3, Z 3 are each independently -(O-SiZ 31 2) p -(CH2) q -Z 32 -SiZ 33 3, Z 31 are each independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 311 3, Z 311 are each independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 3111 3, Z 3111are each independently a hydrocarbon group having 1 to 10 carbon atoms, Z 32 is O or CH2, Z 33 are each independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 331 3, Z 331 are each independently a hydrocarbon group having 1 to 10 carbon atoms, p is an integer from 0 to 196, and q is an integer from 0 to 10. [Item 2] The polymer according to Item 1, having a tackiness of 600 gf or less. [Item 3] The polymer according to Item 1 or 2, which has a tackiness of 300 gf or less. [Term 4] X is X 1 and X 2 is a divalent group consisting of one or more members selected from the group consisting of X 1 is a group consisting of one or more selected from the group consisting of a direct bond, —O—, —C(═O)—, —C(═NR′)—, —S—, —S(═O)2-, —NR′—, and —C(OR′)R′- (wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms), X 2 Item 4. The polymer according to any one of Items 1 to 3, wherein is a direct bond or an optionally substituted hydrocarbon group having 1 to 22 carbon atoms. [Item 5] The polymer according to any one of Items 1 to 4, wherein X is a direct bond or a hydrocarbon group having 1 to 22 carbon atoms which may have a substituent. [Section 6] Z 1 is Z 11 and Z 12 is a divalent group consisting of one or more members selected from the group consisting of Z 11 is a group consisting of one or more selected from the group consisting of a direct bond, —O—, —C(═O)—, —C(═NR″)—, —S—, —S(═O)2—, —NR″—, and —C(OR″)R″— (wherein R″ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms); Z 12 Item 6. The polymer according to any one of items 1 to 5, wherein is a direct bond or an optionally substituted hydrocarbon group having 1 to 22 carbon atoms. [Section 7] Z 1 Item 7. The polymer according to any one of items 1 to 6, wherein is a direct bond or an optionally substituted hydrocarbon group having 1 to 22 carbon atoms. [Section 8]R a Item 8. The polymer according to any one of items 1 to 7, wherein is an organic group containing an ethylenically polymerizable group. [Section 9]R a Item 9. The polymer according to any one of items 1 to 8, wherein is an acryloyl group or a methacryloyl group. [Item 10] The polymer according to any one of Items 1 to 9, further comprising a repeating unit derived from a hydrophobic monomer (2) having a hydrocarbon group having 2 to 40 carbon atoms. [Item 11] The hydrophobic monomer (2) is represented by the following formula: CH2=C(-R b )-C(=O)-R c -(R d ) k (2) [In the formula, R b is a hydrogen atom, a monovalent organic group, or a halogen atom, R c represents a direct bond, a divalent to tetravalent hydrocarbon group having one carbon atom, -C6H4-, -O-, -S-, -C(=O)-, -S(=O)2-, and -NR C1 -(R C1 is a divalent to tetravalent group consisting of at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 4 carbon atoms, k is 1 to 3, R d is a hydrocarbon group having 2 to 40 carbon atoms. Item 11. The polymer according to item 10, wherein the monomer is represented by the formula: [Item 12] The polymer according to Item 10 or 11, wherein the amount of repeating units derived from the hydrophobic monomer (2) is 20% by weight or more based on the polymer. [Item 13] The polymer according to any one of Items 10 to 13, wherein the amount of the repeating unit derived from the monomer unit (1) is 0.5% by weight or more based on the polymer. [Item 14] The polymer according to any one of Items 1 to 13, which is non-fluorinated. [Section 15]R a is CH2=CHC(=O)-O- or CH2=CCH3C(=O)-O-, X is a direct bond or an alkylene group having 1 to 5 carbon atoms; Item 2. The polymer according to item 1, wherein each Y is independently a hydrogen atom or an alkyl chain having 1 to 3 carbon atoms. [Term 16] α is 1, β is 1, Each Z is independently -Z 1 -SiZ 2 3-m Z 3 m and Z 1 is a single bond or -(CH2) s - and s is an integer from 1 to 3, Z 2 are each independently an alkyl group having 1 to 3 carbon atoms, m is an integer from 1 to 3, Z 3 are each independently -(O-SiZ 31 2) p -(CH2) q -Z 32 -SiZ 33 3, p's are each independently 0 or 1; Each q is independently 0 or 1; Z 31 are each independently an alkyl group having 1 to 3 carbon atoms, Z 32 is —O— or —CH—, Z 33 are each independently an alkyl group having 1 to 3 carbon atoms or -OSiZ 331 3, Z 331are each independently an alkyl group having 1 to 3 carbon atoms, Item 1. The polymer according to item 1, having a tackiness of 300 gf or less. [Section 17]R a is CH2=CHC(=O)-O- or CH2=CCH3C(=O)-O-, X is a direct bond or an alkylene group having 1 to 5 carbon atoms; Y's are each independently a hydrogen atom or an alkyl chain having 1 to 3 carbon atoms; α is 1, β is 1, Each Z is independently -Z 1 -SiZ 2 3-m Z 3 m and Z 1 is a single bond or -(CH2) s - and s is an integer from 1 to 3, Z 2 are each independently an alkyl group having 1 to 3 carbon atoms, m is an integer from 1 to 3, Z 3 are each independently -(O-SiZ 31 2) p -(CH2) q -Z 32 -SiZ 33 3, p's are each independently 0 or 1; Each q is independently 0 or 1; Z 31 are each independently an alkyl group having 1 to 3 carbon atoms, Z 32 is —O— or —CH—, Z 33 are each independently an alkyl group having 1 to 3 carbon atoms or -OSiZ 331 3, Z 331 are each independently an alkyl group having 1 to 3 carbon atoms, 2. The polymer according to claim 1, having a tackiness of 300 gf or less. [Item 18] A composition comprising the polymer according to any one of items 1 to 17 and an emulsifier. [Item 19] The composition according to Item 18, which contains water. [Item 20] A water repellent agent comprising the polymer according to any one of items 1 to 17, or the composition according to item 18 or 19. [Item 21] A water-repellent textile product having the polymer according to any one of items 1 to 14 attached to a textile substrate. [Item 22] The fiber base material is -SO3M 1 (In the formula, M 1 represents a monovalent cation), -COOM 2 (In the formula, M 2 represents a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(wherein, X 1 and X 2 Item 20. The water-repellent textile product according to Item 19, wherein a compound having one or more functional groups selected from the group consisting of monovalent groups represented by the formula: [Item 23] A method for producing a water-repellent textile product, comprising applying the water repellent agent according to item 17 to a textile substrate. [Item 24] Before applying the water repellent to the fiber substrate, -SO3M 1 (In the formula, M 1 represents a monovalent cation), -COOM 2 (In the formula, M 2 represents a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(wherein, X 1 and X 2 and each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms. [Effects of the Invention]

[0007] The polymers of the present disclosure have low tack and can impart excellent water and oil repellency to substrates. DETAILED DESCRIPTION OF THE INVENTION

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

[0009] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, resulting from the elimination of a hydrogen atom from a hydrocarbon. Such hydrocarbon groups are not particularly limited, but may be C1-20 hydrocarbon groups, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may contain one or more ring structures. The hydrocarbon group may be substituted with one or more substituents.

[0010] In this specification, when a term (symbol) that may appear multiple times in a chemical structure is defined, that definition applies independently at each occurrence, unless otherwise stated, regardless of whether "independently at each occurrence," "independently of each other," "independently of each other," or similar expressions are explicitly stated.

[0011] The chemical structures described herein should be understood not to encompass chemical structures that would be recognized by those skilled in the art as chemically impossible or extremely unstable.

[0012] <Polymer> The polymer of the present disclosure contains a repeating unit derived from a monomer (1) represented by the following formula (1-1) or formula (1-2), and has a tackiness 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) [In each formula: R a is a polymerizable organic group, X is a single bond or a divalent group; Y's each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; α is an integer from 1 to 3, β is an integer of 1 or 2, Each Z is independently -Z 1 -SiZ 2 3-m Z 3 m and Z 1 is a single bond or a divalent group Z 2 are each independently a hydrocarbon group having 1 to 10 carbon atoms, m is an integer from 1 to 3, Z 3 are each independently -(O-SiZ 31 2) p -(CH2) q -Z 32 -SiZ 33 3, Z 31 are each independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 311 3, Z 311are each independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 3111 3, Z 3111 are each independently a hydrocarbon group having 1 to 10 carbon atoms, Z 32 is O or CH2, Z 33 are each independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 331 3, Z 331 are each independently a hydrocarbon group having 1 to 10 carbon atoms, p is an integer from 0 to 196, and q is an integer from 0 to 10.

[0013] The polymer of the present disclosure, by virtue of having the above characteristics, can impart liquid repellency (water repellency, oil repellency, oil resistance, and / or water resistance) to a substrate (e.g., a fiber substrate, a paper substrate). The polymer of the present disclosure can function as at least one selected from the group consisting of a water repellent, an oil repellent, an oil-resistant agent, and a water-resistant agent. The repellent agent of the present disclosure can effectively impart oil resistance (oil repellency) and / or water resistance (water repellency) to a substrate, and can, for example, effectively impart both oil resistance and water resistance.

[0014] The polymer of the present disclosure has the above characteristics and can impart excellent water and oil repellency to a substrate (for example, a fiber substrate or a paper substrate). The polymer of the present disclosure has the above characteristics, which may result in a low tackiness. The composition and water repellent containing the polymer of the present disclosure may also have a low tackiness. Therefore, contamination of equipment may be reduced.

[0015] [Tackiness] Tackiness is an index showing the strength of adhesive force. The larger the tackiness value, the stronger the adhesive force. The smaller the tackiness value, the weaker the adhesive force. From the viewpoint of reducing facility contamination, a smaller tackiness is preferable.

[0016] The tackiness of the polymer of the present disclosure is 800 gf or less. From the viewpoint of reducing facility contamination, the tackiness of the polymer of the present disclosure may 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, more preferably 300 gf or less.

[0017] The tackiness can be measured by the following method. A water repellent composition (for example, a solution or dispersion containing a polymer) was dried at 50-60°C for 2 hours, or a water repellent composition (for example, a solution or dispersion containing a polymer) was extracted with alcohol and placed on an 80mm diameter metal sample stage and heated at 40°C for 3 minutes, after which it was evaluated using a 50mm diameter probe. The tackiness was measured as the average of three measurements, or if there was variation in the measured value, five measurements were taken, the upper and lower limits were discarded, and the remaining values ​​were averaged. The machine name and test conditions may be as follows: Machine name: RHESCA Tack Tester TAC-II type Test conditions: Constant Load (1) Immersion Speed ​​120 mm / min. (2) Test Speed: 600 mm / min. (3) Preload 500gf (4) Press Time 10 seconds (5) Distance 5mm The larger the measurement result, the greater the adhesiveness.

[0018] The tackiness of the polymer of the present disclosure can be controlled by adjusting the molecular structure of the polymer, the molecular weight of the polymer, and the molecular weight distribution of the polymer. The higher the molecular weight of the polymer, the easier it is to reduce the tackiness. The lower the proportion of low molecular weight polymers in the molecular weight distribution of the polymer, the easier it is to reduce the tackiness. The molecular weight and molecular weight distribution of the polymer can be controlled by known methods. For example, the molecular weight and molecular weight distribution of the polymer can be controlled by adjusting the type and amount of the initiator, using a chain transfer agent, polymerization temperature, monomer concentration, etc.

[0019] [Weight average molecular weight] The weight average molecular weight of the polymer may be 100,000 or more, 120,000 or more, 130,000 or more, 140,000 or more, 150,000 or more, or 200,000 or more. The weight average molecular weight of the polymer may be 1,000,000 or less, 750,000 or less, 500,000 or less, 400,000 or less, or 300,000 or less. [Number average molecular weight] The number average molecular weight of the polymer may be 30,000 or more, 40,000 or more, 50,000 or more, or 60,000 or more. The number average molecular weight of the polymer may be 100,000 or less, 75,000 or less, 50,000 or less, 40,000 or less, or 30,000 or less. The average molecular weight (weight average molecular weight Mw and / or number average molecular weight Mn) of the polymer of the present disclosure can be obtained by the following measurement method. Average molecular weight: The average molecular weight of the copolymer was determined by GPC (gel permeation chromatography) (in terms of polystyrene). For gel permeation chromatography, an HLC-8420GPC EcoSEC Elite-WS (manufactured by Tosoh) was used. Two TSKgel SuperMultiporeHZ-M columns were connected together. An RI detector was used. Standard polystyrene (SRM706a NIST) was used as the standard material. The analytical sample was prepared by dissolving the copolymer in tetrahydrofuran to prepare a 0.1 wt% solution and passing it through a 0.5 μm filter. When measuring the average molecular weight, the column was maintained at 40°C, tetrahydrofuran was used as the eluent, and 10 μL of the analytical sample was injected at a flow rate of 0.35 mL / min.

[0020] The polymer of the present disclosure may be non-fluorine-based. Specifically, the polymer of the present disclosure may not have a perfluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 6 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, or a fluorine atom.

[0021] (1) Monomer The polymer of the present disclosure contains a repeating unit derived from monomer (1). Monomer (1) is represented by the following formula (1-1) or formula (1-2). The contents described below apply independently to formula (1-1) and formula (1-2). R a -X-CY 3-α Z α (1-1) R a -X-NY 2-β Z β (1-2)

[0022] [R a ] R a is a polymerizable organic group.

[0023] The polymerizable organic group is an organic group that has the property of undergoing a chemical reaction and cleavage or decomposition of a part of the molecule in response to an external stimulus such as heat, light, or radicals, thereby causing a polymerization reaction. The polymerization may be chain polymerization and / or step-growth polymerization. The polymerizable organic group may be, for example, a radically polymerizable organic group, a cationically polymerizable organic group, an anionically polymerizable organic group, a ring-opening polymerizable organic group, a polycondensation organic group, or a polyaddition organic group.

[0024] R amay be an organic group containing an ethylenically polymerizable group. The ethylenically polymerizable group is a group having an ethylenically unsaturated bond (i.e., a carbon-carbon double bond). A monomer having an organic group containing an ethylenically polymerizable group can form a polymer by a polymerization reaction such as radical polymerization. Such a monomer is also called an ethylenically unsaturated monomer.

[0025] The organic group containing an ethylenically polymerizable group is not particularly limited, and may be a vinyl group, a vinylene group, a vinylidene group, an acryloyl group, a methacryloyl group, or a derivative thereof.

[0026] R a is expressed by the following formula: CR a1 R a2 =C(-R a3 )-R a4 - [In formula: R a1 , R a2 , and R a3 are each independently a hydrogen atom, a monovalent organic group, or a halogen atom, R a4 is a single bond or a divalent group. It may be a group represented by the following formula:

[0027] R a1 , R a2 , and R a3 are each independently a hydrogen atom, a monovalent organic group, or a halogen atom.

[0028] R a1 , R a2 , and R a3 R may each independently be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. a1 , R a2 , and R a3 are each independently a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, or a cyano group. a1 , R a2 , and R a3are preferably each independently a hydrogen atom, a methyl group, or a chlorine atom.

[0029] R a4 is a single bond or a divalent group. a4 is preferably a divalent group.

[0030] R a4 is R a41 and R a42 It may be a group consisting of one or more selected from the group consisting of: R a41 is a group consisting of one or more selected from the group consisting of a direct bond, —O—, —C(═O)—, —C(═NR′)—, —S—, —S(═O)2-, —NR′—, and —C(OR′)R′- (wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (e.g., 1 to 5, 1 to 3, or 1 carbon atom)), R a42 is a direct bond or a hydrocarbon group having 1 to 22 carbon atoms.

[0031] R a41 Examples include: direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, —C(═O)—NR′—, -SO2-, -SO2NR'-, -C(OR')R'-, etc. (In the formula, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) Examples include:

[0032] R a42 may be a hydrocarbon group having 1 to 22 carbon atoms, and the number of carbon atoms in the hydrocarbon group may 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 may be 22 or less, 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0033] R a42 A specific example of this is -(CH2) q -. q is an integer from 1 to 22. q may 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. q may be 22 or less, 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0034] R a4 The molecular weight of R may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more. a4 may have a molecular weight of 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[0035] From the viewpoint of improving water repellency, R a may be an acryloyl group or a methacryloyl group. a may be CH2=CHC(=O)- or CH2=CCH3C(=O)-.

[0036] The acryloyl group or methacryloyl group may be a derivative. Examples of the derivative of the acryloyl group or methacryloyl group include: CH2=CHC(=O)-O- CH2=CCH3C(=O)-O- CH2=CHC(=O)-NR'- CH2=CCH3C(=O)-NR'- CH2=CHC(=O)-SR'- CH2=CCH3C(=O)-SR'-, etc. (In the formula, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) Examples include:

[0037] R a Specific examples include: CH2=CH-, CH2=CCH3-, CH2=CHC(=O)-O-, CH2=CCH3C(=O)-O-, CH2=CHC(=O)-NH-, or CH2=CCH3C(=O)-NH- Examples include:

[0038] [X] X is a single bond or a divalent group, and is preferably a divalent group.

[0039] X is X 1 and X 2 is a divalent group consisting of one or more members selected from the group consisting of X 1 is a group consisting of one or more selected from the group consisting of a direct bond, —O—, —C(═O)—, —C(═NR′)—, —S—, —S(═O)2-, —NR′—, and —C(OR′)R′- (wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (e.g., 1 to 5, 1 to 3, or 1 carbon atom)), X 2 may be a direct bond or a divalent hydrocarbon group having 1 to 22 carbon atoms which may have a substituent.

[0040] The molecular weight of X may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more. The molecular weight of X may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[0041] [X 1 〕 X 1 is a non-hydrocarbon linker.

[0042] X 1 is a direct bond or a divalent group. 1 is preferably not only a direct bond.

[0043] X 1 The molecular weight of X may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less. 1 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more.

[0044] X 1 is -O-, -C(=O)-, -S(=O)2-, -NR'-, and -C(OR')R'- (wherein R', in each occurrence, is independently one or more selected from the group consisting of a hydrogen atom or a group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms). Y 1 Examples include: direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, —C(═O)—NR′—, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2 etc. (In the formula, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) Examples include:

[0045] [X 2 〕 X 2 is a direct bond or a divalent hydrocarbon group which may have a substituent.

[0046] X 2 The number of carbon atoms in may 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. 2 may have 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 carbon atoms.

[0047] The divalent hydrocarbon group may be a divalent aliphatic hydrocarbon group or a divalent hydrocarbon aromatic ring. The aliphatic hydrocarbon group may be a cyclic, branched, or straight-chain hydrocarbon group. The divalent aliphatic hydrocarbon group may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group may 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 may be 22 or less, 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0048] X 2 The hydrocarbon group in may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (wherein R' is, independently in each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an 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.

[0049] X 2 A specific example of this is -(CH2) q-. q is an integer from 1 to 22. q may 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. q may be 22 or less, 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0050] Specific examples of divalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4 or less, 3 or less, or 2.

[0051] The divalent hydrocarbon aromatic ring may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and a halogen atom (wherein R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an 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 substituted hydrocarbon aromatic ring, the ratio of carbon atoms to the total 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 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0052] [Example of X] An example of X is -X 1 -, -X 1 -X 2 -, -X 1 -X 2 -X 1 -, -X 1 -X 2 -X 1 -X2 -, -X 2 -, -X 2 -X 1 -, -X 2 -X 1 -X 2 -, -X 2 -X 1 -X 2 -X 1 -, etc. Preferred examples of X include -X 1 -X 2 -, -X 2 - are some examples.

[0053] X may be a direct bond or a hydrocarbon group of 1 to 22 carbon atoms which may have a substituent. Preferably, X may be a hydrocarbon group of 1 to 22 carbon atoms which may have a substituent. The number of carbon atoms in the hydrocarbon group of X may 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 group of 1 to 22 carbon atoms of X may be 22 or less, 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0054] Specific examples of X include -(CH2) q -. q is an integer from 1 to 22. q may 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. q may be 22 or less, 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0055] Specific examples of X include a direct bond or an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms.

[0056] [Y] Each Y is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Y is preferably a branched or linear (preferably long-chain linear) hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group. A -CH group has a lower surface free energy than -CH- and is more likely to exhibit liquid repellency. For this reason, a structure with many branches and many -CH groups is preferred. On the other hand, long-chain alkyl groups of a certain length exhibit high liquid repellency due to their crystallinity. Therefore, the compound may be a branched hydrocarbon group (for example, a branched alkyl group), particularly a t-butyl group or an isopropyl group, a group with a multi-branched structure, or a long-chain hydrocarbon group (or a long-chain linear hydrocarbon group), such as an alkyl group.

[0057] Each Y may independently be a hydrogen atom.

[0058] The carbon number of the hydrocarbon having 1 to 10 carbon atoms represented by Y may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more. The carbon number of the hydrocarbon having 1 to 10 carbon atoms represented by Y may be 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0059] For example, Y is -(CH2) n n may be -CH3. n may be 0 to 9, and may be 0 or more, 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more, or may be 9 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0060] [α] α means the number of Z groups in formula (1-1). α is an integer of 1 to 3. α is 1, 2 or 3.

[0061] In one embodiment, α is 1.

[0062] [β] β means the number of Z groups in formula (1-2), and is an integer of 1 or 2.

[0063] [Z] Each Z is independently -Z1 -SiZ 2 3-m Z 3 m Z is a group having a siloxane bond.

[0064] [Z 1 〕 -Z 1 -SiZ 2 3-m Z 3 m In Z 1 is a single bond or a divalent group. 1 is preferably a divalent group.

[0065] Z 1 is Z 11 and Z 12 is a divalent group consisting of one or more members selected from the group consisting of Z 11 may be a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR'')-, -S-, -S(=O)2-, -NR''-, and -C(OR'')R''- (wherein R'' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (e.g., 1 to 5, 1 to 3, or 1 carbon atom).

[0066] Z 1 may have a molecular weight of 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more. The molecular weight of Y may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[0067] In one embodiment, Z 1 is a single bond.

[0068] (Z 11 ) Z 11 is a non-hydrocarbon linker.

[0069] Z11 is a direct bond or a divalent group. 11 is preferably not only a direct bond.

[0070] Z 11 The molecular weight of X may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less. 1 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more.

[0071] Z 11 is -O-, -C(=O)-, -S(=O)2-, -NR'-, and -C(OR')R'- (wherein R', in each occurrence, is independently one or more selected from the group consisting of a hydrogen atom or a group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms). Z 11 Examples include: direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, —C(═O)—NR′—, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2 etc. (In the formula, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) Examples include:

[0072] (Z 12 ) Z 12 is a direct bond or a hydrocarbon group which may have a substituent.

[0073] Z 12 The number of carbon atoms in Z may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, or 8 or more. 12 may have 10 or fewer, 9 or fewer, 8 or fewer, 7 or fewer, 6 or fewer, or 5 or fewer carbon atoms.

[0074] Z 12 The hydrocarbon group in may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (wherein R' is, independently in each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an 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.

[0075] Z 12 A specific example of this is -(CH2) q -. q is an integer from 1 to 22. q may 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. q may be 22 or less, 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0076] (Z 1 (Example) Z 1 For example, -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 -Z12 -Z 11 -, etc. Z 1 Preferred examples of -Z 11 -Z 12 -, -Z 12 - are some examples.

[0077] Z 1 may be a direct bond or a hydrocarbon group having 1 to 22 carbon atoms which may have a substituent. 1 Z may be a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. 1 The hydrocarbon group may 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 The carbon number of the hydrocarbons having 1 to 22 carbon atoms may 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.

[0078] Z 1 A specific example of this is -(CH2) s -. s is an integer from 1 to 22. s may 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. s may be 22 or less, 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0079] [Z 2 〕 -Z 1 -SiZ 2 3-m Z 3 m In Z 2 are each independently a hydrocarbon group having 1 to 10 carbon atoms. 2 is preferably a branched or linear (preferably long linear) hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group.

[0080] Z 2The number of carbon atoms in the hydrocarbon having 1 to 10 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more. 2 The number of carbon atoms in the hydrocarbon having 1 to 10 carbon atoms may be 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less. 2 may be an alkyl group having 1 to 3 carbon atoms. 2 may be a methyl group.

[0081] [m] Each m is independently an integer of 1 to 3. m is 1, 2, or 3. In one embodiment, m is 2 or 3. In one embodiment, m is 1 or 2.

[0082] [Z 3 〕 -Z 1 -SiZ 2 3-m Z 3 m In Z 3 are each independently -(O-SiZ 31 2) p -(CH2) q -Z 32 -SiZ 33 It is 3.

[0083] (Z 31 ) -(O-SiZ 31 2) p -(CH2) q -Z 32 -SiZ 33 In 3, Z 31 are each independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 311 It is 3.

[0084] Z 31 The number of carbon atoms in the hydrocarbon having 1 to 10 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more. 31 The number of carbon atoms in the hydrocarbon having 1 to 10 carbon atoms may be 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less. 31may be a methyl group.

[0085] The above OSiZ 31 Two Zs in 2 31 At least one Z 31 Ha-OSiZ 311 3. 31 Two Zs in 2 31 -OSiZ 311 Alternatively, it may be a hydrocarbon group having 1 to 10 carbon atoms.

[0086] (Z 311 ) Z 311 are each independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 3111 It is 3.

[0087] Z 311 The number of carbon atoms in the hydrocarbon having 1 to 10 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more. 311 The number of carbon atoms in the hydrocarbon having 1 to 10 carbon atoms may be 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less. 311 may be a methyl group.

[0088] The above OSiZ 311 Three Zs in 3 311 At least one Z 311 Ha-OSiZ 3111 3. 311 Three Zs in 3 311 -OSiZ 3111 The above-mentioned OSiZ may be either a hydrocarbon group having 3 carbon atoms or a hydrocarbon group having 1 to 10 carbon atoms. 311 Three Zs in 3 311 At least two Zs 311 Ha-OSiZ 3111 It can be 3.

[0089] (Z 3111 ) Z 3111 are each independently a hydrocarbon group having 1 to 10 carbon atoms. 3111The number of carbon atoms in the hydrocarbon having 1 to 10 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more. 3111 The number of carbon atoms in the hydrocarbon having 1 to 10 carbon atoms may be 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less. 3111 may be a methyl group.

[0090] (Z 32 ) -(O-SiZ 31 2) p -(CH2) q -Z 32 -SiZ 33 In 3, Z 32 is -O- (oxygen atom) or -CH2-.

[0091] In one embodiment, Z 32 is -O- (oxygen atom).

[0092] (Z 33 ) -(O-SiZ 31 2) p -(CH2) q -Z 32 -SiZ 33 In 3, Z 33 are each independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 331 3. In one embodiment, Z 33 represents an alkyl group having 1 to 3 carbon atoms or -OSiZ 331 It can be 3.

[0093] Z 33 The number of carbon atoms in the hydrocarbon having 1 to 10 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more. 33 The number of carbon atoms in the hydrocarbon having 1 to 10 carbon atoms may be 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less. 33 may be an alkyl group having 1 to 3 carbon atoms. 33 may be a methyl group.

[0094] The above SiZ33 Three Zs in 3 33 At least one Z 33 Ha-OSiZ 331 3. The above SiZ 33 Three Zs in 3 33 is OSiZ 331 The SiZ group may be either a hydrocarbon group having 3 carbon atoms or a hydrocarbon group having 1 to 10 carbon atoms. 33 Three Zs in 3 33 At least two Zs 33 OSiZ 331 It can be 3.

[0095] (Z 331 ) Z 331 are each independently a hydrocarbon group having 1 to 10 carbon atoms.

[0096] Z 331 The number of carbon atoms in the hydrocarbon having 1 to 10 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more. 331 The number of carbon atoms in the hydrocarbon having 1 to 10 carbon atoms may be 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less. 331 may be a methyl group.

[0097] Z 331 may each independently be an alkyl group having 1 to 3 carbon atoms.

[0098] [p] p is an integer from 0 to 196. p may be 0 or more, 10 or more, 20 or more, 30 or more, 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, 90 or more, or 100 or more. p may be 196 or less, 190 or less, 180 or less, 170 or less, 160 or less, 150 or less, 140 or less, 130 or less, 120 or less, 110 or less, or 100 or less.

[0099] The total value of p in formula (1-1) or (1-2) may not exceed 196.

[0100] In one embodiment, p is 0.

[0101] [q] q is an integer from 0 to 10. q may be 0 or more, 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more, and may be 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, or 5 or less.

[0102] In one embodiment, q is 0.

[0103] The terminal portion of the monomer (1) of the present disclosure has a trialkylsiloxy group (—OSiR Si 3) may contain a trialkylsiloxy group-containing structure bonded thereto (R Si is a hydrocarbon group having 1 to 10 carbon atoms, which will be described in detail below.

[0104] The Si atom at the terminal portion in the above means a trialkylsiloxy group (-OSiR Si 3) is composed of a trialkylsiloxy group (-OSiR Si 3) and bonded to the Si atom. Si ) may be bonded.

[0105] The trialkylsiloxy group (—OSiR Si 3) The number is an integer from 1 to 3. The terminal portion of the monomer (1) of the present disclosure means the terminal portion on the Z side in the above formula, and is the portion located within Z.

[0106] Specifically, the terminal portion of the monomer (1) of the present disclosure is represented by the following formula: -Si(-OSiR Si 3) X R Si 3-X [In formula: R Si are each independently a hydrocarbon group having 1 to 10 carbon atoms, x is an integer from 1 to 3. It may include a structure represented by:

[0107] R Si is a hydrocarbon group having 1 to 10 carbon atoms. Si The number of carbon atoms in the hydrocarbon having 1 to 10 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more. Si The number of carbon atoms in the hydrocarbon having 1 to 10 carbon atoms may be 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less. Si may be an alkyl group having 1 to 3 carbon atoms. Si may be a methyl group.

[0108] x is an integer of 1 to 3. x may be 1 or more, 2 or more, or 3 or less, 2 or less, or 1 or less.

[0109] The trialkylsiloxy group (-OSiR) bonded to the Si atom at the terminal of the monomer (1) Si 3) As explained above - OSiZ 331 3 is an example.

[0110] The monomer (1) of the present disclosure has the following formula: TIFF0007817613000001.tif3593[in formula: X is a single bond or a divalent organic group; R 1 and R 2 are each independently a trialkylsiloxy group (-OSiR Si 3) an alkyl group, alkoxy group, aryl group, or aralkyl group having 1 to 10 carbon atoms; L 1 is a silylalkyl group represented by the following formula when i=1: TIFF0007817613000002.tif3294 (in the formula, X is a single bond or a divalent organic group; R 1 and R 2 are each independently a trialkylsiloxy group (-OSiR Si 3) an alkyl group, alkoxy group, aryl group, or aralkyl group having 1 to 10 carbon atoms; i is an integer from 1 to 10 indicating the total number of hierarchical layers of the above-mentioned silylalkyl group, preferably 1 to 5, more preferably 1 to 3, still more preferably 1 or 2, L i+1 is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, an aralkyl group, and the above-mentioned silylalkyl group, provided that when i = c (c is an integer from 1 to 10 indicating the layer of the above-mentioned silylalkyl group, preferably 1 to 5, more preferably 1 to 3, still more preferably 1 or 2), L i+1 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryl group or an aralkyl group, when i < c, it is the above-mentioned silylalkyl group, a i is an integer from 0 to 3, preferably 0 to 2, more preferably 0 to 1, still more preferably 0), and may have a branched siloxy structure represented by {}.

[0111] X is a single bond or a divalent group. X is preferably a divalent organic group.

[0112] The divalent organic group is not particularly limited, and examples thereof include -O- (oxygen atom), a substituted or unsubstituted, linear or branched divalent hydrocarbon group having 1 to 30 carbon atoms.

[0113] Examples of the substituted or unsubstituted, linear or branched divalent hydrocarbon group having 1 to 30 carbon atoms include linear or branched alkylene groups having 1 to 30 carbon atoms such as methylene group, dimethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, etc.; alkenylene groups having 2 to 30 carbon atoms such as vinylene group, arylene group, butenylene group, hexenylene group, octenylene group, etc.; arylene groups having 6 to 30 carbon atoms such as phenylene group, diphenylene group, etc.; an alkylenearylene group having 7 to 30 carbon atoms, such as a dimethylenephenylene group; and Examples of such groups include groups in which the hydrogen atoms bonded to the carbon atoms are at least partially substituted with halogen atoms such as fluorine, or organic groups including carbinol groups, epoxy groups, glycidyl groups, acyl groups, carboxyl groups, amino groups, methacryl groups, mercapto groups, amide groups, and oxyalkylene groups.

[0114] The divalent hydrocarbon group is preferably an unsubstituted divalent saturated hydrocarbon group having 1 to 30 carbon atoms, and is preferably a linear or branched alkylene group having 1 to 6 carbon atoms, with a dimethylene group being particularly preferred.

[0115] For example, the divalent organic group is TIFF0007817613000003.tif4652(in the formula, R 3 represents a substituted or unsubstituted, linear or branched divalent hydrocarbon group having 1 to 30 carbon atoms, as described above, which may have a substituent, as described above; R 3’ is expressed by the following formula: TIFF0007817613000004.tif7691) The general formula -R can be introduced by the reaction of a silicon-bonded hydrogen atom with an alkenyl group. 3 -or-R 3 -R 3’ Similarly, a divalent organic group represented by the general formula -R, which can be introduced by the reaction of a silicon-bonded hydrogen atom with an unsaturated carboxylic acid functional group, is preferred. 3 -COO-R 3 -or-R 3 -COO-R 3’ Divalent organic groups represented by - are also suitable.

[0116] In particular, the above X is preferably -O- (oxygen atom) or a linear or branched alkylene group having 1 to 30 carbon atoms, and particularly preferably -O- (oxygen atom) or a dimethylene group (ethylene group).

[0117] Examples of the alkyl group, alkoxy group, aryl group, or aralkyl group having 1 to 10 carbon atoms include linear or branched alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group; cyclic alkyl groups having 3 to 10 carbon atoms, such as a cyclopentyl group and a cyclohexyl group; a linear or branched alkoxy group having 1 to 10 carbon atoms, such as a methoxy group, an ethoxy group, or a butoxy group; aryl groups having 6 to 10 carbon atoms, such as a phenyl group, a tolyl group, or a xylyl group; an aralkyl group having 7 to 10 carbon atoms, such as a benzyl group; and Examples of such groups include groups in which the hydrogen atoms bonded to the carbon atoms are at least partially substituted with halogen atoms such as fluorine, or with organic groups including a carbinol group, an epoxy group, a glycidyl group, an acyl group, a carboxyl group, an amino group, a methacryl group, a mercapto group, an amide group, an oxyalkylene group, etc. The alkyl group, alkoxy group, aryl group, or aralkyl group is preferably an unsubstituted alkyl group, alkoxy group, aryl group, or aralkyl group having 1 to 10 carbon atoms, more preferably an unsubstituted alkyl group or aryl group having 1 to 6 carbon atoms, and particularly preferably a methyl group, ethyl group, or phenyl group.

[0118] Trialkylsiloxy group (-OSiR Si 3) is as above.

[0119] The branched siloxy structure may be a chemical structure that is highly branched radially from one silicon atom, and i, which indicates the total number of generations of the silylalkyl group, indicates the degree of branching.

[0120] As the branched siloxy structure, the following are particularly preferred. TIFF0007817613000005.tif3139 (wherein X and R 2 is the same as above) TIFF0007817613000006.tif3267 (wherein X and R 2 is the same as above)

[0121] The monomer (1) having a branched siloxy structure is, for example, a monomer represented by the following formula: TIFF0007817613000007.tif3186 (in the formula, R a is a polymerizable organic group, as defined above; X, R 1 , R 2 , L 1 and a i is the same as above) It is expressed as:

[0122] The monomer (1) having a branched siloxy structure is CH2=C(-R b )-C(=O)-OR c - (In the formula, R b is a hydrogen atom or a methyl group, and R c is an alkylene group having 1 to 10 carbon atoms, or CH2=C(-R b )-C(=O)-NH-R c - (In the formula, R b and R c is the same as above.) an organic group containing an acrylic group or a methacrylic group represented by the general formula: TIFF0007817613000008.tif2765(in the formula, R 6 is a hydrogen atom or a methyl group, and R 7 is an alkyl group having 1 to 10 carbon atoms, and R 8 is an alkylene group having 1 to 10 carbon atoms, b is an integer of 0 to 4, and c is 0 or 1.) and those having a group selected from the group consisting of alkenylaryl group-containing organic groups represented by the following formula: and alkenyl groups having 2 to 10 carbon atoms are preferred.

[0123] Monomer (1) having a branched siloxy structure can be produced, for example, according to the method for producing a branched siloxane-silalkylene copolymer described in Japanese Patent Application Laid-Open No. 11-1530 (Japanese Patent Application No. 9-171154). For example, a monomer having the general formula: R a -Si-(OSiR 2 2H)3 (In the formula, R a and R 2 is the same as above) These compounds can be produced by subjecting a silicon-bonded hydrogen atom-containing silicon compound represented by the formula (I) to a hydrosilylation reaction with an alkenyl group-containing organosilicon compound. Examples of silicon compounds represented by the formula (I) include 3-methacryloxypropyltris(dimethylsiloxy)silane, 3-acryloxypropyltris(dimethylsiloxy)silane, and 4-vinylphenyltris(dimethylsiloxy)silane. Examples of alkenyl group-containing organosilicon compounds include vinyltris(trimethylsiloxy)silane, vinyltris(dimethylphenylsiloxy)silane, and 5-hexenyltris(trimethylsiloxy)silane. It is preferable that this hydrosilylation reaction be carried out in the presence of a transition metal catalyst such as chloroplatinic acid or a platinum-vinylsiloxane complex.

[0124] [(1) Examples of monomers] Monomer (1) is a monomer having the following formula: 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 [In formula: R a5 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R a6 are each independently —O— or —NH—; Each X is independently -(CH2) q - and each q is independently an integer of 1 to 10; Y's each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; Z is -Z 1 -SiZ 2 3-m Z 3 m and Z 1 is a single bond or -(CH2) s - and s is an integer from 1 to 3, Z 2 are each independently an alkyl group having 1 to 10 carbon atoms, m is an integer from 1 to 3, Z 3 are each independently -(O-SiZ 31 2) p -(CH2) q -Z 32 -SiZ 33 3, p's are each independently 0 or 1; Each q is independently 0 or 1; Z 31 are each independently an alkyl group having 1 to 3 carbon atoms, Z 32 is —O— or —CH—, Z 33 are each independently an alkyl group having 1 to 10 carbon atoms or -OSiZ 331 3, Z 331 are each independently an alkyl group having 1 to 10 carbon atoms.] The monomer may be represented by the following formula:

[0125] R a5 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.

[0126] R a6 is —O— or —NH—, preferably —O—.

[0127] X is -(CH2) q -It is. q is an integer of 1 to 10. q may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more, and may be 10 or less, 9 or less, 8 or less, 6 or less, or 5 or less. Each Y is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.

[0128] Z is -Z 1 -SiZ 2 3-m Z 3 m is. m is an integer of 1 to 3, and is 1, 2, or 3.

[0129] Z 1 is a single bond or -(CH2) s - and s is an integer of 1 to 3. Z 2 are each independently 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.

[0130] Z 3 are each independently -O-SiZ 33 It is 3.

[0131] Z 31 are each independently an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. Z 32 is —O— or —CH2—. Z 33 are each 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, more preferably a methyl group.

[0132] Z 331are each independently 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.

[0133] [(1) Examples of monomers] Examples of the monomer (1) include, but are not limited to, compounds represented by the following formula: In the following formula, TMS means -Si(CH3)3.

[0134] Formula (A) TIFF0007817613000009.tif2461

[0135] Formula (B) TIFF0007817613000010.tif3271

[0136] Formula (C) TIFF0007817613000011.tif3069

[0137] Formula (D) TIFF0007817613000012.tif3978

[0138] Formula (E) TIFF0007817613000013.tif3466

[0139] Formula (F) TIFF0007817613000014.tif3263

[0140] Formula (G) TIFF0007817613000015.tif3355

[0141] Formula (H) TIFF0007817613000016.tif4374

[0142] Formula (I) TIFF0007817613000017.tif1666

[0143] Formula (J) TIFF0007817613000018.tif1640

[0144] Formula (K) TIFF0007817613000019.tif3359

[0145] Formula (L) TIFF0007817613000020.tif3565

[0146] Of the above formulas (A) to (L), formulas (A), (B), (C), (D), (E), (F), (G) and (H) are preferred.

[0147] Monomer (1) may be polymerized using a known synthesis method, or a commercially available product may be used. Monomer (1) can be synthesized, for example, as follows.

[0148] The following formula (1-1a) or (1-2a): QX-CY 3-α (-Z 1 -SiZ 2 3-m R Si m ) α (1-1a) QX-NY 2-β (-Z 1 -SiZ 2 3-m R Si m ) β (1-2a) [In the formula, Q is independently F, Cl, Br, or I; R Si -OR 1Si and R 1Si is a hydrocarbon group having 1 to 10 carbon atoms, The other symbols have the same meanings as above.] A precursor compound represented by the following formula is prepared. In the above formula, -Si-R Si mThe group represented by the formula: corresponds to a hydrolyzable silyl group.

[0149] Next, the precursor compound is reacted with an Si-H group-containing 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 group-containing organosilicon compound. The reaction can be further accelerated by using a Lewis acid such as tris(pentafluorophenyl)borane during the reaction.

[0150] Examples of the precursor compound represented by formula (1-1a) or (1-2a) include silane compounds such as (3-chloropropyl)diethoxy(methyl)silane and (3-chloropropyl)trimethoxysilane.

[0151] As the Si-H group-containing organosilicon compound, the above Z 3 Examples of the siloxane compound include hydrosilanes such as trimethoxyhydrosilane, triethoxyhydrosilane, and triethylsilane; dimethylpolysiloxanes containing an Si—H group at one end such as 1,1,3,3,3-pentamethyldisiloxane and 1,1,1,3,3,5,5-heptamethyltrisiloxane; and dimethylpolysiloxanes containing an Si—H group in the side chain such as 1,1,1,3,5,5,5-heptamethyltrisiloxane.

[0152] The precursor compound is reacted with an Si-H group-containing organosilicon compound to form a hydrolyzable silyl group "R Si " is an Si-H group-containing organosilicon compound "Z 3 " is substituted with a group containing the following formula (1-1b) or (1-2b): QX-CY 3-α (-Z 1 -SiZ 2 3-m Z 3 m ) α (1-1b) QX-NY 2-β (-Z 1 -SiZ 2 3-m Z 3m ) β (1-2b) [In the formula, Q is independently F, Cl, Br, or I; Each symbol other than Q has the same meaning as above.] A compound represented by the formula:

[0153] A compound represented by formula (1-1b) or (1-2b) and a polymerizable organic group R a and a compound having the following formula (1-1) or (1-2): R a -X-CY 3-α Z α (1-1) R a -X-NY 2-β Z β (1-2) The monomer (1) represented by the following formula can be obtained.

[0154] Polymerizable organic group R a The compound having the polymerizable organic group R preferably has a functional group capable of reacting with Q, such as a carboxylic acid, an amine, or a derivative thereof. a Examples of compounds having the formula include (meth)acrylic acid and (meth)acrylamide.

[0155] Monomer (1) of the present disclosure can be produced in accordance with the contents described in, for example, WO2020 / 142474, WO2020 / 142441, JP-A-2019-89715, WO2020 / 142388, etc.

[0156] (2) Hydrophobic monomer The polymer of the present disclosure may further contain a repeating unit derived from a hydrophobic monomer (2) having a hydrocarbon group having 2 to 40 carbon atoms.

[0157] The hydrocarbon group contained in the monomer (2) may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched or linear, and more preferably linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may have 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 carbon atoms, and preferably 10 or more, 12 or more, 14 or more, or 16 or more carbon atoms. The hydrocarbon group may have 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less carbon atoms, and preferably 30 or less, 25 or less, or 20 or less.

[0158] Monomer (2) may contain an amide group, a urea group, or a urethane group. The hydrocarbon-based monomer may be a combination of a hydrocarbon-based monomer having an amide group, a urea group, or a urethane group and a hydrocarbon-based monomer not having an amide group, a urea group, or a urethane group. By including such a group in monomer (2), the effects of the present disclosure can be effectively achieved.

[0159] The hydrophobic monomer (2) is represented by the following formula: CH2=C(-R b )-C(=O)-R c -(R d ) k (2) [In the formula, R b is a hydrogen atom, a monovalent organic group, or a halogen atom, R c represents a direct bond, a divalent to tetravalent hydrocarbon group having one carbon atom, -C6H4-, -O-, -S-, -C(=O)-, -S(=O)2-, and -NR C1 -(R C1 is a divalent to tetravalent group consisting of at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 4 carbon atoms, k is 1 to 3, R d is a hydrocarbon group having 2 to 40 carbon atoms. It is a monomer represented by the formula:

[0160] [R b ] R b is a hydrogen atom, a monovalent organic group, or a halogen atom.

[0161] R b R may be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. 12 Examples of R are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. 12 is preferably a hydrogen atom, a methyl group, or a chlorine atom. 12 More preferably, R is a methyl group. 12 When R is a methyl group, higher liquid repellency is obtained. 12 may be a hydrogen atom, particularly from the viewpoint of reactivity.

[0162] [R c ] R c represents a direct bond, a divalent to tetravalent hydrocarbon group having one carbon atom, -C6H4-, -O-, -S-, -C(=O)-, -S(=O)2-, and -NR C1 -(R C1 is a divalent to tetravalent group consisting of at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 4 carbon atoms, k is 1 to 3.

[0163] R c is preferably a divalent group. Examples of the divalent to tetravalent hydrocarbon group having 1 carbon atom include -CH2-, -CH= having a branched structure, and -C≡ having a branched structure.

[0164] R c -R Y -, -R Y -R Y -, -R Y -C(=O)-, -C(=O)-R Y -, -R Y -C(=O)-R Y -, -R Y -RX -, -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 - [In the formula, R Y are each independently a direct bond, -O-, or -NR C11 -(R C11 is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms or -S(=O)2-, R X Ha-(CH2) m -(m is an integer of 1 to 5), a linear hydrocarbon group having an unsaturated bond of 1 to 5 carbon atoms, a hydrocarbon group having a branched structure of 1 to 5 carbon atoms, or -(CH2) l -C6H4-(CH2) l - (each l is independently an integer of 0 to 5, and -C6H4- is a phenylene group). R c is preferably not only a divalent hydrocarbon group.

[0165] R c Specific examples are -O-, -NH-, -OC(=O)-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, -NH-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2)m -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, particularly 2 or 4].

[0166] R c is -O-, -NH-, -O-(CH2) m -O-C(=O)-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -NH-S(=O)2- or -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -O-C(=O)-, -NH-(CH2) m-NH-C(=O)-, -NH-(CH2) m -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -NH-C(=O)-NH- [In the formula, m is an integer of 1 to 5, particularly 2 or 4.] It is preferable that R c is -O-, -O-(CH2) m -OC(=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-, especially -O-(CH2) m It is more preferably -NH-C(=O)-.

[0167] [R d ] R d is a hydrocarbon group having 2 to 40 carbon atoms.

[0168] R d is preferably a branched or linear (preferably long-chain linear) hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. The -CH3 group has a lower surface free energy than -CH2- and is more likely to exhibit liquid repellency. For this reason, a structure with many branches and many -CH3 groups is preferred. On the other hand, long-chain alkyl groups of a certain length exhibit high liquid repellency due to their crystallinity. Therefore, R may be a branched hydrocarbon group (for example, a branched alkyl group), particularly a t-butyl group or an isopropyl group, a group with a multi-branched structure, or a long-chain hydrocarbon group (or a long-chain linear hydrocarbon group), for example, an alkyl group. d The number of carbon atoms in R may 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, and is preferably 10 or more. d may have 40 or fewer, 30 or fewer, 25 or fewer, 20 or fewer, 15 or fewer, or 12 or fewer carbon atoms.

[0169] [k] k is 1, 2 or 3. R c In the case where R has a tetravalent hydrocarbon group having one carbon atom, k=3. c In the case where R has a trivalent hydrocarbon group having one carbon atom, k=2. c does not have a trivalent or tetravalent hydrocarbon group having one carbon atom (for example, R c has (for example, 1 to 6) divalent hydrocarbon groups (-CH2-) having one carbon atom, then k=1.

[0170] Examples of monomer (2) are: Formula (a1): CH2=C(-X a1 )-C(=O)-Y a1 -R a1 [In the formula, R a1 is a hydrocarbon group having 6 to 40 carbon atoms, X a1 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y a1 is —O— or —NH—.] A monomer represented by the formula: Formula (a2): CH2=C(-X a2 )-C(=O)-Y a21 -Z(-Y a22 -R a2 ) n [In the formula, R a2 are each independently a hydrocarbon group having 6 to 40 carbon atoms, X a2 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y a21 is —O— or —NH—, Y a22 are each independently a direct bond or a group consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, and -CH2-, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms; n is 1 or 2. It is a monomer represented by the formula:

[0171] (a1) Monomer The monomer (a1) has the formula: CH2=C(-X a1 )-C(=O)-Y a1 -R a1 [In the formula, R a1 is a hydrocarbon group having 6 to 40 carbon atoms, X a1 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y a1 is —O— or —NH—.] It is a compound represented by the formula:

[0172] The monomer (a1) is Y a1 a long chain acrylate ester monomer in which Y is —O—; a1 is a long-chain acrylamide monomer in which is -NH-. R a1 is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. a1 In the formula (I), the hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 carbon atoms, and particularly preferably 18 to 22 carbon atoms. X a1 may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0173] Preferred specific examples of the long-chain acrylate ester monomer are lauryl (meth)acrylate, stearyl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl alpha chloroacrylate, icosyl alpha chloroacrylate, and behenyl alpha chloroacrylate. Specific preferred examples of the long-chain acrylamide monomer are stearyl (meth)acrylamide, icosyl (meth)acrylamide, and behenyl (meth)acrylamide.

[0174] (a2) Monomer 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 selected from -O-, -C(=O)-, -S(=O)2-, -NH-, and -CH2-. The monomer (a2) has the formula: CH2=C(-X a2 )-C(=O)-Y a21 -Z(-Y a22 -R a2 ) n [In the formula, R a2 are each independently a hydrocarbon group having 6 to 40 carbon atoms, X a2 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y a21 is —O— or —NH—, Y a22 are each independently a direct bond or a group consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, and -CH2-, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms; n is 1 or 2. The compound may be represented by the formula: Y a22 and / or Z may not be a direct bond. a22 and Z may not be a direct bond at the same time.

[0175] R a2 is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. a2 In the formula (I), the hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 or 15 to 26, and particularly preferably 18 to 22 or 17 to 22 carbon atoms.

[0176] X a2may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0177] Y a22 -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'- wherein each Y' independently represents a direct bond, -O-, -NH-, or -S(=O)2-; R' is -(CH2) m -(m is an integer of 1 to 5), a linear hydrocarbon group having an unsaturated bond of 1 to 5 carbon atoms, a hydrocarbon group having a branched structure of 1 to 5 carbon atoms, or -(CH2) l -C6H4-(CH2) l - (each l is independently an integer of 0 to 5, and -C6H4- is a phenylene group). It may be.

[0178] Y a22 Specific examples include direct bond, -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O)2-, -S (=O)2-NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, -NH-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m-OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -NH-(CH2) m -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, -NH-(CH2) m -NH-C6H4- [In the formula, m is an integer of 1 to 5.] is.

[0179] Y a22 is preferably -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O)2-, -S(=O)2-NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-. Y a22 It is more preferred that Y is -NH-C(=O)-, -C(=O)-NH-, -OC(=O)-NH-, -NH-C(=O)-O- or -NH-C(=O)-NH-. a22 may not be a direct bond.

[0180] Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and may have a straight-chain or branched structure. Z preferably has 2 to 4 carbon atoms, and particularly 2. Specific examples of Z include a direct bond, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH= having a branched structure, -CH2(CH-)CH2- having a branched structure, -CH2CH2CH= having a branched structure, -CH2CH2CH2CH2CH= having a branched structure, -CH2CH2(CH-)CH2- having a branched structure, and -CH2CH2CH2CH= having a branched structure. Z does not have to be a direct bond.

[0181] Monomer (a2) is CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-R a2 , CH2=C(-X a2 )-C(=O)-O-(CH2) m -OC(=O)-NH-R a2 , CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-OR a2 , CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-NH-R a2 Preferably, R 3 and X a2 has the same meaning as above.] Monomer (a2) is CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-R a2 It is particularly preferred that:

[0182] Monomer (a2) can be produced by reacting a hydroxyalkyl (meth)acrylate or a hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate, such as lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, or behenyl isocyanate. Alternatively, monomer (a2) can be produced by reacting a (meth)acrylate having an isocyanate group in the side chain, such as 2-methacryloyloxyethyl methacrylate, with a long-chain alkylamine or long-chain alkylalcohol. Examples of long-chain alkylamines include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine. Examples of long-chain alkylalcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

[0183] Preferred examples of the monomer (2) are as follows: Stearyl (meth)acrylate, behenyl (meth)acrylate, stearyl alpha chloroacrylate, behenyl alpha chloroacrylate, butyl (meth)acrylate, t-butyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, icosyl (meth)acrylate, icosyl alpha chloroacrylate, stearamidoethyl (meth)acrylate, 2-stearamidoethyl acrylate, CH2=CHC(=O)OC2H4NHSO2C 18 H 37 ; Stearyl (meth)acrylamide, Behenyl (meth)acrylamide;

[0184] TIFF0007817613000021.tif2453

[0185] TIFF0007817613000022.tif2253 TIFF0007817613000023.tif2152 TIFF0007817613000024.tif2155

[0186] TIFF0007817613000025.tif2357 TIFF0007817613000026.tif2256 TIFF0007817613000027.tif2156

[0187] TIFF0007817613000028.tif2051 TIFF0007817613000029.tif2054 TIFF0007817613000030.tif2352 TIFF0007817613000031.tif2659

[0188] TIFF0007817613000032.tif2046

[0189] TIFF0007817613000033.tif2249 [In the above formula, n is a number from 6 to 40, and m is a number from 1 to 5.] The compound of the above chemical formula is an acrylic compound in which the α-position is a hydrogen atom, but specific examples include a methacrylic compound in which the α-position is a methyl group and an α-chloroacrylic compound in which the α-position is a chlorine atom.

[0190] The amount of monomer (a2) in monomer (2) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, or 80% by weight or more, and is preferably 30% by weight or more.

[0191] The polymer of the present disclosure may further contain repeating units derived from one or more monomers selected from the following monomers (3) to (8).

[0192] (3) Hydrophilic group-containing monomer The polymer of the present disclosure may contain a hydrophilic group-containing monomer (3). Monomer (3) is a monomer other than monomer (1) that has a hydrophilic group. The hydrophilic group is preferably an oxyalkylene group (the alkylene group has 2 to 6 carbon atoms), particularly an oxyethylene group. In particular, monomer (3) is preferably an oxyalkylene (meth)acrylate, such as polyalkylene (or monoalkylene) glycol mono(meth)acrylate and / or polyalkylene (or monoalkylene) glycol di(meth)acrylate, or polyalkylene (or monoalkylene) glycol mono(meth)acrylamide.

[0193] Monomer (3) is formula: CH2=CX b C(=O)-Y b -(R b O) n -A b [In the formula, X b is a hydrogen atom or a methyl group, Y b is —O— or —NH—, R b are each independently an alkylene group having 2 to 6 carbon atoms, A b is a hydrogen atom, an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, or CH2=CX b C(=O)-present, and n is an integer from 1 to 90. It is preferable that the oxyalkylene (meth)acrylate is an oxyalkylene (meth)acrylate represented by the following formula:

[0194] An example of the monomer (3) is a monomer of the formula: CH2=CX b C(=O)-O-(R b O)n -A bi (b1) and CH2=CX b C(=O)-O-(R b O) n -C(=O)CX b =CH2(b2), CH2=CX b C(=O)-NH-(R b O) n -A bi (b3) [In the formula, X b are each independently a hydrogen atom or a methyl group, A bi are each independently a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, R b are each independently an alkylene group having 2 to 6 carbon atoms, n is an integer between 1 and 90 ] It is preferable that the ion exchange coefficient be expressed by the following formula:

[0195] n may be, for example, 1 to 50, particularly 1 to 30, and especially 1 to 15 or 2 to 15. Alternatively, n may be, for example, 1. R b may be a linear or branched alkylene group, for example, of the formula -(CH) x -or-(CH2) x1 -(CH(CH3)) x2 -[wherein x1 and x2 are 0 to 6, for example, 2 to 5, and the sum of x1 and x2 is 1 to 6. -(CH2) x1 - and -(CH(CH3)) x2 The order of - is not limited to the depicted formula and may be random. -(R b O) n In -, R may be two or more types (for example, two to four types, particularly two types), and -(R b O) n - is, for example, -(R 1 O) n1 -and-(R2 O) n2 -[wherein, R 1 and R 2 are different from each other and are alkylene groups having 2 to 6 carbon atoms, n1 and n2 are numbers of 1 or more, and the sum of n1 and n2 is 2 to 90.

[0196] R in formulas (b1), (b2) and (b3) b is particularly preferably an ethylene group, a propylene group, or a butylene group, and particularly preferably a butylene group. b R may be a combination of two or more alkylene groups. In this case, it is preferable that at least one of R is an ethylene group, a propylene group, or a butylene group. b Examples of the combination include an ethylene group / propylene group combination, an ethylene group / butylene group combination, and a propylene group / butylene group combination. The monomer (3) may be a mixture of two or more types. In this case, at least one of the monomers (3) is a mixture of R in formula (b1), (b2), or (b3). b is preferably an ethylene group, a propylene group, or a butylene group. When a polyalkylene glycol di(meth)acrylate represented by formula (b2) is used, it is not preferable to use it alone as the monomer (3), but it is preferable to use it in combination with a monomer (b1). In that case, it is also preferable to keep the content of the compound represented by formula (b2) to less than 30% by weight of the monomer (3) used.

[0197] Specific examples of the monomer (3) include, but are not limited to, the following: CH2=CHCOO-CH2CH2O-H CH2=CHCOO-CH2CH2CH2O-H CH2=CHCOO-CH2CH(CH3)OH CH2=CHCOO-CH(CH3)CH2O-H CH2=CHCOO-CH2CH2CH2CH2O-H CH2=CHCOO-CH2CH2CH(CH3)OH CH2=CHCOO-CH2CH(CH3)CH2O-H CH2=CHCOO-CH(CH3)CH2CH2O-H CH2=CHCOO-CH2CH(CH2CH3)OH CH2=CHCOO-CH2C(CH3)2O-H CH2=CHCOO-CH(CH2CH3)CH2O-H CH2=CHCOO-C(CH3)2CH2O-H CH2=CHCOO-CH(CH3)CH(CH3)OH CH2=CHCOO-C(CH3)(CH2CH3)OH CH2=CHCOO-(CH2CH2O)2-H CH2=CHCOO-(CH2CH2O)4-H CH2=CHCOO-(CH2CH2O)5-H CH2=CHCOO-(CH2CH2O)6-H CH2=CHCOO-(CH2CH2O)5-CH3 CH2=CHCOO-(CH2CH2O)9-CH3 CH2=CHCOO-(CH2CH2O) 23 -CH3 CH2=CHCOO-(CH2CH2O) 90 -CH3

[0198] CH2=CHCOO-(CH2CH(CH3)O)9-H CH2=CHCOO-(CH2CH(CH3)O)9-CH3 CH2=CHCOO-(CH2CH(CH3)O) 12 -CH3 CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=CHCOO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9 CH2=CHCOO-(CH2CH2O) 23 -OOC(CH3)C=CH2 CH2=CHCOO-(CH2CH2O) 20 -(CH2CH(CH3)O)5-CH2-CH=CH2

[0199] CH2=CHCOO-(CH2CH2O)9-H CH2=C(CH3)COO-CH2CH2O-H CH2=C(CH3)COO-CH2CH2CH2O-H CH2=C(CH3)COO-CH2CH(CH3)O-H CH2=C(CH3)COO-CH(CH3)CH2O-H CH2=C(CH3)COO-CH2CH2CH2CH2O-H CH2=C(CH3)COO-CH2CH2CH(CH3)O-H CH2=C(CH3)COO-CH2CH(CH3)CH2O-H CH2=C(CH3)COO-CH(CH3)CH2CH2O-H CH2=C(CH3)COO-CH2CH(CH2CH3)O-H CH2=C(CH3)COO-CH2C(CH3)2O-H CH2=C(CH3)COO-CH(CH2CH3)CH2O-H CH2=C(CH3)COO-C(CH3)2CH2O-H CH2=C(CH3)COO-CH(CH3)CH(CH3)O-H CH2=C(CH3)COO-C(CH3)(CH2CH3)O-H CH2=C(CH3)COO-(CH2CH2O)2-H CH2=C(CH3)COO-(CH2CH2O)4-H CH2=C(CH3)COO-(CH2CH2O)5-H CH2=C(CH3)COO-(CH2CH2O)6-H CH2=C(CH3)COO-(CH2CH2O)9-H CH2=C(CH3)COO-(CH2CH2O)5-CH3 CH2=C(CH3)COO-(CH2CH2O)9-CH3 CH2=C(CH3)COO-(CH2CH2O) 23 -CH3 CH2=C(CH3)COO-(CH2CH2O) 90 -CH3 CH2=C(CH3)COO-(CH2CH(CH3)O)9-H

[0200] CH2=C(CH3)COO-(CH2CH(CH3)O)9-CH3 CH2=C(CH3)COO-(CH2CH(CH3)O) 12 -CH3 CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=C(CH3)COO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9 CH2=C(CH3)COO-(CH2CH2O) 23 -OOC(CH3)C=CH2 CH2=C(CH3)COO-(CH2CH2O) 20 -(CH2CH(CH3)O)5-CH2-CH=CH2

[0201] CH2=CH-C(=O)-NH-CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH(CH3)O-H CH2=CH-C(=O)-NH-CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH(CH3)O-H CH2=CH-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH(CH3)CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH(CH2CH3)O-H CH2=CH-C(=O)-NH-CH2C(CH3)2O-H CH2=CH-C(=O)-NH-CH(CH2CH3)CH2O-H CH2=CH-C(=O)-NH-C(CH3)2CH2O-H CH2=CH-C(=O)-NH-CH(CH3)CH(CH3)OH CH2=CH-C(=O)-NH-C(CH3)(CH2CH3)OH CH2=CH-C(=O)-NH-(CH2CH2O)2-H CH2=CH-C(=O)-NH-(CH2CH2O)4-H CH2=CH-C(=O)-NH-(CH2CH2O)5-H CH2=CH-C(=O)-NH-(CH2CH2O)6-H CH2=CH-C(=O)-NH-(CH2CH2O)9-H CH2=CH-C(=O)-NH-(CH2CH2O)5-CH3 CH2=CH-C(=O)-NH-(CH2CH2O)9-CH3 CH2=CH-C(=O)-NH-(CH2CH2O) 23 -CH3 CH2=CH-C(=O)-NH-(CH2CH2O) 90 -CH3

[0202] CH2=CH-C(=O)-NH-(CH2CH(CH3)O)9-H CH2=CH-C(=O)-NH-(CH2CH(CH3)O)9-CH3 CH2=CH-C(=O)-NH-(CH2CH(CH3)O) 12 -CH3 CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=CH-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0203] CH2=C(CH3)-C(=O)-NH-CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)OH CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH(CH3)OH CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH2CH3)OH CH2=C(CH3)-C(=O)-NH-CH2C(CH3)2O-H CH2=C(CH3)-C(=O)-NH-CH(CH2CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-C(CH3)2CH2O-H CH2=C(CH3)-C(=O)-NH-CH(CH3)CH(CH3)OH CH2=C(CH3)-C(=O)-NH-C(CH3)(CH2CH3)OH CH2=C(CH3)-C(=O)-NH-(CH2CH2O)2-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)4-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)6-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 23 -CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 90 -CH3

[0204] CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)9-H CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)9-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O) 12 -CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0205] The monomer (3) is X 2 is a hydrogen atom. Monomer (3) is particularly preferably hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxyethyl acrylamide.

[0206] (4) Monomer containing ion donor groups The polymer of the present disclosure may contain an ion-donating group-containing monomer (4). The monomer (4) is preferably a monomer (particularly an acrylic monomer) containing an olefinic carbon-carbon double bond and an ion-donating group. The ion-donating group is an anion-donating group and / or a cation-donating group.

[0207] Examples of the monomer having an anion donating group include a monomer having a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Specific examples of the monomer having an anion donating group include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, (meth)acrylate phosphate, vinylbenzenesulfonic acid, acrylamido-tertiarybutylsulfonic acid, and salts thereof.

[0208] Salts of anion-donating groups include alkali metal salts, alkaline earth metal salts, and ammonium salts, such as methylammonium salts, ethanolammonium salts, and triethanolammonium salts.

[0209] In the monomer having a cation donating group, examples of the cation donating group include an amino group, preferably a tertiary amino group or a quaternary amino group. In the tertiary amino group, the two groups bonded to the nitrogen atom are preferably the same or different and are an aliphatic group (particularly an alkyl group) having 1 to 5 carbon atoms, an aromatic group (an aryl group) having 6 to 20 carbon atoms, or an araliphatic group (particularly an aralkyl group, such as a benzyl group (CH-CH-)) having 7 to 25 carbon atoms. In the quaternary amino group, the three groups bonded to the nitrogen atom are preferably the same or different and are an aliphatic group (particularly an alkyl group) having 1 to 5 carbon atoms, an aromatic group (an aryl group) having 6 to 20 carbon atoms, or an araliphatic group (particularly an aralkyl group, such as a benzyl group (CH-CH-)) having 7 to 25 carbon atoms. In the tertiary amino group and the quaternary amino group, the remaining group bonded to the nitrogen atom may have a carbon-carbon double bond. The cation donating group may be in the form of a salt.

[0210] The cation-donating group in the form of a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, such as carboxylic acids having 1 to 20 carbon atoms (particularly monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid), are preferred. Dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and salts thereof are preferred.

[0211] Specific examples of the monomer having a cation donor group are as follows: CH2=CHCOO-CH2CH2-N(CH3)2 and its salts (e.g. acetate) CH2=CHCOO-CH2CH2-N(CH2CH3)2 and its salts (e.g. acetate) CH2=C(CH3)COO-CH2CH2-N(CH3)2 and its salts (e.g. acetate) CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2 and its salts (e.g. acetate salts) CH2=CHC(O)N(H)-CH2CH2CH2-N(CH3)2 and its salts (e.g. acetate) CH2=CHCOO-CH2CH2-N(-CH3)(-CH2-C6H5) and its salts (e.g. acetate) CH2=C(CH3)COO-CH2CH2-N(-CH2CH3)(-CH2-C6H5) and its salts (e.g. acetate) CH2=CHCOO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH2-N + (-CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (-CH2CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Br - CH2=C(CH3)COO-CH2CH2-N +(CH3)3I - CH2=C(CH3)COO-CH2CH2-N + (CH3)3O - SO3CH3 CH2=C(CH3)COO-CH2CH2-N + (CH3)(-CH2-C6H5)2Br -

[0212] The ion-donating group-containing monomer (4) is preferably methacrylic acid, acrylic acid, or dimethylaminoethyl methacrylate, and more preferably methacrylic acid or dimethylaminoethyl methacrylate.

[0213] (5) Halogenated olefin monomers The polymer of the present disclosure may have a repeating unit derived from a halogenated olefin monomer (5). The halogenated olefin monomer (5) may not have a fluorine atom. The halogenated olefin monomer (5) is preferably an olefin having 2 to 20 carbon atoms and substituted with 1 to 10 chlorine atoms, bromine atoms, or iodine atoms. The halogenated olefin monomer (5) is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms and 1 to 5 chlorine atoms. Preferred examples of the halogenated olefin monomer (5) include vinyl halides such as vinyl chloride, vinyl bromide, and vinyl iodide, and vinylidene halides such as vinylidene chloride, vinylidene bromide, and vinylidene iodide. Vinyl chloride or vinylidene chloride is preferred because it enhances water repellency (particularly water repellency durability). The presence of repeating units derived from the halogenated olefin monomer (5) enhances the washing durability of the polymer of the present disclosure.

[0214] (6) Crosslinkable monomer In the polymer of the present disclosure, the crosslinkable monomer has at least two reactive groups and / or ethylenically unsaturated double bonds (preferably, (meth)acrylate groups), and the crosslinkable monomer (6) may be a monomer that does not contain a fluorine atom. It may also be a compound that does not contain a fluorine atom. The crosslinkable monomer (6) may be a compound that has at least two ethylenically unsaturated double bonds (preferably, (meth)acrylate groups), or a compound that has at least one ethylenically unsaturated double bond and at least one reactive group. Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, and a carboxyl group.

[0215] The crosslinking monomer may be a mono(meth)acrylate, di(meth)acrylate or di(meth)acrylamide having a reactive group.

[0216] One example of a crosslinkable monomer is a vinyl monomer having a reactive group.

[0217] Examples of crosslinkable monomers include, but are not limited to, diacetone (meth)acrylamide, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

[0218] (7) Cyclic hydrocarbon group-containing monomer The polymer of this article may have a repeating unit derived from a cyclic hydrocarbon group-containing monomer (7). The cyclic hydrocarbon group-containing monomer (7) is a monomer having a cyclic hydrocarbon group, and may be a monomer having one ethylenically unsaturated double bond and a cyclic hydrocarbon group.

[0219] The cyclic hydrocarbon group-containing monomer (7) preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, and may have, for example, a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0220] The cyclic hydrocarbon group may be alicyclic or aromatic, preferably alicyclic. The cyclic hydrocarbon group may be saturated or unsaturated, preferably saturated. The cyclic hydrocarbon group may be a monocyclic group, a polycyclic group, or a bridged ring group, preferably a bridged ring group. The cyclic hydrocarbon group may have a chain group (e.g., a linear or branched chain hydrocarbon group).

[0221] The cyclic hydrocarbon group may have 4 or more, 6 or more, or 8 or more carbon atoms, and may have 30 or less, 26 or less, 22 or less, 18 or less, or 14 or less carbon atoms.

[0222] Specific examples of cyclic hydrocarbon groups include cyclohexyl, t-butylcyclohexyl, adamantyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, bornyl, isobornyl, norbornyl, dicyclopentanyl, dicyclopentenyl, benzyl, phenyl, naphthyl, 2-t-butylphenyl, residues obtained by removing one or more hydrogen atoms from these groups (e.g., cyclohexylene, adamantylene, phenylene, naphthylene, etc.), and groups that are substitution products thereof.

[0223] Specific examples of the cyclic hydrocarbon group-containing monomer include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and compounds in which these acrylates are substituted with acrylamide, etc. These may be used alone or in combination of two or more.

[0224] (8) Other monomers The other monomers are not limited to these examples and include acrylonitrile, organosiloxane-containing (meth)acrylates, short-chain alkyl (meth)acrylates, vinyl acetate, styrene, α-methylstyrene, p-methylstyrene, vinyl alkyl ethers, etc. The other monomers (8) may be used alone or in combination of two or more.

[0225] <Polymer composition> The combination of the monomers (1) to (8) constituting the repeating units of the polymer is not particularly limited as long as it contains (1), and examples are as follows (brackets are omitted): (1) (1)+(2) (1)+(2)+(3) (1)+(3) (1)+(4) (1)+(2)+(3)+(4) (1)+(2)+(3)+(4)+(5) (1)+(2)+(3)+(4)+(5)+(6) (1)+(2)+(3)+(4)+(5)+(6)+(7) Furthermore, other monomers (8) may be used in combination with the above combination. In the case of textile products, it is preferable to use the monomers (1) and (2) in combination.

[0226] [(1) Amount of Monomer] The amount of repeating units derived from monomer (1) may be 0.1% by weight or more, 0.5% by weight 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, based on the polymer. The amount of repeating units derived from monomer (1) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 50% by weight or less, 45% by weight or less, 35% by weight or less, 33% by weight or less, 30% by weight or less, 27% by weight or less, 25% by weight or less, 20% by weight or less, 17% by weight or less, 15% by weight or less, 10% by weight or less, or 5% by weight or less, based on the polymer.

[0227] The amount of repeating units derived from the monomer (1) may be 100% by weight based on the polymer, that is, the polymer of the present disclosure may be a polymer of the monomer (1).

[0228] [(2) Amount of hydrophobic monomer] The amount of repeating units derived from monomer (2) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the polymer. The amount of repeating units derived from monomer (2) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the polymer.

[0229] The amount of the repeating units derived from monomer (2) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of the repeating units derived from monomer (1). The amount of repeating units derived from monomer (2) may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the amount of repeating units derived from monomer (1).

[0230] In one embodiment, the amount of repeating units derived from monomer (2) may be less than the amount of repeating units derived from monomer (1).

[0231] [(3) Amount of Hydrophilic Group-Containing Monomer] The amount of repeating units derived from monomer (3) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the polymer. The amount of repeating units derived from monomer (3) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the polymer. The amount of the repeating units derived from monomer (3) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of the repeating units derived from monomer (1). The amount of repeating units derived from monomer (3) may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the amount of repeating units derived from monomer (1).

[0232] [(4) Amount of ion-donor group-containing monomer] The amount of repeating units derived from monomer (4) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the polymer. The amount of repeating units derived from monomer (4) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the polymer. The amount of the repeating units derived from monomer (4) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of the repeating units derived from monomer (1). The amount of repeating units derived from monomer (4) may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the amount of repeating units derived from monomer (1).

[0233] [(5) Amount of halogenated olefin monomer] The amount of repeating units derived from monomer (5) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the weight of the polymer. The amount of repeating units derived from monomer (5) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the polymer. The amount of the repeating units derived from monomer (5) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of the repeating units derived from monomer (1). The amount of repeating units derived from monomer (5) may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the amount of repeating units derived from monomer (1).

[0234] [(6) Amount of crosslinkable monomer] The amount of repeating units derived from monomer (6) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the weight of the polymer. The amount of repeating units derived from monomer (6) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the polymer. The amount of the repeating units derived from monomer (6) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of the repeating units derived from monomer (1). The amount of repeating units derived from monomer (6) may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the amount of repeating units derived from monomer (1).

[0235] [(7) Amount of Cyclic Hydrocarbon Group-Containing Monomer] The amount of repeating units derived from monomer (7) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the weight of the polymer. The amount of repeating units derived from monomer (7) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the polymer. The amount of the repeating units derived from monomer (7) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of the repeating units derived from monomer (1). The amount of repeating units derived from monomer (7) may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the amount of repeating units derived from monomer (1).

[0236] [(8) Amount of other monomers] The amount of repeating units derived from monomer (8) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the weight of the polymer. The amount of repeating units derived from monomer (8) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the polymer. The amount of the repeating units derived from monomer (8) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of the repeating units derived from monomer (1). The amount of repeating units derived from monomer (8) may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the amount of repeating units derived from monomer (1).

[0237] <Method of producing polymer> The polymers of the present disclosure can be produced by any conventional polymerization method, and the polymerization reaction conditions can be selected arbitrarily. Such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.

[0238] In solution polymerization, a method is employed in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, the mixture is heated and stirred at a temperature in the range of 30 to 120°C for 30 minutes to 48 hours, for example, 3 to 24 hours. Examples of polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, per 100 parts by weight of the monomer.

[0239] The organic solvent is inert to the monomers and dissolves them, and may be, for example, an ester (e.g., an ester having 2 to 30 carbon atoms, specifically, ethyl acetate, butyl acetate), a ketone (e.g., a ketone having 2 to 30 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone), or an alcohol (e.g., an alcohol having 1 to 30 carbon atoms, specifically, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, 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 organic solvent is used in an amount of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight, relative to 100 parts by weight of the total of the monomers.

[0240] Emulsion polymerization involves emulsifying monomers in water in the presence of a polymerization initiator and an emulsifier, purging with nitrogen, and then stirring at 50 to 80°C for 30 minutes to 48 hours, e.g., 3 to 24 hours, to polymerize. Polymerization initiators include water-soluble initiators such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, and ammonium persulfate, as well as oil-soluble initiators such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 10 parts by weight per 100 parts by weight of monomer.

[0241] To obtain a polymer aqueous dispersion with excellent shelf stability, it is desirable to polymerize the monomer by microparticulating it in water using an emulsifying device capable of applying powerful crushing energy, such as a high-pressure homogenizer or ultrasonic homogenizer. Furthermore, various anionic, cationic, or nonionic emulsifiers can be used as emulsifiers, and are used in a range of 0.5 to 20 parts by weight per 100 parts by weight of the monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. If the monomers are not completely compatible, it is preferable to add a compatibilizer, such as a water-soluble organic solvent or a low-molecular-weight monomer, that will fully compatibilize these monomers. Addition of a compatibilizer can improve emulsifiability and copolymerizability.

[0242] 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, which may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of water. Examples of low-molecular-weight monomers include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate, which may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of the total amount of monomers.

[0243] A chain transfer agent may be used in the polymerization. The molecular weight of the polymer can be changed depending on the amount of chain transfer agent used. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (e.g., having 1 to 30 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite. The amount of chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, per 100 parts by weight of the total amount of monomers.

[0244] The polymer is preferably produced by emulsion polymerization or solution polymerization. After producing the polymer by polymerization, it is preferable to add water (or an aqueous medium) to disperse the polymer in water. Water (or an aqueous medium) may be added after producing the polymer by polymerization. For example, after producing a polymer by polymerizing monomers in the presence of an organic solvent, water may be added to the polymer mixture, the organic solvent may be distilled off, and the polymer may be dispersed in water. The organic solvent does not have to be distilled off. A surfactant may be added before or after polymerization, or it may not be added. A good aqueous dispersion can be obtained even when a surfactant is not added.

[0245] <Composition> The composition of the present disclosure includes the polymer of the present disclosure. The composition of the present disclosure can be obtained by combining the polymer of the present disclosure with additional components (e.g., an emulsifier, a liquid medium, a wax, etc.). The composition of the present disclosure can be obtained by polymerizing monomer (1), or monomer (1) and a hydrophobic monomer (2), in the presence of the additional components of the present disclosure (e.g., a surfactant, a liquid medium, a wax, etc.).

[0246] The composition can be an emulsion composition by including the polymer of the present disclosure, an emulsifier, and water.

[0247] [Surfactants] The composition of the present disclosure may include a surfactant as an additional component. In the composition, the surfactant may include a nonionic surfactant. Furthermore, the surfactant may include one or more surfactants selected from cationic surfactants, anionic surfactants, and amphoteric surfactants. It is preferable to use a combination of a nonionic surfactant and a cationic surfactant.

[0248] (nonionic surfactant) Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides.

[0249] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0250] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a mono- to hexa-hydric (particularly di- to penta-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0251] An example of an ester ether is a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. An example of an alcohol is a mono- to hexa-hydric (particularly di- to penta-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0252] An example of an alkanolamide is formed from a fatty acid and an alkanolamine. The alkanolamide may be a monoalkanolamide or a dialkanolamine. An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, and having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0253] The polyhydric alcohol may be a dihydric to pentahydric alcohol having 10 to 30 carbon atoms. The amine oxide may be an oxide (having, for example, 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0254] The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic surfactant is generally preferably 2 to 100. The nonionic surfactant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides, and is preferably a nonionic surfactant having an oxyalkylene group.

[0255] The nonionic surfactant may be an alkylene oxide adduct of a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, etc. Among these, those in which the structure of the alkylene oxide adduct moiety and the polyalkylene glycol moiety is polyoxyethylene (POE), polyoxypropylene (POP), or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Furthermore, the nonionic surfactant preferably has a structure that does not contain an aromatic group in view of environmental issues (biodegradability, environmental hormones, etc.).

[0256] The nonionic surfactants are those having the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [In the formula, R 1 is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or acyl group having 2 to 22 carbon atoms, R 2 are independently the same or different and are alkylene groups having 3 or more carbon atoms (e.g., 3 to 10), R 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number greater than or equal to 2, q is a number of 0 or 1 or more. The compound may be a compound represented by the formula:

[0257] R 1 R preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. 1 Preferred specific examples include a lauryl group, a tridecyl group, and an oleyl group. R 2 Examples of the alkyl group include a propylene group and a butylene group. In the nonionic surfactant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R 2 O) q - may form a polyoxyalkylene chain. The nonionic surfactant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) at the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, and among these, an oxypropylene chain is preferred.

[0258] Specific examples of nonionic surfactants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkanes (C 12 -C 16 ) Thiol, Sorbitan Mono Fatty Acid (C7-C 19 ) or alkyl (C 12 -C 18 ) amines and the like.

[0259] The proportion of the polyoxyethylene block can be 5 to 80% by weight, for example 30 to 75% by weight, particularly 40 to 70% by weight, based on the molecular weight of the nonionic surfactant (copolymer). The average molecular weight of the nonionic surfactant is generally 300 to 5,000, for example, 500 to 3,000. The nonionic surfactant may be a mixture of a compound having an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. An example of a compound having an HLB of less than 15 is a sorbitan fatty acid ester. An example of a compound having an HLB of 15 or more is a polyoxyethylene alkyl ether. The weight ratio of the compound having an HLB of less than 15 to the compound having an HLB of 15 or more may be 90:10 to 20:80, for example 85:15 to 55:45. The nonionic surfactant may be used alone or in combination of two or more kinds.

[0260] (cationic surfactant) The cationic surfactant is preferably a compound having no amide group.

[0261] The cationic surfactant may be an amine salt, a quaternary ammonium salt, or an oxyethylene adduct ammonium salt. Specific examples of the cationic surfactant include, but are not limited to, amine salt surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines, and quaternary ammonium salt surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and benzethonium chloride.

[0262] Preferred examples of the cationic surfactant are: R 21 -N + (-R 22 )(-R 23 )(-R 24 ) X - [In the formula, R 21 , R 22 , R 23 and R 24 is a hydrocarbon group having 1 to 40 carbon atoms, X is an anionic group. is a compound of R 21 , R 22 , R 23 and -R 24 Specific examples of X include alkyl groups (for example, methyl, butyl, stearyl, and palmityl groups). Specific examples of X include halogens (for example, chlorine) and acids (for example, hydrochloric acid and acetic acid). The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl having 4 to 40 carbon atoms).

[0263] Preferably, the cationic surfactant is an ammonium salt. The cationic surfactant has the formula: R 1 p - N + R 2 q X - [In the formula, R 1 is C12 or higher (e.g., C 12 ~C 50 ) linear and / or branched aliphatic (saturated and / or unsaturated) groups, R 2 is H or a C1-4 alkyl group, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50) (CH3 and C2H5 are particularly preferred), X is a halogen atom (for example), a C1-C4 fatty acid base, p is 1 or 2, q is 2 or 3, and p+q=4. R 1 may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0264] Specific examples of cationic surfactants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0265] (anionic surfactants) Examples of anionic surfactants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonic acid salts, N-acylamino acid surfactants, phosphoric acid mono- or diester surfactants, and sulfosuccinate esters.

[0266] (Amphoteric surfactant) Examples of amphoteric surfactants include alanines, imidazolinium betaines, amido betaines, and acetic acid betaine, and specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetic acid betaine, and fatty acid amidopropyl dimethylamino acetic acid betaine.

[0267] The surfactant may be a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant, each of which may be one type or a combination of two or more types.

[0268] (amount of surfactant) The amount of the surfactant may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the polymer. The amount of the surfactant may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the polymer.

[0269] The surfactants exemplified in this disclosure can also be used as emulsifiers, i.e., the nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants exemplified in this disclosure can be used as nonionic emulsifiers, cationic emulsifiers, anionic emulsifiers, and amphoteric emulsifiers.

[0270] [Liquid medium] The composition of the present disclosure may contain a liquid medium as an additional component. The liquid medium is water, an organic solvent, or a mixture of water and an organic solvent. A mixture of water and an organic solvent is preferred.

[0271] Examples of organic solvents include esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate and butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically, naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxy group (e.g., polyhydric alcohols such as alcohols, glycol-based solvents, ethers of polyhydric alcohols (e.g., monoethers), etc.). These may be used alone or in combination.

[0272] (amount of liquid medium) The amount of the liquid medium may 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, based on the composition. The amount of the liquid medium may 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, based on the composition.

[0273] The amount of organic solvent 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, based on the composition. The amount of organic solvent 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, based on the composition.

[0274] The amount of the organic solvent may be 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, or 40% by weight or more, based on the liquid medium. The amount of the organic solvent may be 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, 12.5% ​​by weight or less, 7.5% by weight or less, or 5.0% by weight or less, based on the liquid medium.

[0275] The amount of the organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more, relative to 100 parts by weight of the polymer. The amount of the organic solvent may be 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 100 parts by weight of the polymer.

[0276] The amount of the organic solvent may 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, relative to 100 parts by weight of water. The amount of the organic solvent may be 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 25 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of water.

[0277] [silicone] The composition of the present disclosure may contain a silicone in addition to the monomer (1) and the hydrophobic monomer (2).

[0278] Silicones have the formula: (R 53 )3Si-O-[-Si(R 51 )2-O-] a -[-Si(R 51 )2-O-] b -Si(R 53 )3(S1) [In the formula, R 51each independently represents 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; R 53 each independently represents 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; a represents an integer of 0 or more, b represents an integer of 1 or more, and (a+b) is 5 to 200. The polymer may be represented by the formula:

[0279] R 51 and R 53 In the above, the alkyl group having 1 to 40 carbon atoms and the aryl group having 6 to 40 carbon atoms may be unsubstituted or substituted. R 51 and R 53 Specific examples of R include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group; a cyclopentyl group, a cyclohexyl group, a cycloheptyl group; a phenyl group, a tolyl group, a naphthyl group, or a group in which some or all of the hydrogen atoms bonded to these groups have been substituted with a halogen atom, an amino group, a cyano group, or the like. 51 and R 53 is preferably a methyl group or an ethyl group. R 51 and R 53 In the above formula, the alkoxy group having 1 to 40 carbon atoms may be linear or branched. Examples of the alkoxy group having 1 to 40 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

[0280] The silicone may have at least one long chain hydrocarbon group. For example, R 51 At least one of R 53 At least one of or R 51 and R 53 may be a long chain hydrocarbon group, and 51At least one (for example, one) of the above may be a long-chain hydrocarbon group. Here, the long-chain hydrocarbon group may be a saturated hydrocarbon group having 6 or more, 10 or more, 15 or more, or 20 or more carbon atoms, preferably 10 or more or 23 or more carbon atoms. Here, the hydrocarbon group may be linear or branched, and is preferably an alkyl group. Specific examples of hydrocarbon groups include a hexyl group (6 carbon atoms), an octyl group (8 carbon atoms), a lauryl group (12 carbon atoms), a myristyl group (14 carbon atoms), a stearyl group (18 carbon atoms), a behenyl group (22 carbon atoms), a tricosyl group (23 carbon atoms), a lignoceryl group (tetracosyl group, 24 carbon atoms), a cellotyl group (hexacosyl group, 26 carbon atoms), a monthyl group (octacosyl group, 28 carbon atoms), a melissyl group (triacontane group, 30 carbon atoms), and a dotriacontane group (32 carbon atoms).

[0281] The long-chain hydrocarbon group R is preferred because it is easy to produce industrially and is readily available. 51 and R 53 Other than R 51 and R 53 is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

[0282] a is an integer of equal to or greater than 0. In terms of ease of industrial production and availability, a may be equal to or less than 40, equal to or less than 30, or equal to or less than 20, and is preferably equal to or less than 30.

[0283] The sum of a and b is 5 to 200. From the viewpoints of ease of industrial production, availability, and handling, the sum of a and b is preferably 10 to 100, and more preferably 40 to 60. a may be 0 to 150, for example, 1 to 100. The lower limit of b may be 1, 2, or 3, and the upper limit of b may be 150, 10, or 5.

[0284] When a or b is 2 or more, multiple R 51 and R 52 may be the same or different.

[0285] R51 and R 53 group (for example, when represented by the following formula (S2), R 51 and R 52 Group and R 53 It is preferred that 50 mol % or more of the total of the alkyl groups) are methyl groups.

[0286] The order of the repeating units bound by a or b is not limited to the order shown in the chemical formula, and can be any order. That is, the silicone may be a random polymer or a block polymer.

[0287] For example, silicones may have the formula: (R 53 )3Si-O-[-Si(R 51 )2-O-] a -[-Si(R 51 )(R 52 )-O-] b -Si(R 53 )3(S2) [In the formula, R 51 each independently represents 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; R 52 each independently represents a long chain hydrocarbon group; R 53 each independently represents 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; a represents an integer of 0 or more, b represents an integer of 1 or more, and (a+b) is 5 to 200. The polymer may be represented by the formula: In formula (S2), R 51 and R 53 may have an alkyl group having 3 to 40 carbon atoms or an unsaturated hydrocarbon group having 6 to 40 carbon atoms (for example, a hydrocarbon group having an aromatic ring), but it is preferable that it does not have these groups.

[0288] Examples of silicones are: [ka] [In the formula, a represents an integer of 0 to 150, b represents an integer from 1 to 150; (a+b) is 5 to 200, and n is an integer of 1 to 36 (preferably n is a long-chain hydrocarbon group).

[0289] Silicone can be synthesized by a conventionally known method, for example, by subjecting silicone having a SiH group to a hydrosilylation reaction with an α-olefin.

[0290] Examples of silicones having SiH groups include methylhydrogensilicones with a degree of polymerization of 10 to 200, or copolymers of dimethylsiloxane and methylhydrogensiloxane. Among these, methylhydrogensilicones are preferred due to their ease of industrial production and availability. Hydrogensilicones (e.g., methylhydrogensilicones) are polydiorganosiloxanes in which a portion of the side chain is substituted with hydrogen, and the hydrogen atoms are directly bonded to silicon atoms. When using hydrogensilicones, a catalyst may be used to improve reactivity. For example, zinc, tin, manganese, cobalt, iron, and amine-based catalysts can be used. Metal salts of organic acids are preferred as these catalysts, and fatty acids are preferred as organic acids. From the viewpoint of easy handling, zinc stearate or the like can be used. The catalyst is preferably used in an amount of 10 to 40% relative to the methylhydrogensilicone, as this facilitates its effectiveness. Two or more of amino-modified, epoxy-modified, carboxy-modified, and methylhydrogensilicones may be mixed. All of these silicones have reactive groups, and it is preferable that they have film-forming properties. The term "film-forming ability" refers to the ability of the silicone to form a solid film, rather than an oil or gel film, after being attached to the surface of a fiber in an emulsion state.

[0291] α-olefins are compounds from which long-chain hydrocarbon groups in silicones are derived. Specific examples of α-olefins include 1-tricosene, 1-tetracosene, 1-hexacosene, 1-octacosene, 1-triacontene, and 1-dotriacontene. The hydrosilylation reaction may be carried out by reacting the above-mentioned silicone having an SiH group with an α-olefin in stages or all at once, if necessary in the presence of a catalyst.

[0292] The amounts of the SiH group-containing silicone and the α-olefin used in the hydrosilylation reaction can be appropriately selected depending on the SiH group equivalent weight or number average molecular weight of the SiH group-containing silicone.

[0293] Examples of catalysts used in the hydrosilylation reaction include platinum and palladium compounds, with platinum compounds being preferred, such as platinum(IV) chloride.

[0294] The reaction conditions for the hydrosilylation reaction are not particularly limited and can be adjusted appropriately. The reaction temperature is, for example, 10 to 200° C., preferably 50 to 150° C. The reaction time can be, for example, 3 to 12 hours when the reaction temperature is 50 to 150° C. The hydrosilylation reaction is preferably carried out under an inert gas atmosphere. Examples of inert gases include nitrogen and argon. The reaction proceeds without a solvent, but a solvent may also be used. Examples of solvents include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

[0295] (reactive silicone) The silicone may include a reactive silicone. Examples of reactive silicones include polysiloxanes having reactive groups in the side chain, one end, both ends, or the side chain and both ends. However, from the viewpoint of achieving excellent slip resistance and water repellency at the same time, polysiloxanes having reactive groups in the side chain and / or both ends may also be used. The reactive silicone is not particularly limited as long as it has a reactive group in the molecule, and examples include amino-modified silicone, epoxy-modified silicone, carboxy-modified silicone, and hydrogen-modified silicone. The reactive silicone may be one in which one or more substituents in the above formula (S1) or formula (S2) have been replaced with a reactive group.

[0296] Examples of amino-modified silicones include those having a structure in which an amino group is bonded to an organic group directly bonded to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. The alkylene group preferably has 2 or more carbon atoms. The divalent aromatic group preferably has 6 or more carbon atoms. The amino group may be any of a primary amino group, a secondary amino group, and a tertiary amino group. Examples of organic groups having an amino group bonded thereto include the following: 2-aminoethyl group, N-methyl-2-aminoethyl group, N,N-dimethyl-2-aminoethyl group, N-ethyl-2-aminoethyl group, N,N-diethyl-2-aminoethyl group, N,N-methylethyl-2-aminoethyl group, 3-aminopropyl group, N-methyl-3-aminopropyl group, N,N-dimethyl-3-aminopropyl group, N-ethyl-3-aminopropyl group, N,N-diethyl-3-aminopropyl group, and N,N-methylethyl-3-aminopropyl group. These functional groups may be located on the side chains of the polysiloxane or at the terminals.

[0297] Epoxy-modified silicones include those having a structure in which an epoxy group is bonded to an organic group directly bonded to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. Typically, the bond between the organic group and the epoxy group is in the form of a glycidyl ether. Examples of such functional groups include 3-glycidoxypropyl and 2-glycidoxyethyl groups. These functional groups may be present on the side chain or at the terminal of the polysiloxane.

[0298] Examples of carboxy-modified silicones include those having a structure in which a carboxy group is bonded to an organic group directly bonded to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. The alkylene group preferably has two or more carbon atoms. The divalent aromatic group preferably has six or more carbon atoms. Examples of such functional groups include a 3-carboxypropyl group and a 2-carboxyethyl group. These functional groups may be present on the side chain of the polysiloxane or at the terminal.

[0299] (Silicone resin) The silicone may include a silicone resin. The silicone resin may be RSiO 1 / 2 Unit (M unit), RSiO 3 / 2 Units (T units) and SiO 4 / 2 The silicone resin (3) is a silicone resin consisting of at least one selected from R2SiO 2 / 2 It is preferable that the unit (D unit) is not contained in order to exert the effect of the present invention.

[0300] 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, and stearyl groups. However, in terms of stability when the silicone resin (3) is in a sol state, ease of raw material availability, and cost, R is preferably a methyl group, and it is particularly preferred that 90% or more of all R are methyl groups. Note that different types of groups may be used in combination as R.

[0301] Silicone resin with R2SiO 2 / 2 If the silicone resin contains D units, the low slip properties of the composition may be impaired. Also, if the silicone resin contains only Q units, the water repellency of the composition may be impaired.

[0302] Examples of the silicone resin structure include (i) silicone resins consisting of M units and Q units, (ii) M units, T units and Q units, (iii) M units and T units, (iv) T units and Q units, and (v) silicone resins consisting only of T units. (i) Silicone resins consisting of M units and Q units and (v) silicone resins consisting only of T units are preferred. (i) The molar ratio of M units to Q units (M / Q) in silicone resins consisting of M units and Q units is preferably 0.6 to 1.3, more preferably 0.8 to 1.1. Two or more of these silicone resins may be used in combination.

[0303] The silicone resin (3) may also contain a structural unit containing a hydroxyl group bonded to a silicon atom. Specifically, (HO)RSiO 2 / 2 Units and (HO)2RSiO 1 / 2 Units: (HO)SiO 3 / 2 Units: (HO)2SiO 2 / 2 Units: (HO)3SiO 1 / 2 Some of the hydroxyl groups may be alkoxy groups represented by RO groups.

[0304] As described in Patent No. 3852921, sols containing silicone resins can be obtained by a manufacturing method in which organodisiloxane, tetraalkoxysilane, and their partial hydrolysis condensates are uniformly dispersed and polymerized in water containing a surfactant, or by a manufacturing method in which the following silane compounds are hydrolyzed in water.

[0305] The production method of hydrolyzing a silane compound in water will now be described in detail. Any silane compound can be used as a raw material for production, as long as the hydrolyzable group is chloro or alkoxy, the compound contains one, three, or four hydrolyzable groups, and the compound has an alkyl group that satisfies the above conditions.Specifically, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrichlorosilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrichlorosilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrichlorosilane, Trichlorosilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrichlorosilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, hexyltrichlorosilane, hexyltrimethoxysilane, hexyltriethoxysilane, 2-ethylhexyltrichlorosilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, decyltrichlorosilane, decyltrimethoxysilane, decyltriethoxysilane, cetyltrichlorosilane, cetyltrimethoxysilane, cetyltriethoxy Silane, stearyl trichlorosilane, stearyl trimethoxysilane, stearyl triethoxysilane, trimethyl chlorosilane, trimethyl methoxysilane, trimethyl ethoxysilane, trimethyl isopropoxysilane, dimethyl ethyl chlorosilane, dimethyl ethyl methoxysilane, dimethyl ethyl ethoxysilane, dimethyl propyl chlorosilane, dimethyl propyl methoxysilane, dimethyl propyl ethoxysilane, dimethyl isopropyl chlorosilane, dimethyl isopropyl methoxysilane, dimethyl isopropyl ethoxysilane, di Usable silane compounds include, but are not limited to, methylhexyl chlorosilane, dimethylhexyl methoxysilane, dimethylhexyl ethoxysilane, dimethyldecyl chlorosilane, dimethyldecyl methoxysilane, dimethyldecyl ethoxysilane, dimethyl cetyl chlorosilane, dimethyl cetyl methoxysilane, dimethyl cetyl ethoxysilane, dimethylstearyl chlorosilane, dimethylstearyl methoxysilane, dimethylstearyl ethoxysilane, and partial hydrolysates thereof.From the viewpoints of operability, ease of distilling off by-products, and ease of obtaining raw materials, it is more preferable to use methoxysilane or ethoxysilane. One or a mixture of two or more of these silane compounds may be used.

[0306] As a method for hydrolyzing a silane compound in water, a commonly known common method can be used, such as a method in which the hydrolysis reaction is carried out while the silane compound is dropped into water, or a method in which water and the silane compound are mixed together and then the hydrolysis reaction is carried out. A hydrolysis catalyst may be used when carrying out the hydrolysis reaction. Conventional catalysts can be used as the hydrolysis catalyst, and it is preferable to use an acidic or alkaline catalyst. In the case of an acidic catalyst, hydrogen halide, carboxylic acid, sulfonic acid, acidic or weakly acidic inorganic salt, solid acid such as ion exchange resin is preferred. In the case of an alkaline catalyst, alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate, alkali metal silanolates such as sodium silanolate and potassium silanolate, amines such as triethylamine, diethylamine, and aniline, and aqueous ammonia can be used. The amount of catalyst added is preferably adjusted so that the pH of the aqueous solution is 2 to 7 or 7 to 12. Furthermore, after completion of the reaction, a neutralizing agent to neutralize the acidic or alkaline catalyst may be added as needed.

[0307] A surfactant may be added to the aqueous solution to disperse the silane compound and the hydrolysis reaction product in water. The surfactant is not particularly limited, but examples include anionic surfactants such as alkyl sulfates, alkylbenzene sulfonates, and alkyl phosphates; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene oxypropylene alkyl ethers, polyoxyethylene alkyl phenyl 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. These surfactants can be used alone or in combination. Surfactants that exhibit acidic or alkaline properties can also be used as hydrolysis catalysts. The amount of surfactant added is not particularly limited, but is preferably 1 to 50 parts by weight per 100 parts by weight of the silane compound. Less than 1 part by weight of the surfactant will not be effective, while more than 50 parts by weight may impair the water repellency of the water repellent agent.

[0308] A hydrolysis catalyst and surfactant may be added to a mixture of water and silane compound, if necessary, and the hydrolysis reaction may be carried out at 0 to 90°C for 10 minutes to 24 hours. A neutralization reaction may then be carried out as necessary to obtain a silicone resin. Furthermore, by-products such as alcohols and neutralized salts produced by the hydrolysis reaction may be removed by vacuum distillation or filtration. Various additives may be added to this silicone resin. For example, preservatives, thickeners, etc. may be added depending on the purpose.

[0309] (amount of silicone) The amount of silicone may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the polymer. The amount of silicone may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the polymer.

[0310] [wax] The composition of the present disclosure preferably contains a wax in addition to the monomer (1) and the hydrophobic monomer (2). By including a wax, the composition can have good water repellency. The composition of the present disclosure may contain both a silicone and a wax, or may contain only one of a silicone and a wax.

[0311] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, animal and vegetable wax, and mineral wax. Paraffin wax is preferred. Specific examples of compounds constituting the wax include normal alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane), and normal alkenes (e.g., 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane). The number of carbon atoms in the compound constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be 200 to 2000, for example, 250 to 1500, or 300 to 1000. These may be used alone or in combination of two or more.

[0312] The melting point of the wax may be 50° C. or higher, 55° C. or higher, 60° C. or higher, 65° C. or higher, or 70° C. or higher, preferably 55° C. or higher, more preferably 60° C. or higher. The melting point of the wax is measured in accordance with JIS K 2235-1991.

[0313] (amount of wax) The amount of wax may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the polymer. The amount of wax may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the polymer.

[0314] [Organic acid] The composition of the present disclosure may contain an organic acid as an additional component. Known organic acids can be used. Preferred organic acids include carboxylic acids, sulfonic acids, sulfinic acids, etc., with carboxylic acids being particularly preferred. Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, and citric acid, with formic acid or acetic acid being particularly preferred. In the present disclosure, one organic acid may be used, or two or more organic acids may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0315] (amount of organic acid) The amount of organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, per 100 parts by weight of the polymer. The amount of organic acid may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, per 100 parts by weight of the polymer. The amount of organic acid may be adjusted so that the pH of the composition is 3 to 10, for example, 5 to 9, particularly 6 to 8. The composition may be acidic (pH 7 or less, for example, 6 or less).

[0316] [Hardening agent] The composition may contain a curing agent (an active hydrogen reactive compound or an active hydrogen containing compound) which may be added to the composition after polymerization to obtain a polymer.

[0317] The curing agent (crosslinking agent) in the composition can effectively cure the polymer. The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen-reactive groups of the polymer. Examples of the active hydrogen-reactive compound include polyisocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of the active hydrogen-containing compound include hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0318] The curing agent may be a polyisocyanate compound. A polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound functions as a crosslinking agent. Examples of the polyisocyanate compound include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates.

[0319] Examples of aliphatic polyisocyanates are 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, 2,6-di ... Aliphatic diisocyanates such as isocyanatomethyl caproate, and aliphatic triisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane. These may be used alone or in combination of two or more.

[0320] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used alone or in combination of two or more.

[0321] Examples of araliphatic polyisocyanates include araliphatic diisocyanates and araliphatic triisocyanates. Specific examples of araliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used alone or in combination of two or more.

[0322] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used alone or in combination of two or more.

[0323] Examples of the polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, uretimines, isocyanurates, and iminooxadiazinediones. These may be used alone or in combination of two or more.

[0324] These polyisocyanates can be used alone or in combination of two or more. As the polyisocyanate compound, it is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of a polyisocyanate compound is blocked with a blocking agent.The use of a blocked polyisocyanate compound is preferable for reasons such as its relative stability in an aqueous solution and its usability in the same aqueous solution as the composition.

[0325] The blocking agent blocks free isocyanate groups. When the blocked polyisocyanate compound is heated to, for example, 100°C or higher, e.g., 130°C or higher, the isocyanate groups are regenerated and can easily react with hydroxyl groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. The polyisocyanate compounds can be used alone or in combination.

[0326] The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. The chloromethyl group-containing compound is a compound having a chloromethyl group. Examples of the chloromethyl group-containing compound include chloromethyl polystyrene. The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound include (poly)acrylic acid and (poly)methacrylic acid.

[0327] Specific examples of the ketone group-containing compound include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of the hydrazide compound include hydrazine, carbohydrazide, and adipic acid hydrazide. Specific examples of the melamine compound include melamine resins and methyl etherified melamine resins.

[0328] (Amount of hardener) The amount of curing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, based on 100 parts by weight of the polymer. The amount of curing agent may be 50 parts by weight or less, 40 parts by weight or more, based on 100 parts by weight of the polymer.

[0329] [Hydrophilic particles] The composition of the present disclosure may contain hydrophilic particles as an additional component. Here, hydrophilicity refers to the property of particles easily dispersing in an aqueous solvent without agglomeration. For example, when 1.0 wt % of particle powder and an optional dispersant are added to an aqueous solvent, the mixture is stirred at 700 rpm for 10 minutes using a homomixer, and then allowed to stand for 1 hour, and no precipitation or aggregation of the particles is visually observed, the composition is considered to have hydrophilicity. Furthermore, the particles contained in commercially available aqueous particle dispersions in which particles are dispersed in an aqueous solvent are also considered to have hydrophilicity.

[0330] The hydrophilic particles may have hydrophilic groups on their surfaces. Examples of the hydrophilic groups include cationic groups, anionic groups, amino groups, and hydroxyl groups. The surfaces of the hydrophilic particles may be subjected to a hydrophilization treatment, but are generally not subjected to a hydrophobic treatment.

[0331] The hydrophilic particles are not particularly limited as long as they are hydrophilic. Examples include inorganic particles (e.g., inorganic oxide particles) such as alumina, silica, and titania, and organic particles such as latex, acrylic, and nylon. Among these, inorganic particles are preferred due to their ease of handling, and at least one selected from the group consisting of silica and alumina is particularly preferred. Examples of commercially available products include silicon oxide particles such as "Snowtex ST-OYL," "Snowtex ST-AK-L," and "Snowtex ST-AK-YL" (all manufactured by Nissan Chemical Industries Co., Ltd.), titanium oxide particles such as "TA300" and "TA300D" (both manufactured by Fuji Titanium Industry Co., Ltd.), and aluminum oxide particles such as "TM-5D" (manufactured by Taimei Chemical Industry Co., Ltd.). These may be used alone or in combination.

[0332] (Average primary particle size) The average primary particle diameter of the hydrophilic particles may 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 diameter of the hydrophilic particles may 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. A diameter within the above range ensures good water repellency. The average primary particle diameter can be measured using a microscope (scanning electron microscope or transmission electron microscope). Specifically, an arbitrary position on the fabric is observed from above using a microscope at an arbitrary magnification. Next, if the particle shape is spherical, the diameter is considered to be the particle diameter (particle size). If the particle shape is non-spherical, the average of the longest and shortest diameters is considered to be the particle size (particle size). The particle size of all particles present in the field of view is measured, and then the field of view is moved and the particle size is measured again. This process is repeated until particle sizes are measured at 10 or more points, and the average value is taken as the average primary particle size.

[0333] (Turbidity) The turbidity of an aqueous dispersion prepared by dispersing hydrophilic particles in water at a concentration of 10 g / L and adjusting the pH to 7 may be 0.1 ppm or more, 1 ppm or more, 5 ppm or more, or 10 ppm or more. The turbidity of an aqueous dispersion prepared by dispersing hydrophilic particles in water at a concentration of 10 g / L and adjusting the pH to 7 may be 200 ppm or less, 100 ppm or less, 50 ppm or less, 20 ppm or less, 10 ppm or less, 5 ppm or less, or 2.5 ppm or less, preferably 20 ppm or less. By being in the above range, water repellency, slip resistance, and storage stability can be excellently combined. The turbidity can be calculated based on a calibration curve (0 to 1000 ppm range) prepared using an integrating sphere turbidimeter PT200 manufactured by Nitto Seiko Analytech Co., Ltd., based on JIS K0101, Drinking Water Testing Method, using the turbidity of a standard sample, kaolin (pigment), based on the calibration curve.

[0334] (zeta potential) The zeta potential of an aqueous dispersion prepared by dispersing hydrophilic particles in water at a concentration of 10 g / L and adjusting the pH to 7 may 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 prepared by dispersing hydrophilic particles in water at a concentration of 10 g / L and adjusting the pH to 7 may 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. Having a turbidity within the above range ensures good water repellency, slip resistance, and storage stability. The zeta potential can be measured, for example, using a commercially available zeta potential measuring device.

[0335] (amount of hydrophilic particles) The amount of hydrophilic particles may be 0.01 wt% or more, 0.1 wt% or more, 0.3 wt% or more, 0.5 wt% or more, 1 wt% or more, 2 wt% or more, 3 wt% or more, or 5 wt% or more, preferably 0.5 wt% or more, particularly preferably 2 wt% or more, based on the total amount of the polymer and the hydrophilic particles. The amount of hydrophilic particles may be 60 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, 5 wt% or less, 3 wt% or less, or 2 wt% or less, preferably 12 wt% or less, based on the total amount of the polymer and the hydrophilic particles. By having the amount of hydrophilic particles in the above range, good water repellency can be achieved.

[0336] The silicone, wax, hydrophilic particles, liquid medium, dispersant, surfactant, or curing agent described above may be added after the polymer is produced, or the polymer may be produced by polymerizing the monomers of the polymer in the presence of the silicone, wax, hydrophilic particles, liquid medium, dispersant, surfactant, or curing agent described above.

[0337] [Other ingredients] The composition may contain other components in addition to the above components. After the polymer is produced, other components may be added. Examples of other components include water and / or oil repellents, antislip agents, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorizers, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above ingredients, other ingredients may include texture adjusters, fabric softeners, antibacterial agents, flame retardants, paint fixatives, wrinkle inhibitors, drying speed regulators, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage inhibitors, anti-wrinkle agents after washing, shape retention agents, drape retention agents, ironing improvers, whitening agents, fabric softening clay, dye transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain release agents, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Ciba Specialty Chemicals' Chinopal CBS-X), dye fixatives, anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine, and stain removers. Fiber surface modifiers include enzymes such as cellulase, amylase, protease, lipase, and keratinase, and agents that can impart silk texture and functionality such as foam inhibitors and moisture absorption and release properties include silk protein powder, surface-modified products, and emulsified dispersions thereof.Specific examples include K-50, K-30, K-10, A-705, S-702, L-710, and FP series (Idemitsu Petrochemical), hydrolyzed silk liquid (Jomo), Silkgen G Soluble S (Ichimaru Falcos), and stain inhibitors such as nonionic polymeric compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units, such as FR627 manufactured by GOO Chemical Industry and SRC-1 manufactured by Clariant Japan.These may be used alone or in combination.

[0338] (antistatic agent) Examples of antistatic agents include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate ester salts, phosphonates, and phosphate ester salts; amphoteric antistatic agents such as alkylbetaine and its derivatives, imidazoline and its derivatives, alanine and its derivatives, and nonionic antistatic agents such as aminoalcohols and their derivatives, glycerin and its derivatives, and polyethylene glycol and its derivatives. Ion-conductive polymers obtained by polymerizing or copolymerizing monomers having these cationic, anionic, or amphoteric ion-conductive groups may also be used. These may be used alone or in combination.

[0339] (preservatives) Preservatives are primarily used to enhance antiseptic and bactericidal properties and maintain antiseptic properties during long-term storage. Examples of preservatives include isothiazolone organic sulfur compounds, benzisothiazolone organic sulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol. The amount of preservative is preferably 0.0001 to 1 wt% of the total weight of the composition. When the amount of preservative is equal to or greater than the lower limit of the above range, the effect of adding the preservative is sufficiently obtained, and when the amount is equal to or less than the upper limit, the storage stability of the composition is good.

[0340] (ultraviolet absorber) An ultraviolet absorber is a chemical agent that has the effect of protecting against ultraviolet rays, and is a component that absorbs ultraviolet rays and converts them into infrared rays, visible light, etc. Examples of ultraviolet absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, and 4-t-butyl-4'-methoxybenzoylmethane.

[0341] (Antibacterial agent) Antibacterial agents are components that have the effect of suppressing the growth of bacteria on fibers and further suppressing the generation of unpleasant odors caused by microbial decomposition products. Examples of antibacterial agents include cationic disinfectants such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide) zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, and polylysine.

[0342] (Deodorant) Examples of deodorizing agents include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, and aminocarboxylic acid metal complexes (e.g., zinc complex of trisodium methylglycinediacetate described in WO 2012 / 090580).

[0343] (fragrance) The fragrance is not particularly limited, and lists of usable fragrance raw materials can be found in various documents, such as "Perfume and Flavor Chemicals," Vol. I and II, Steffen Arctander, Allured Pub. Co. (1994); "Synthetic Fragrances: Chemistry and Product Knowledge," by Genichi Indo, The Chemical Daily (1996); "Perfume and Flavor Materials of Natural Origin," by Steffen Arctander, Allured Pub. Co. (1994); "Encyclopedia of Fragrances," edited by the Japan Fragrance Manufacturers Association, Asakura Shoten (1989); "Perfumery Material Performance V.3.3," by Boelens Aroma Chemical Information Service (1996); and "Flower Oils and Floral Compounds in Perfumery," by Danute Lajaujis Anonis, Allured Pub. Co. (1993), each of which is incorporated herein by reference.

[0344] (amount of other ingredients) The amount of the other components may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the polymer. The amount of the other components may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the polymer.

[0345] (amount of polymer) The amount of polymer in the composition may 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. The amount of polymer in the composition may 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.

[0346] <Uses of the composition> Examples of applications of the composition of the present disclosure include use as an external treatment agent (surface treatment agent) or internal treatment agent, a repellent (a water repellent, an oil repellent, or a water and oil repellent, etc., particularly a water repellent), an antifouling agent, a dirt release agent, a stripping agent, a release agent (an external release agent or an internal release agent), etc. Alternatively, the composition of the present disclosure can be used as an external treatment agent (surface treatment agent) or internal treatment agent, a repellent (a water repellent, an oil repellent, or a water and oil repellent, etc., particularly a water repellent), an antifouling agent, a dirt release agent, a stripping agent, a release agent (an external release agent or an internal release agent).

[0347] <Method of producing the composition> The method for producing the composition may include a step 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., an emulsifier, a liquid medium, a wax, etc.) to obtain a polymer. Alternatively, the method for preparing the composition may include a step of adding an additional component (e.g., an emulsifier, a liquid medium, a wax, etc.) to a solution or dispersion of the polymer, or a step of mixing a solution or dispersion of the polymer with a solution or dispersion of the additional component (e.g., an emulsifier, a liquid medium, a wax, etc.).

[0348] In order for the composition to exhibit high water repellency, it is preferable to subject the composition to ultrasound (ultrasonic treatment). It is preferable to perform the ultrasonic treatment immediately before applying it to the object to be treated. For example, the composition is applied to the object to be treated 1 minute to 1 hour after the ultrasonic treatment. The ultrasonic treatment can be carried out by subjecting the composition to ultrasound. There are no particular restrictions on the ultrasonic generator, but an output of 500 W or more, for example, 500 to 2000 W, is preferred in terms of efficient mixing. The ultrasonic treatment time may be 0.5 to 60 minutes. For example, a homogeneous composition can be obtained by treating with a 500 W ultrasonic generator for 10 minutes.

[0349] Examples of polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization.

[0350] In solution polymerization, a method is employed in which monomers are dissolved in an organic solvent in the presence of a polymerization initiator, and after purging with nitrogen, the mixture is heated and stirred at a temperature in the range of 30 to 120°C for 1 to 10 hours. Examples of polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, per 100 parts by weight of the monomers.

[0351] The organic solvent is inert to the monomers and dissolves them, and may be, for example, an ester (e.g., an ester having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), a ketone (e.g., a ketone having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone), or an alcohol (e.g., an alcohol having 1 to 40 carbon atoms, specifically, ethanol, butanol, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane. The organic solvent is used in an amount of 10 to 3000 parts by weight, for example, 50 to 2000 parts by weight, relative to 100 parts by weight of the total of the monomers.

[0352] Emulsion polymerization involves emulsifying monomers in water in the presence of a polymerization initiator and an emulsifier, purging with nitrogen, and then polymerizing the mixture at 50-80°C for 1-20 hours with stirring. Polymerization initiators include water-soluble initiators such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, sodium peroxide, potassium persulfate, and ammonium persulfate, as well as oil-soluble initiators such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01-10 parts by weight per 100 parts by weight of monomer.

[0353] To obtain a polymer aqueous dispersion with excellent shelf stability, it is desirable to polymerize the monomer by microparticulating it in water using an emulsifying device capable of applying powerful crushing energy, such as a high-pressure homogenizer or ultrasonic homogenizer. Furthermore, various anionic, cationic, or nonionic emulsifiers can be used as emulsifiers, and are used in an amount ranging from 0.5 to 20 parts by weight per 100 parts by weight of the monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. If the monomers are not completely compatible, it is preferable to add a compatibilizer, such as a water-soluble organic solvent or a low-molecular-weight monomer, that will fully compatibilize these monomers. Addition of a compatibilizer can improve emulsifiability and copolymerizability.

[0354] The water-soluble organic solvent may be any of the organic solvents described above. Examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol. These may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of water. Examples of low-molecular-weight monomers include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate. These may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of the total amount of monomers.

[0355] A chain transfer agent may be used in the polymerization. The molecular weight of the polymer can be changed depending on the amount of chain transfer agent used. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (e.g., having 1 to 40 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite. The amount of chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, per 100 parts by weight of the total amount of monomers.

[0356] The composition may be in the form of a solution, emulsion (especially an aqueous dispersion), or aerosol.

[0357] <Water repellent> The water repellent of the present disclosure includes the polymer of the present disclosure. The water repellent of the present disclosure may be the composition of the present disclosure. In other words, the composition of the present disclosure can be used as a water repellent as is. The water repellent of the present disclosure may be prepared by applying, in addition to the polymer of the present disclosure, various materials and conditions used for preparing the composition of the present disclosure.

[0358] The water repellent agent according to the present disclosure may not contain any compound selected from the group consisting of a compound having a fluoroalkyl group having 8 or more carbon atoms, a compound having a perfluoroalkyl group having 8 or more carbon atoms, a compound having a fluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The water repellent agent according to the present disclosure can impart liquid repellency to a substrate even without containing these fluorine compounds.

[0359] <Applications of water repellent agents> Examples of uses of the water repellent agent in the present disclosure include an external treatment agent (surface treatment agent) or an internal treatment agent, a repellent (a water repellent, an oil repellent, or a water and oil repellent, etc., particularly a water repellent), an antifouling agent, a stain release agent, a stripping agent, a release agent (an external release agent or an internal release agent), and the like.

[0360] <Manufacturing method of treated products> A method of making a treatment product of the present disclosure includes applying a water repellent agent of the present disclosure to a substrate.

[0361] [Processed products] Substrates that can be treated with the water repellent of the present disclosure include textile 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, ceramic products, plastics, painted surfaces, and plaster. Various examples of textile products can be mentioned. Examples include natural fibers of animal and plant origin, such as cotton, linen, wool, and silk; synthetic fibers, such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers, such as rayon and acetate; inorganic fibers, such as glass fiber, carbon fiber, and asbestos fiber; and mixtures of these fibers. As an example of a substrate that can be treated with the water repellent, woven and knitted fabrics will be described in detail below.

[0362] (woven and knitted fabrics) ·Method of manufacturing knitted fabrics Woven and knitted fabrics can be obtained by weaving and knitting long and short fiber yarns made of the above-mentioned fibers to obtain a greige fabric, which is then post-processed and subjected to a water-repellent treatment. The weaving and knitting can be carried out using known looms and knitting machines, and known equipment can also be used for the preparation process prior to the weaving and knitting.

[0363] The woven or knitted fabric can be post-processed using known scouring and dyeing methods and equipment suitable for the fiber material of the woven or knitted fabric.

[0364] After the post-processing, the woven or knitted fabric may be subjected to a water-repellent treatment. In the water-repellent treatment, first, an aqueous solution containing a water repellent (which may be the water repellent or composition of the present disclosure) is prepared. Next, the aqueous solution is applied to the woven or knitted fabric after the post-processing using a padding method, a spray method, a kiss roll coater method, a slit coater method, or the like, and then dried and subjected to a dry heat treatment. The aqueous solution may also contain a crosslinking agent, a softener, an antistatic agent, or the like, as necessary. After the water-repellent treatment, the woven or knitted fabric may be calendered to further improve the water-repellent performance.

[0365] The woven and knitted fabrics are suitable for use in clothing applications requiring water repellency, particularly sportswear applications for outdoor activities, skiing, snowboarding, golf, etc., and uniform applications.

[0366] Laminated fabric The woven / knitted fabric of the present disclosure may be provided as a laminated fabric having a moisture-permeable waterproof layer on one side thereof. The moisture-permeable waterproof layer may be laminated directly onto the woven / knitted fabric, or may be laminated onto the woven / knitted fabric via an adhesive layer. When the laminated fabric of the present disclosure is used for clothing or the like, the woven / knitted fabric side is arranged to repel rainwater and the like.

[0367] Breathable waterproof layer The moisture-permeable waterproof layer is a layer that covers one side of a woven or knitted fabric, and is a layer formed of a waterproof and moisture-permeable resin or structural film.

[0368] The moisture-permeable waterproof layer may be formed by applying a resin (the resin that constitutes the moisture-permeable waterproof layer) directly to the woven or knitted fabric, or may be laminated to one side of the woven or knitted fabric via an adhesive layer described below.

[0369] The resin constituting the moisture-permeable waterproof layer is not particularly limited, but may be: Both non-porous and porous resins are used. For non-porous materials, polyurethane resins and polyester elastomer resins containing hydrophilic components are used to provide moisture permeability. For porous materials, polyurethane resins that form wet-process porous membranes and polyurethane resins that are made porous by electrospinning are used, as well as porous PTFE membranes and porous membranes made of PE or PP.

[0370] As the polyurethane resin, a conventionally known resin obtained by reacting a polyisocyanate component with a polyol component can be used.

[0371] A moisture-permeable waterproof membrane having a microporous structure can be obtained by wet coagulation of a DMF solution of a polyurethane resin containing inorganic fine powder. Examples of inorganic fine powder include fine powders made of silicon dioxide, aluminum dioxide, or titanium dioxide. The average primary particle size of the inorganic fine powder is preferably about 7 to 40 nm. The amount of inorganic fine powder is preferably 3 to 50 wt %, and more preferably 5 to 50 wt %, of the total weight of the moisture-permeable waterproof layer.

[0372] The thickness of the moisture-permeable waterproof layer is preferably 5 μm or more, and more preferably 10 to 30 μm. A thickness within this range provides an excellent balance between waterproofness and moisture permeability, and is also advantageous in terms of texture.

[0373] ·Adhesive layer The laminated fabric preferably includes an adhesive layer. That is, the woven or knitted fabric and the moisture-permeable waterproof layer are preferably laminated via an adhesive layer. In addition, it is preferable that the adhesive layer is a discontinuous layer such as a dot or grid pattern in terms of moisture permeability.

[0374] The type of adhesive that constitutes the adhesive layer is not particularly limited, but it is preferable that it has excellent compatibility with the moisture-permeable waterproof layer. For example, if a resin containing polyurethane resin as the main component is selected as the resin that constitutes the moisture-permeable waterproof layer, it is preferable to use an adhesive layer made of a polyurethane-based adhesive. The polyurethane-based adhesive may be any of ether-based, ester-based, polycarbonate-based, etc.

[0375] The adhesive layer may be formed over the entire surface of one side of the woven or knitted fabric, or may be formed in a pattern from the viewpoint of moisture permeability, texture, etc. The pattern shape is not particularly limited, but examples include dots, lines, a grid, a checkerboard pattern, a tortoiseshell pattern, etc., and it is preferable that any of these patterns be uniformly arranged over the entire surface.

[0376] The thickness of the adhesive layer is preferably about 10 to 100 μm, and more preferably 20 to 80 μm.

[0377] Lining fabric In the laminated fabric of the present disclosure, a lining fiber fabric may be laminated on the moisture-permeable waterproof layer (on the side of the moisture-permeable waterproof layer opposite to the side on which the woven or knitted fabric of the present disclosure is laminated). The lining fiber fabric can protect the moisture-permeable waterproof layer and can provide even better waterproofness (water pressure resistance) and strength.

[0378] Examples of lining fiber fabrics include various woven and knitted fabrics. Among them, knitted fabrics are preferred because, compared with woven fabrics, the constituent yarns tend to protrude from the surface, resulting in an uneven surface, and the knitted fabric exhibits a stronger anchoring effect, making it less likely to peel from the moisture-permeable waterproof layer. Tricot knitted fabrics are also preferred because they can be knitted into long gray fabrics with few seams, allowing them to be evenly layered on the moisture-permeable waterproof layer.

[0379] The material of the fibers constituting the lining fiber fabric is not particularly limited and can be selected as appropriate, but nylon fiber is preferred. This is because acid dyes are generally used in nylon fibers, which makes it less likely for the disperse dye to migrate and sublimate into the moisture-permeable waterproof layer, a problem that occurs with polyester fibers, etc., which use disperse dyes. The form (long fiber, short fiber, or spun yarn) or fineness of the fibers constituting the lining fiber fabric are not particularly limited and can be selected as appropriate as long as the effects of the present disclosure are not impaired.

[0380] · Properties of laminated fabric The laminated fabric has excellent waterproofness. A suitable example of the waterproofness of the laminated fabric of the present disclosure is a water level measured according to the water resistance test specified in JIS L 1092:2009 Method A (low water pressure method) of 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.

[0381] The laminated fabric has excellent moisture permeability. A suitable example of the moisture permeability of the laminated fabric of the present disclosure is a fabric having a moisture permeability of, for example, 10,000 g / m 2 as measured according to JIS L 1099:2021 B-1 method (potassium acetate method). 224 hours or more, preferably 15,000 g / m 2 24 hours or more, more preferably 20,000 g / m 2 The upper limit of the moisture permeability is not particularly limited, but for example, 40,000 g / m 2 24h or 35,000g / m 2 24h mm. In addition, the moisture permeability measured in accordance with JIS L 1099:2021 A-1 method (calcium chloride method) is, for example, 4000 g / m 2 24 hours or more, preferably 8000g / m 2 24 hours or more, more preferably 10,000 g / m 2 The upper limit of the moisture permeability is 13,000 to 15,000 g / m², which is the limit of the measurement method. 2 Approximately 24 hours.

[0382] In the laminated fabric of the present disclosure, the peel strength between the woven or knitted fabric and the breathable waterproof layer, as measured according to the method of JIS K 6404-2, is preferably, for example, 2.55 N / 2.54 cm or more for clothing applications, and may be preferably 5 N / 2.54 cm or more for use in applications.

[0383] ·Laminated fabric manufacturing method The method for producing the laminated fabric is not particularly limited, but examples thereof include the first and second production methods described below. First manufacturing method: The first manufacturing method includes a step of forming the moisture-permeable waterproof layer by applying a resin that constitutes the moisture-permeable waterproof layer to the surface of a woven or knitted fabric. Second manufacturing method: This method includes the steps of forming an adhesive layer on the woven or knitted fabric or the moisture-permeable waterproof layer, and bonding the woven or knitted fabric and the moisture-permeable waterproof layer together via the adhesive layer.

[0384] In the first manufacturing method, the resin that constitutes the moisture-permeable waterproof layer can be applied to the surface of the woven or knitted fabric by, for example, a coating method. A knife coater or a comma coater can be used in the coating method. From the viewpoint of providing excellent moisture permeability, it is preferable to obtain the moisture-permeable waterproof layer by a wet method.

[0385] In the second manufacturing method, examples of the method for forming an adhesive layer on a woven or knitted fabric or a moisture-permeable waterproof layer include a lamination method. In the lamination method, a resin solution or a hot melt method can be used to form the adhesive layer. First, a moisture-permeable waterproof layer-forming resin composition (e.g., a resin composition containing a resin and an organic solvent) is applied to the surface of a release material (such as release paper, release cloth, or release film) with a clearance, and a moisture-permeable waterproof layer is formed while adjusting the thickness. The layer is then dried and heat-treated to allow the reaction to complete, yielding a film. The release material can be removed as appropriate after lamination or aging. Furthermore, when laminating using a hot melt method, the release material can be peeled off and the film can be laminated alone. In addition, the breathable waterproof membrane can be bonded to membranes produced using solvent-free extrusion methods such as the T-die method and inflation, porous membranes produced using the electrospinning method, and porous membranes made of PTFE, PE, PP, etc.

[0386] An adhesive layer is then formed on the woven or knitted fabric or the moisture-permeable waterproof layer. For example, if a resin solution is used, a two-component curing polyurethane resin solution with a viscosity in the range of 500 to 5,000 mPa·s may be applied to the entire surface or in a pattern. The resulting solution is then dried to form an adhesive layer. The woven or knitted fabric and the moisture-permeable waterproof layer are then bonded together via the adhesive layer, and the two are then pressure-bonded or thermocompression-bonded to complete the second manufacturing method.

[0387] On the other hand, in the case of hot melt, it is preferable to use a moisture-curing resin that reacts with moisture in the air, and in practical use, it is more preferable to use one that melts in a temperature range of about 80 to 150°C. In this case, the hot melt resin is first melted while taking into consideration the melting point of the resin and its viscosity when melted. The molten resin is then applied to the woven or knitted fabric or the moisture-permeable waterproof layer and allowed to mature while cooling at room temperature to form an adhesive layer. The woven or knitted fabric and the moisture-permeable waterproof layer are then bonded together via the adhesive layer, thereby completing the second manufacturing method. Alternatively, if texture is important, the resin can be applied in a pattern to the moisture-permeable waterproof membrane and then bonded to the woven or knitted fabric.

[0388] Thereafter, a lining fiber fabric can be laminated on the moisture-permeable waterproof layer using any known appropriate method.

[0389] ·Applications of laminated fabric The laminated fabric has excellent water repellency and breathable waterproof properties, and the breathable waterproof layer does not peel off even in harsh environments, making it suitable for use in fields such as uniforms, sportswear, and outdoor products used outdoors.

[0390] [Processing method] The water repellent agent of the present disclosure can be applied to a substrate (particularly a fiber substrate) as a treatment agent (particularly a surface treatment agent) by conventionally known methods. The water repellent agent of the present disclosure may be dispersed and diluted in an organic solvent or water, if necessary, and applied to the surface of the substrate by known methods such as dip coating, spray coating, or foam coating, followed by drying. After drying, a fiber product is obtained with the solid components of the water repellent attached. If necessary, the water repellent agent may be applied together with an appropriate crosslinking agent and cured. Furthermore, the water repellent agent of the present disclosure can also be used in combination with various additives such as water and / or oil repellents, antislip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, wrinkle inhibitors, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, and antifoaming agents. Examples of various additives may be the same as those described in the "Other Components" section of the composition above. The concentration of the polymer in the treatment agent to be brought into contact with the substrate may be changed appropriately depending on the application, but may be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0391] [Textile products] Various examples of the fiber substrate as the substrate include cloth products and paper products. The fiber product as the substrate is also called a fiber substrate.

[0392] Examples of textile products include natural fibers of animal or plant origin such as cotton, linen, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber, or mixtures of these fibers. Textile products include woven fabrics, knitted fabrics, and nonwoven fabrics, clothing fabrics, and carpets, but the treatment may also be applied to fibers, yarns, and intermediate textile products (for example, slivers or rovings) in a state before they are made into textiles.

[0393] Examples of paper products include paper made from bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp or thermomechanical pulp, recycled paper pulp such as recycled newspaper, recycled magazine paper, recycled corrugated cardboard or deinked recycled paper, paper containers, paper molded articles, etc. Specific examples of paper products include food packaging paper, gypsum board base paper, coated base paper, medium-quality paper, general liners and corrugating mediums, neutral white roll paper, neutral liners, rust-proof liners and metal interleaving 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, molded paper (molded containers), etc.

[0394] The water repellent can be applied to a textile substrate (e.g., fabric) by any of the known methods for treating the substrate with a liquid. The textile substrate may be immersed in the water repellent, or the solution may be applied or sprayed onto the textile substrate. The treated textile substrate is preferably dried and cured by heating to develop water repellency. The heating temperature may be, for example, 80°C to 250°C, 100°C to 170°C, or 100°C to 120°C. The heating temperature may preferably be 100°C to 170°C. In the present disclosure, good performance can be obtained even with low-temperature heating (e.g., 100°C to 140°C). In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes.

[0395] Alternatively, the water repellent may be applied to the textile substrate by a cleaning method, such as in a laundry application or a dry cleaning method.

[0396] The treated fibrous substrate may be a fabric, including woven fabrics, knitted fabrics, and nonwoven fabrics, clothing fabrics, carpets, etc., but may also be a fiber or yarn or intermediate fiber product (e.g., sliver or roving, etc.) The water repellent agents of the present disclosure are particularly effective in making textile products (e.g., synthetic fibers) water repellent.

[0397] The fibers constituting the fibrous substrate may be natural fibers, synthetic fibers, semi-synthetic fibers, regenerated fibers, or inorganic fibers. The fibers may be used alone or in combination of two or more types.

[0398] Examples of natural fibers include cotton, flax, cellulose fibers such as pulp, chitin, chitosan, wool, and silk. Specific examples of wood pulp include mechanical pulps such as ground wood pulp (GP), pressure-raised ground wood pulp (PGW), and thermomechanical pulp (TMP), chemical pulps such as high-yield unbleached softwood kraft pulp (HNKP; N wood), bleached softwood kraft pulp (NBKP; N wood, NB wood), unbleached hardwood kraft pulp (LUKP; L wood), and bleached hardwood kraft pulp (LBKP; L wood), recycled paper pulps such as deinking pulp (DIP) and waste pulp (WP), and semi-chemical pulp (CP).

[0399] Examples of synthetic fibers include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and copolymer polyester; polyolefins such as linear low-density polyethylene, low-density polyethylene, high-density polyethylene, and polypropylene; polyamides such as nylon 6, nylon 66, nylon 610, and nylon 46; acrylic fibers such as polyacrylonitrile; polyvinyl alcohol, polyurethane, and polyvinyl chloride. Examples of semi-synthetic fibers include acetate and triacetate. Examples of regenerated fibers include rayon, cupro, polynosic rayon, lyocell, and Tencel. Examples of inorganic fibers include glass fiber and carbon fiber.

[0400] Alternatively, the fibrous substrate may be leather. The manufacturing polymer may be applied to the leather from an aqueous solution or emulsion at various stages of leather processing, for example, during wet processing of the leather or during finishing of the leather, to render the leather hydrophobic and oleophobic. Alternatively, the fibrous substrate may be paper. The manufacturing polymer may be applied to preformed paper or may be applied at various stages of papermaking, for example, during the drying period of the paper.

[0401] "Treatment" means applying the water repellent to a substrate by immersion, spraying, coating, or the like. The treatment allows the polymer, which is the active ingredient of the water repellent, to penetrate into the substrate and / or adhere to the surface of the substrate. In other words, the treatment results in a substrate (e.g., a textile) to which the polymer in the water repellent of the present disclosure is adhered. Such a substrate is a textile having water repellency, i.e., a water-repellent textile.

[0402] [Pretreatment of fiber substrates] The fibrous substrate may be pretreated before being treated with the water repellent of the present disclosure. Pretreatment of the fibrous substrate can impart excellent durability to the fibrous substrate after treatment with the water repellent.

[0403] Examples of pretreatments of fiber substrates include cationization treatment by reaction with a reactive quaternary ammonium salt, anionization treatment such as sulfonation, carboxylation, and phosphate, acetylation treatment after anionization treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, and polymer coating treatment.

[0404] The method for pretreating the fibrous substrate is not limited, and the fibrous substrate can be pretreated by a conventionally known method. The pretreatment liquid may be dispersed and diluted in an organic solvent or water as necessary, and applied to the surface of the fibrous substrate by a known method such as dip coating, spray coating, foam coating, etc., followed by drying. The pH and temperature of the pretreatment liquid may be adjusted depending on the desired degree of treatment. As an example of a method for pretreating a fibrous substrate, a method for pretreating a fibrous substrate with a hydrocarbon-based water repellent will be described in detail.

[0405] The pretreatment method for the fiber substrate is to add -SO3M to the fiber. 1 (In the formula, M 1 represents a monovalent cation), -COOM 2 (In the formula, M 2 represents a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(wherein, X 1 and X 2and each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) (hereinafter, also referred to as a "specific functional group").

[0406] M 1 Examples of M include H, K, Na, and ammonium ions which may have a substituent. 2 Examples of X include H, K, Na, and an ammonium ion which may have a substituent. 1 or X 2 When is an alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms, and more preferably an alkyl group having 4 to 12 carbon atoms.

[0407] The fibers containing the specific functional groups (hereinafter, sometimes referred to as "functional group-containing fibers") can be prepared, for example, by the following method. (i) A compound having the specific functional group is attached to a fiber material. The attachment of the compound may be in a state where a part of the compound is chemically bonded to a part of the fiber, to the extent that a sufficient amount of the specific functional group remains. (ii) A fiber is prepared in which the specific functional group is directly introduced into the material that constitutes the fiber.

[0408] In the case of (i), for example, functional group-containing fibers can be obtained by a functional group introduction step in which a fiber material is treated with a pretreatment liquid containing one or more compounds having the above-mentioned specific functional groups.

[0409] The material of the fiber material is not particularly limited, and examples thereof include natural fibers such as cotton, linen, silk, and wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene, and composite fibers and blended fibers thereof. The form of the fiber material may be any of fibers (tow, sliver, etc.), yarn, knitted fabric (including interwoven fabric), woven fabric (including interwoven fabric), nonwoven fabric, paper, etc.

[0410] In this embodiment, from the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use textile materials containing polyamide and polyester as raw materials, and it is particularly preferable to use nylons such as nylon 6 and nylon 6,6, polyesters such as polyethylene terephthalate (PET), polytrimethyl terephthalate and polylactic acid, and mixed fibers containing these.

[0411] Above -SO3M 1 A phenolic polymer can be used as the compound having the formula:

[0033] Such a phenolic polymer can be, for example, one containing at least one compound represented by the following general formula:

[0412] [ka] [In formula (2), X 2 Ha-SO3M 3 (In the formula, M 3 represents a monovalent cation) or a group represented by the following general formula, and n is an integer of 20 to 3000.

[0413] [ka] [In the formula, M 4 represents a monovalent cation.]

[0414] The above M 3 Examples of the cation include H, K, Na, and an ammonium ion which may have a substituent.

[0415] The above M 4 Examples of the cation include H, K, Na, and an ammonium ion which may have a substituent.

[0416] The compound represented by the above general formula may be, for example, a formalin condensate of phenolsulfonic acid or a formalin condensate of sulfonated bisphenol S.

[0417] Above - COOM 2 Examples of compounds having the formula include polycarboxylic acid polymers.

[0418] As the polycarboxylic acid polymer, for example, a polymer synthesized by a conventionally known radical polymerization method using acrylic acid, methacrylic acid, maleic acid, or the like as a monomer, or a commercially available product can be used.

[0419] Examples of methods for producing polycarboxylic acid polymers include adding a radical polymerization initiator to an aqueous solution of the above-mentioned monomer and / or its salt and reacting the mixture at 30 to 150°C for 2 to 5 hours. At this time, an alcohol such as methanol, ethanol, or isopropyl alcohol, or an aqueous solvent such as acetone may be added to the aqueous solution of the above-mentioned monomer and / or its salt. Examples of radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; redox-based polymerization initiators such as combinations of persulfates and sodium bisulfite; hydrogen peroxide; and water-soluble azo-based polymerization initiators. These radical polymerization initiators may be used alone or in combination. Furthermore, during radical polymerization, a chain transfer agent (e.g., octyl thioglycolate) may be added to adjust the degree of polymerization.

[0420] In addition to the above-mentioned monomers, copolymerizable monomers can be used in radical polymerization. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, acrylamide, acrylates, and methacrylates. Preferred acrylates and methacrylates have a hydrocarbon group having 1 to 3 carbon atoms, which may have a substituent such as a hydroxyl group. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, and propyl methacrylate. These copolymerizable monomers may be used alone or in combination.

[0421] The carboxyl group in the polycarboxylic acid polymer may be free or may be neutralized with an alkali metal, an amine compound, etc. Examples of the alkali metal include sodium, potassium, and lithium, and examples of the amine compound include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0422] The weight average molecular weight of the polycarboxylic acid polymer is preferably from 1,000 to 20,000, more preferably from 3,000 to 15,000, from the viewpoint of improving the water repellency of the resulting textile product.

[0423] As the polycarboxylic acid polymer, commercially available products such as "Neocrystal 770" (trade name, manufactured by Nicca Chemical Co., Ltd.) and "Ceropol PC-300" (trade name, manufactured by Sanyo Chemical Industries, Ltd.) can be used.

[0424] Above -OP(O)(OX 1 )(OX 2 ) includes, for example, phosphate ester compounds represented by the following general formula: [ka] [where, X 1 or X 2 is the same as above, and X 3 represents an alkyl group having 1 to 22 carbon atoms.]

[0425] As the phosphate ester compound, phosphate monoesters, diesters and triesters, in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, and mixtures thereof can be used.

[0426] From the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use lauryl phosphate and decyl phosphate.

[0427] As the phosphate ester compound, for example, commercially available products such as "Phosphanol ML-200" (trade name, manufactured by Toho Chemical Industry Co., Ltd.) can be used.

[0428] The pretreatment liquid containing one or more compounds having the specific functional group may be, for example, an aqueous solution of the compounds described above. The pretreatment liquid may also contain an acid, an alkali, a surfactant, a chelating agent, etc.

[0429] Methods for treating textile materials with the pretreatment solution include, for example, padding, immersion, spraying, and coating. Examples of padding include methods using padding devices, such as those described on pages 396-397 of "Textile Dyeing and Processing Dictionary" (published by Nikkan Kogyo Shimbun, 1963) and pages 256-260 of "Color Dyeing Chemistry III" (published by Jikkyo Publishing Co., Ltd., 1975). Examples of coating include methods using coating machines, such as those described on pages 473-477 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). Examples of immersion include methods using batch dyeing machines, such as those described on pages 196-247 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). These machines include jet dyeing machines, air jet dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, and cheese dyeing machines. Examples of spray treatments include air spraying, which sprays the treatment liquid in a mist form using compressed air, and methods using hydraulic atomization air spraying. The treatment conditions, such as the concentration of the treatment liquid and the heat treatment after application, can be appropriately adjusted taking into account various conditions, such as the purpose and performance. Furthermore, if the pretreatment liquid contains water, it is preferable to dry the pretreatment liquid after application to the fiber material to remove the water. The drying method is not particularly limited, and can be either a dry heat method or a wet heat method. The drying temperature is also not particularly limited, and can be, for example, drying at room temperature to 200°C for 10 seconds to several days. If necessary, heat treatment at a temperature of 100 to 180°C for 10 seconds to 5 minutes may be performed after drying.

[0430] When the textile material is to be dyed, the treatment with the pretreatment liquid may be carried out before dyeing or in the same bath as the dyeing. However, when reduction soaping is carried out, there is a risk that the compound having the above-mentioned specific functional group (e.g., a phenolic polymer compound) adsorbed during the process may fall off, so it is preferable to carry out the treatment after reduction soaping after dyeing.

[0431] The treatment temperature in the immersion treatment can be set to 60 to 130° C. The treatment time can be set to 5 to 60 minutes.

[0432] In the functional group introduction step using a pretreatment liquid, the amount of the compound having the specific functional group attached is preferably 1.0 to 7.0 parts by weight per 100 parts by weight of the textile material. Within this range, durable water repellency and texture can both be achieved at high levels.

[0433] The pH of the pretreatment liquid is preferably adjusted to 3 to 5. The pH can be adjusted using a pH adjuster such as acetic acid or malic acid.

[0434] The pretreatment solution may contain a salt in order to effectively adsorb the compound having the specific functional group onto the fiber material by the salting-out effect. Examples of salts that can be used include sodium chloride. Examples of suitable ammonium carbonate include sodium carbonate, sodium carbonate, ammonium sulfate, and sodium sulfate.

[0435] In the functional group introduction step using a pretreatment liquid, it is preferable to remove the compound having the specific functional group that has been treated in excess. An example of a removal method is washing with water. By performing sufficient removal, it is possible to prevent the development of water repellency in the subsequent water repellent treatment from being hindered, and in addition, the feel of the resulting textile product is improved. Furthermore, it is preferable to thoroughly dry the resulting functional group-containing fiber before contacting it with a hydrocarbon-based water repellent.

[0436] (ii) An example of a fiber in which the specific functional group is directly introduced into the material that constitutes the fiber is cationic dyeable polyester (CD-PET).

[0437] From the viewpoint of improving the water repellency of the resulting textile product, the functional group-containing fiber preferably has a surface zeta potential of −100 to −0.1 mV, more preferably −50 to −1 mV. The zeta potential of the fiber surface can be measured, for example, using a zeta potential / particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0438] The pulp base material can be treated by an internal treatment method in which a repellent is added to pulp (e.g., pulp slurry) before papermaking, or an external treatment method in which a repellent is applied to pulp (e.g., pulp product) after papermaking. Examples of internal treatment methods include mixing and immersion, and may include a step of adding a repellent to pulp slurry and stirring and mixing. Examples of external treatment methods include spraying and application, and specific examples include pond-type two-roll size presses, gate-roll type, and rod-metering size presses. The treatment may be an external treatment or an internal treatment. For example, when the pulp base material is paper, the repellent may be coated on the paper, or the solution may be attached or sprayed on the paper, or the repellent may be mixed with the pulp slurry before papermaking.

[0439] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims. [Example]

[0440] Examples of the present disclosure will be specifically described below, but the present disclosure is not limited to these examples.

[0441] <Test Method> The test procedure is as follows. [Molecular weight distribution] Average molecular weight: The average molecular weight of the copolymer was determined by GPC (gel permeation chromatography) (in terms of polystyrene). For gel permeation chromatography, an HLC-8420GPC EcoSEC Elite-WS (manufactured by Tosoh) was used. Two TSKgel SuperMultiporeHZ-M columns were connected together. An RI detector was used. Standard polystyrene (SRM706a NIST) was used as the standard material. The analytical sample was prepared by dissolving the copolymer in tetrahydrofuran to prepare a 0.1 wt% solution and passing it through a 0.5 μm filter. When measuring the average molecular weight, the column was maintained at 40°C, tetrahydrofuran was used as the eluent, and 10 μL of the analytical sample was injected at a flow rate of 0.35 mL / min.

[0442] [Tackiness] A solution containing the polymer was dried at 50-60°C for 2 hours, or a solution containing the polymer was extracted with alcohol, and placed on an 80mm diameter metal sample stage and heated at 40°C for 3 minutes, after which it was evaluated using a 50mm diameter probe. The tackiness was measured as the average of three measurements, or if there was variation in the measured values, five measurements were taken, the upper and lower limits were discarded, and the remaining values ​​were averaged. Machine name: RHESCA Tack Tester TAC-II type Test conditions: Constant Load (1) Immersion Speed ​​120 mm / min. (2) Test Speed: 600 mm / min. (3) Preload 500gf (4) Press Time 10 seconds (5) Distance 5mm The larger the measurement result, the greater the adhesiveness.

[0443] [Water repellency] The water repellency of the treated test fabric was evaluated according to the spray method of JIS-L-1092 (AATCC-22). Water repellency was evaluated according to the following criteria. The higher the score, the better the water repellency. Depending on the condition, intermediate scores (95, 85, 75, 65, 55) were assigned. 100 No wetting or water droplets were observed on the surface. 90 The surface did not wet, but small water droplets were observed to adhere. Wetting was observed on small individual water droplets on the surface. 70 Half of the surface showed wetting, with small individual wettings observed penetrating the fabric. 50 Wetting was observed over the entire surface. 0 Wetting was observed on the entire front and back surfaces.

[0444] [Light oil repellency] The test cloth was treated with an oil blend of oleic acid and PEG at a ratio of 1:9, and the oil repellency was evaluated using the following four-point scale. Depending on the condition, an intermediate value (B+, B-, C+, C-) was assigned. A: The droplets are clear (not wet) and round. B: The edges and bottom of the droplets are slightly dark and rounded. C: Some droplets have soaked into the fabric. D: The droplet is completely saturated.

[0445] [Chalk mark resistance] Each test cloth was placed on a flat surface, and the surface of the test cloth was lightly scratched with a fingernail, and the chalk-like scratch marks left by the fingernail were visually evaluated. ◎○: The trajectory is almost invisible ○: The trajectory is barely visible ○△: The trail appears faint △: The trajectory is visible △×: The trail appears slightly dark

[0446] Si-based monomer (A) Silaplane TM-0701T manufactured by JNC Corporation shown below was used as the Si-based monomer (A). JPEG0007817613000038.jpg3384

[0447] Si-based monomer (B) [Preparation of Monomer] (Synthesis of Intermediate 1) A four-neck flask was equipped with a thermometer, a dropping funnel, and a nitrogen line, and the flask was immersed in an ice bath. Next, 14.74 g of 1,1,1,3,3-pentamethyldisiloxane (as a siloxane compound), 0.04 g of tris(pentafluorophenyl)borane, and 30 mL of toluene were added to the flask and stirred. After creating a nitrogen atmosphere in the flask, 5.1 mL of (3-chloropropyl)diethoxy(methyl)silane (as a silane compound) and 10 mL of toluene were added to the dropping funnel, and this solution was slowly added to the flask. After the addition was complete, the ice bath was removed and stirring was continued 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. After stirring, the alumina mixture was filtered through a 0.45 μm filter to obtain a solution. The resulting solution was evaporated to dryness using a rotary evaporator, yielding Intermediate 1 as a transparent liquid. Intermediate 1 was characterized by 1H-NMR and GC. (Synthesis of Si-based monomer (B)) A four-neck flask was equipped with a thermometer, a dropping funnel, and a nitrogen line, and immersed in an ice bath. 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 then added to the flask to obtain a mixture. After creating a nitrogen atmosphere, the flask 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 was dried over sodium sulfate, and the resulting mixture was filtered to obtain the Si-based monomer (B) as a clear liquid. The Si-based monomer (B) was characterized by 1H-NMR and GC. TIFF0007817613000039.tif71140

[0448] Si-based monomer (C) In accordance with WO2020 / 142474, the Si-based monomer (C) shown below was obtained. TIFF0007817613000040.tif3787

[0449] Si-based monomer (D) In accordance with JP 2019-89715 A, the following Si-based monomer (D) was obtained. TIFF0007817613000041.tif54108

[0450] Si-based monomer (E) [Preparation of Monomer] (Synthesis of Intermediate 2) The same procedure as in (Synthesis of Intermediate 1) was carried out, except that (3-chloropropyl)trimethoxysilane was used as the silane compound. (Synthesis of Si-based monomer (E)) The same procedure as in (Synthesis of Si-based monomer (B)) was carried out using intermediate 2, and Si-based monomer (E) was obtained as a transparent liquid. TIFF0007817613000042.tif84126

[0451] Si-based monomer (F) [Preparation of Monomer] (Synthesis of Intermediate 3) The same procedure as in (Synthesis of Intermediate 1) was carried out, except that 1,1,1,3,5,5,5-heptamethyltrisiloxane was used as the siloxane compound and (3-chloropropyl)trimethoxysilane was used as the silane compound. (Synthesis of Si-based monomer (F)) The same procedure as in (Synthesis of Si-based monomer (B)) was carried out, and intermediate 3 was used to obtain Si-based monomer (F) as a transparent liquid. TIFF0007817613000043.tif82118

[0452] Si-based monomer (G) The Si-based monomer (G) shown below was obtained in accordance with WO2020 / 142388. TIFF0007817613000044.tif47104

[0453] Si-based monomer (H) The Si-based monomer (H) shown below was obtained in accordance with WO2020 / 142441. TIFF0007817613000045.tif4898

[0454] [Preparation of raw materials] (Example of production of silicone polymer-containing aqueous dispersion) Manufacturing Example 1 A 500 ml plastic container was charged with 15 g of a water-soluble glycol solvent as an organic solvent, 100 g of pure water and 100 g of Si-based monomer (A) as liquid media, and 4 g of sorbitan fatty acid ester, 4 g of cationic emulsifier, and 3 g of polyoxyethylene alkyl ether as surfactants, and the mixture was heated to 80°C, stirred at 2000 rpm for 1 minute with a homomixer, and then emulsified and dispersed with ultrasound for 15 minutes. Next, this mixture was transferred to a 500 ml four-neck separable flask, and after purging with nitrogen, 0.1 g of lauryl mercaptan was added as a chain transfer agent. Furthermore, 0.3 g of an azo-group-containing water-soluble initiator was added as a polymerization initiator, and the mixture was heated to 60°C and reacted for 4 hours to obtain an aqueous dispersion of a silicone polymer (water-repellent resin). This dispersion was further diluted with pure water to prepare an aqueous dispersion containing a silicone polymer with a nonvolatile content of 30% (more specifically, an aqueous dispersion containing a silicone polymer, a surfactant, and a liquid medium).

[0455] Manufacturing Examples 2 to 8 An aqueous dispersion containing a silicone polymer, a surfactant, and a liquid medium was prepared in the same manner as in Production Example 1, except that the formulation was changed according to Table 1-1.

[0456] Manufacturing Example 9 A 500 ml plastic container was charged with 15 g of a water-soluble glycol solvent as an organic solvent, 100 g of pure water as a liquid medium, 75 g of Si-based monomer (A), 25 g of stearyl acrylate as a long-chain aliphatic hydrocarbon group-containing (meth)acrylate, and 4 g of sorbitan fatty acid ester, 4 g of a cationic emulsifier, and 3 g of polyoxyethylene alkyl ether as surfactants, and the mixture was heated to 80°C, stirred at 2000 rpm for 1 minute with a homomixer, and then emulsified and dispersed with ultrasound for 15 minutes. Next, this mixture was transferred to a 500 ml four-neck separable flask, and after purging with nitrogen, 0.1 g of lauryl mercaptan was added as a chain transfer agent. Furthermore, 0.3 g of an azo-group-containing water-soluble initiator was added as a polymerization initiator, and the mixture was heated to 60°C and reacted for 4 hours to obtain an aqueous dispersion of a silicone-acrylic polymer (water-repellent resin). This dispersion was further diluted with pure water to prepare an aqueous dispersion containing a silicone-acrylic polymer with a nonvolatile content of 30% (more specifically, an aqueous dispersion containing a silicone-acrylic polymer, a surfactant, and a liquid medium).

[0457] Manufacturing Examples 10, 11, 16-22 Aqueous dispersions containing a silicone-acrylic polymer, a surfactant, and a liquid medium were prepared in the same manner as in Production Example 1, except that the formulation was changed according to Tables 1-1 and 1-2.

[0458] Manufacturing Example 12 A 500 ml plastic container was charged with 15 g of a water-soluble glycol solvent as an organic solvent, 100 g of pure water as a liquid medium, 30 g of Si-based monomer (A), 56 g of stearyl acrylate as a long-chain aliphatic hydrocarbon group-containing (meth)acrylate, and 4 g of sorbitan fatty acid ester, 4 g of a cationic emulsifier, and 3 g of polyoxyethylene alkyl ether as surfactants, and the mixture was heated to 80°C, stirred at 2000 rpm for 1 minute with a homomixer, and then emulsified and dispersed with ultrasound for 15 minutes. This mixture was then transferred to a 500 ml autoclave, and after purging with nitrogen, 0.1 g of lauryl mercaptan and 14 g of vinyl chloride were added as a chain transfer agent. 0.3 g of an azo-containing water-soluble initiator was then added as a polymerization initiator, and the mixture was heated to 60°C and reacted for 4 hours to obtain an aqueous dispersion of a silicone-acrylic polymer. This dispersion was then diluted with pure water to prepare an aqueous dispersion with a non-volatile concentration of 30%.

[0459] Manufacturing Examples 13-15 An aqueous dispersion containing a silicone-acrylic polymer, a surfactant, and a liquid medium was prepared in the same manner as in Production Example 12, except that the formulation was changed according to Table 1-2.

[0460] Comparative Manufacturing Examples 1-2 Comparative aqueous dispersions were prepared in the same manner as in Production Example 1, except that the formulation was changed according to Table 1-2.

[0461] The aqueous dispersion of the silicone polymer or silicone-acrylic polymer (water-repellent resin) was centrifuged at 14,000 rpm for 1 hour, after which the supernatant was discarded, isopropyl alcohol was added, and the mixture was centrifuged at 14,000 rpm for an additional 30 minutes to separate the polymer. The average molecular weight and tackiness of the separated polymer were evaluated as described above. The results are shown in Tables 1-1 and 1-2.

[0462] [Table 1-1] The numbers in the table are the amount of ingredients (g).

[0463] [Table 1-2] The numbers in the table are the amount of ingredients (g).

[0464] Example 1 The aqueous dispersion with a nonvolatile content of 30% prepared in Production Example 1 was diluted with tap water to prepare a treatment solution with a nonvolatile content of 0.9%. Polyester fabric, nylon fabric, and polyester / spandex fabric were immersed in this treatment solution and then squeezed with a mangle. The treated fabrics were passed through a pin tenter at 170°C for 1 minute, dried, and cured. The treated test fabrics were evaluated for water repellency, light oil repellency, and chalk mark resistance as described above. The evaluation results are shown in Table 2.

[0465] Examples 2 to 22 A treatment solution with a non-volatile content of 0.9% was prepared in the same manner as in Example 1, except that the formulation was changed according to Table 2. Fabric was treated with this treatment solution in the same manner as in Example 1, and the water repellency, light oil repellency, and chalk mark resistance were evaluated. The results are shown in Table 2.

[0466] Comparative Examples 1-2 A treatment solution with a non-volatile content of 0.9% was prepared in the same manner as in Example 1, except that the formulation was changed according to Table 2. Fabric was treated with this treatment solution in the same manner as in Example 1, and the water repellency, light oil repellency, and chalk mark resistance were evaluated. The results are shown in Table 2.

[0467] [Table 2] [Industrial Applicability]

[0468] The polymers of the present disclosure have low tack and can be used to impart water and oil repellency to a variety of products (e.g., paper, textiles, etc.).

Claims

1. A water repellent for fibers, comprising a polymer containing a repeating unit derived from a monomer (1) represented by the following formula (1-1) or formula (1-2), and having a tackiness of 800 gf or less and a weight average molecular weight of 300,000 or less: R ａ -X-CY ３－α Z α (1-1) R ａ -X-NY ２－β Z β (1-2) [In each formula: R ａ is an acryloyl group or a methacryloyl group, X is a single bond or a divalent group; Each Y is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, α is an integer from 1 to 3, β is an integer of 1 or 2, Each Z is independently -Z １ -SiZ ２ ３－ｍ Z ３ ｍ and Z １ is a single bond or a divalent group, Z ２ are each independently a hydrocarbon group having 1 to 10 carbon atoms, m is an integer from 1 to 3, Z ３ are each independently -(O-SiZ ３１ ２ ) ｐ - (CH ２ ) ｑ -Z ３２ -SiZ ３３ ３ and Z ３１ are each independently a hydrocarbon group having 1 to 10 carbon atoms or —OSiZ ３１１ ３ and Z ３１１ are each independently a hydrocarbon group having 1 to 10 carbon atoms or —OSiZ ３１１１ ３ and Z ３１１１ are each independently a hydrocarbon group having 1 to 10 carbon atoms, Z ３２ is O or CH ２ and Z ３３ are each independently a hydrocarbon group having 1 to 10 carbon atoms or —OSiZ ３３１ ３ and Z ３３１ are each independently a hydrocarbon group having 1 to 10 carbon atoms, p is an integer from 0 to 196; and q is an integer from 0 to 10.

2. The water repellent for fibers according to claim 1, having a tackiness of 600 gf or less.

3. The water repellent for fibers according to claim 1, having a tackiness of 300 gf or less.

4. X is X １ and X ２ is a divalent group consisting of one or more members selected from the group consisting of X １ represents a direct bond, —O—, —C(═O)—, —C(═NR′)—, —S—, —S(═O) ２ a group consisting of one or more selected from the group consisting of -, -NR'-, and -C(OR')R'- (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms); X ２ The water repellent for fibers according to claim 1, wherein is a direct bond or a hydrocarbon group having 1 to 22 carbon atoms which may have a substituent.

5. 2. The water repellent for fibers according to claim 1, wherein X is a direct bond or a hydrocarbon group having 1 to 22 carbon atoms which may have a substituent.

6. Z １ Is Z １１ and Z １２ is a divalent group consisting of one or more members selected from the group consisting of Z １１ represents a direct bond, —O—, —C(═O)—, —C(═NR″)—, —S—, —S(═O) ２ a group consisting of one or more selected from the group consisting of -, -NR"-, and -C(OR")R"- (wherein R" is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms); Z １２ The water repellent for fibers according to claim 1, wherein is a direct bond or a hydrocarbon group having 1 to 22 carbon atoms which may have a substituent.

7. Z １ The water repellent for fibers according to claim 1, wherein is a direct bond or a hydrocarbon group having 1 to 22 carbon atoms which may have a substituent.

8. R is an acryloyl group or a methacryloyl group. ａ is expressed by the following formula: CH 2 =CHC(=O)-O- CH 2 =CCH 3 C(=O)-O- CH 2 =CHC(=O)-NR'-, or CH 2 =CCH 3 C(=O)-NR'- (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms).

2. The water repellent for fibers according to claim 1, which is a derivative of an acryloyl group or a derivative of a methacryloyl group selected from the group consisting of:

9. A water repellent for fibers as described in claim 1, wherein the polymer further contains a repeating unit derived from a hydrophobic monomer (2) having a hydrocarbon group having 2 to 40 carbon atoms.

10. The hydrophobic monomer (2) is represented by the following formula: CH ２ =C(-R ｂ )-C(=O)-R ｃ -(R ｄ ) ｋ (2) [In the formula, R ｂ is a hydrogen atom, a monovalent organic group, or a halogen atom, R ｃ represents a direct bond, a divalent to tetravalent hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -S-, -C(=O)-, -S(=O) ２ - and -NR Ｃ１ - (R Ｃ１ is a divalent to tetravalent group consisting of at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 4 carbon atoms, k is 1 to 3; R ｄ is a hydrocarbon group having 2 to 40 carbon atoms. The water repellent for fibers according to claim 9, wherein the monomer is represented by the formula:

11. 10. The water repellent for fibers according to claim 9, wherein the amount of repeating units derived from the hydrophobic monomer (2) is 20% by weight or more based on the weight of the polymer.

12. 12. The water repellent for fibers according to claim 11, wherein the amount of repeating units derived from the monomer (1) is 0.5% by weight or more based on the polymer.

13. A water repellent for fibers as described in claim 1, wherein the polymer is non-fluorine-based.

14. X is a direct bond or an alkylene group having 1 to 5 carbon atoms, 2. The water repellent for fibers according to claim 1, wherein each Y is independently a hydrogen atom or an alkyl chain having 1 to 3 carbon atoms.

15. α is 1, β is 1, Each Z is independently -Z １ -SiZ ２ ３－ｍ Z ３ ｍ and Z １ is a single bond or -(CH ２ ) ｓ - and s is an integer from 1 to 3; Z ２ are each independently an alkyl group having 1 to 3 carbon atoms, m is an integer from 1 to 3, Z ３ are each independently -(O-SiZ ３１ ２ ) ｐ - (CH ２ ) ｑ -Z ３２ -SiZ ３３ ３ and Each p is independently 0 or 1; Each q is independently 0 or 1; Z ３１ are each independently an alkyl group having 1 to 3 carbon atoms, Z ３２ is —O— or —CH ２ - and Z ３３ are each independently an alkyl group having 1 to 3 carbon atoms or —OSiZ ３３１ ３ and Z ３３１ are each independently an alkyl group having 1 to 3 carbon atoms, The water repellent for fibers according to claim 1, having a tackiness of 300 gf or less.

16. X is a direct bond or an alkylene group having 1 to 5 carbon atoms, Each Y is independently a hydrogen atom or an alkyl chain having 1 to 3 carbon atoms; α is 1, β is 1, Each Z is independently -Z １ -SiZ ２ ３－ｍ Z ３ ｍ and Z １ is a single bond or -(CH ２ ) ｓ - and s is an integer from 1 to 3; Z ２ are each independently an alkyl group having 1 to 3 carbon atoms, m is an integer from 1 to 3, Z ３ are each independently -(O-SiZ ３１ ２ ) ｐ - (CH ２ ) ｑ -Z ３２ -SiZ ３３ ３ and Each p is independently 0 or 1; Each q is independently 0 or 1; Z ３１ are each independently an alkyl group having 1 to 3 carbon atoms, Z ３２ is —O— or —CH ２ - and Z ３３ are each independently an alkyl group having 1 to 3 carbon atoms or —OSiZ ３３１ ３ and Z ３３１ are each independently an alkyl group having 1 to 3 carbon atoms, The water repellent for fibers according to claim 1, having a tackiness of 300 gf or less.

17. A water-repellent textile product comprising a textile substrate to which the polymer contained in the water repellent agent for textiles according to any one of claims 1 to 16 is attached.

18. The fiber substrate -SO ３ M １ (In the formula, M １ represents a monovalent cation), -COOM ２ (In the formula, M ２ represents a monovalent cation), and -O-P(O)(OX １ ) (OX ２ ) (wherein, X １ and X ２ and each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms.

19. A method for producing a water-repellent textile product, comprising applying the water repellent agent according to claim 1 to a textile substrate.

20. Before applying the water repellent agent to the fibrous substrate, -SO ３ M １ (In the formula, M １ represents a monovalent cation), -COOM ２ (In the formula, M ２ represents a monovalent cation), and -O-P(O)(OX １ ) (OX ２ ) (wherein, X １ and X ２ and each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms.

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