Dispensing agent

Abstract

To provide a novel repelling agent or a novel polymer suitable for repellent applications.SOLUTION: The present invention provides a repelling agent including a polymer selected from polymers (I)-(III), which are defined as follows. (I) A polymer having a repeat unit (1) that is represented by the formula -[CH2C(-Q1)C(=O)R1]- (where each symbol in this formula is as defined in the description), and a repeat unit (2) that is represented by the formula -[CH2C(-Q2)C(=O)NHR2OH]- (where each symbol in this formula is as defined in the description). (II) A polymer that has an alternating arrangement (A) comprising the repeat unit (1) and the repeat unit (2). (III) A polymer that has an alternating arrangement (E) comprising a repeat unit (3) that is represented by the formula -[CH2C(-Q3)C(=O)OH]- (where each symbol in this formula is as defined in the description), and a repeat unit (4) that is represented by the formula -[CH2C(-Q4)C(=O)OR41OC(=O)NHR42]- (where each symbol in this formula is as defined in the description).SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a repellent.

Background Art

[0002] Non-Patent Document 1 discloses a method for synthesizing an alternating copolymer consisting only of acrylamide units from one type of monomer by using a divinyl monomer.

Prior Art Documents

Non-Patent Documents

[0003]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Non-Patent Document 1 does not describe or suggest the application of the polymer to the use as a repellent. Further, Non-Patent Document 1 only discloses an alternating copolymer consisting only of acrylamide units and does not describe or suggest a polymer having acrylate units. An object of the present disclosure is to provide a novel repellent or a novel polymer that can be used for a repellent use.

Means for Solving the Problems

[0005] The present disclosure includes the following aspects: [Item 1] A repellent containing a polymer selected from polymers (I) to (III) defined below. (I) The following formula: -[CH2C(-Q 1 )C(=O)R 1 - [In the formula, Q 1 is a hydrogen atom, a monovalent organic group or a halogen atom, R 1 is -NH(R 11 ) or -N(R 11 )2, where R 11 is, independently at each occurrence, a monovalent organic group having a hydrocarbon group with 4 to 40 carbon atoms.] The repeating unit (1) represented by, and The following formula: -[CH2C(-Q 2 )C(=O)NHR 2 OH]- [In the formula, Q 2 is a hydrogen atom, a monovalent organic group or a halogen atom, R 2 is an alkylene group having 1 to 10 carbon atoms.] A polymer having the repeating unit (2) represented by. (II) A polymer having an alternating arrangement (A) composed of the repeating unit (1) and the repeating unit (2). (III) The following formula: -[CH2C(-Q 3 )C(=O)OH]- [In the formula, Q 3 is a hydrogen atom, a monovalent organic group or a halogen atom.] The repeating unit (3) represented by and The following formula: -[CH2C(-Q 4 )C(=O)OR 41 OC(=O)NHR 42 - [In the formula, Q 4 is a hydrogen atom, a monovalent organic group or a halogen atom, R 41 is an alkylene group having 1 to 10 carbon atoms, R 42 is a monovalent organic group having a hydrocarbon group with 4 to 40 carbon atoms.] The repeating unit (4) represented by and A polymer having an alternating arrangement (E) composed of. [Item 2] The water - repellent agent according to Item 1, comprising the polymer (II). [Item 3] The water-repellent agent according to Item 1 or 2, comprising polymer (III). [Item 4] The amount of the repeating unit (1) is 15% by weight or more in the polymer, and the amount of the repeating unit (2) is 15% by weight or more in the polymer; or The amount of the alternating sequence (A) and / or the alternating sequence (E) is 30% by weight or more in the polymer. The water-repellent agent according to any one of Items 1 to 3. [Item 5] The water-repellent agent according to any one of Items 1 to 4, comprising a liquid medium that is water, an organic solvent, or a mixture of water and an organic solvent. [Item 6] The water-repellent agent according to any one of Items 1 to 5, which is for fibers or paper. [Item 7] A substrate to which the polymer in the water-repellent agent according to any one of Items 1 to 6 is adhered. [Item 8] A method for manufacturing a treated substrate, comprising applying the water-repellent agent according to any one of Items 1 to 6 to a substrate. [Item 9] A polymer selected from polymer (II) and polymer (III) defined below. (II) The following formula: -[CH2C(-Q 1 )C(=O)R 1 - [In the formula, Q 1 is a hydrogen atom, a monovalent organic group, or a halogen atom, R 1 is -NH(R 11 ) or -N(R 11 )2, where R 11 is, in each occurrence, independently, a monovalent organic group having a hydrocarbon group with 4 to 40 carbon atoms.] The repeating unit (1) represented by and the following formula: -[CH2C(-Q 2 )C(=O)NHR 2 OH]- [In the formula, Q 2is a hydrogen atom, a monovalent organic group or a halogen atom, R 2 is an alkylene group having 1 to 10 carbon atoms.] and the repeating unit (2) represented by to form an alternating arrangement (A), wherein the repeating unit (1) contains two or more R 11 A polymer. (III) The following formula: -[CH2C(-Q 3 )C(=O)OH]- [In the formula, Q 3 is a hydrogen atom, a monovalent organic group or a halogen atom.] and the repeating unit (3) represented by The following formula: -[CH2C(-Q 4 )C(=O)OR 41 OC(=O)NHR 42 - [In the formula, Q 4 is a hydrogen atom, a monovalent organic group or a halogen atom, R 41 is an alkylene group having 1 to 10 carbon atoms, R 42 is a monovalent organic group having a hydrocarbon group having 4 to 40 carbon atoms.] and the repeating unit (4) represented by A polymer having an alternating arrangement (E). [Item 10] The polymer according to Item 9, which is Polymer (II). [Item 11] The polymer according to Item 9, which is Polymer (III). [Item 12] The polymer according to any one of Items 9 to 11, wherein the amount of the alternating arrangement (A) and / or the alternating arrangement (E) is 30% by weight or more in the polymer. [Item 13] A method for producing Polymer (II), comprising: The following formula: CH2=C(-Q 1 )C(=O)-X A-OR 2 NHC(=O)C(-Q 2 )=CH2 [wherein, Q 1 is a hydrogen atom, a monovalent organic group or a halogen atom, X A is a group removable by aminolysis, R 2 is an alkylene group having 1 to 10 carbon atoms, Q 2 is a hydrogen atom, a monovalent organic group or a halogen atom.) A step of cyclopolymerizing the divinyl monomer (A) represented by to obtain a precursor (A); and said precursor (A) and the following formula: NH2(R 11 ) or NH(R 11 )2 [wherein, R 11 is, independently at each occurrence, a monovalent organic group having a hydrocarbon group having 4 to 40 carbon atoms.) A step of reacting with an amine compound represented by, said polymer (II) being the following formula: -[CH2C(-Q 1 )C(=O)R 1 - [wherein, Q 1 is a hydrogen atom, a monovalent organic group or a halogen atom, R 1 is -NH(R 11 ) or -N(R 11 )2, where R 11 is, independently at each occurrence, a monovalent organic group having a hydrocarbon group having 4 to 40 carbon atoms.) The repeating unit (1) represented by and the following formula: -[CH2C(-Q 2 )C(=O)NHR 2 OH]- [wherein, Q 2 is a hydrogen atom, a monovalent organic group or a halogen atom, R 2 is an alkylene group having 1 to 10 carbon atoms. The repeating unit (2) represented by and The repeating unit (1) contains two or more Rs 11 A method for producing polymer (II). [Item 14] A method for producing polymer (III), comprising: The following formula: CH2=C(-Q 3 )C(=O)O-X E -O-R 41 -OC(=O)C(-Q 4 )=CH2 [In the formula, Q 3 is a hydrogen atom, a monovalent organic group or a halogen atom, X E is a group removable by acid decomposition, Q 4 is a hydrogen atom, a monovalent organic group or a halogen atom, R 41 is an alkylene group having 1 to 10 carbon atoms. Cyclopolymerizing the divinyl monomer (E) represented by to obtain a precursor (E1); Removing X from the precursor (E1) by acid decomposing the precursor (E1) to obtain a precursor (E2); and E Reacting the precursor (E2) with The following formula: The following formula: R 42 -NCO [In the formula, R 42 is a monovalent organic group having a hydrocarbon group having 4 to 40 carbon atoms. And an isocyanate compound represented by The polymer (III) is The following formula: -[CH2C(-Q 3 )C(=O)OH]- [In the formula, Q 3is a hydrogen atom, a monovalent organic group, or a halogen atom. and the repeating unit (3) represented by the following formula: -[CH2C(-Q 4 )C(=O)OR 41 OC(=O)NHR 42 - [wherein, Q 4 is a hydrogen atom, a monovalent organic group, or a halogen atom, R 41 is an alkylene group having 1 to 10 carbon atoms, R 42 is a monovalent organic group having a hydrocarbon group having 4 to 40 carbon atoms. and the repeating unit (4) represented by A method for producing a polymer (III) having an alternating arrangement (E).

Advantages of the Invention

[0006] According to the present disclosure, a novel polymerizable composition or a novel polymer that can be used for a polymerizable composition use is provided.

Modes for Carrying Out the Invention

[0007] <Definition of Terms> As used herein, the term "n-valent group" means a group having n bonds, that is, a group that forms n bonds. Further, the "n-valent organic group" means an n-valent group containing carbon. Such an organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. The derivative of the hydrocarbon group means a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the terminal or in the molecular chain of the hydrocarbon group.

[0008] As used herein, the term "hydrocarbon group" means a group containing carbon and hydrogen, and means a group obtained by removing a hydrogen atom from a hydrocarbon. Such a hydrocarbon group is not particularly limited, but C 1-20Hydrocarbon groups, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups, can be mentioned. The above "aliphatic hydrocarbon group" may be linear, branched or cyclic, and may be saturated or unsaturated. Further, the hydrocarbon group may contain one or more ring structures. The hydrocarbon group may be substituted with one or more substituents.

[0009] In this specification, regardless of whether the expression "independently at each occurrence", "independently of each other", "independently" or a similar expression is explicitly described, when a term (symbol) that can appear multiple times in a chemical structure is defined, the definition is applied independently for each occurrence, except when there is a description to the contrary.

[0010] <Water and oil repellent agent> The water and oil repellent agent in the present disclosure imparts water and oil repellency to a substrate (for example, a fiber substrate, a paper substrate, etc.) and can function as at least one selected from the group consisting of a water repellent agent, an oil repellent agent, an oil resistant agent, and a water resistant agent. In the polymer in the water and oil repellent agent, the coexistence of a hydrogen bonding site such as an amide group and a hydrocarbon group can improve the water and oil repellency. In the polymer in the present disclosure, the alternate arrangement of hydrogen bonding sites such as amide groups makes it easier to form a phase separation structure than a random arrangement, and the water and oil repellency of the alternating copolymer can be improved. Further, in the polymer in the present disclosure, the alternate arrangement of hydrogen bonding sites such as amide groups suppresses molecular motion, and the decrease in water and oil repellency due to temperature can be suppressed.

[0011] The water and oil repellent agent in the present disclosure may not have any 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 and oil repellent agent in the present disclosure can impart water and oil repellency to the substrate even without containing these fluorine compounds.

[0012] 〔Polymer〕 The repellent in the present disclosure includes a polymer selected from polymers (I) to (III) described below. The polymer may correspond to only any one of polymers (I) to (III), or may correspond to any two or all of them. Note that polymer (II) may also correspond to polymer (I) at the same time.

[0013] The polymer in the present disclosure may not have any selected from the group consisting of a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, and a fluorine atom. Even if the polymer in the present disclosure does not contain these fluorine-containing groups, it can impart liquid repellency to the substrate.

[0014] [Polymer (I)] Polymer (I) has repeating unit (1) and repeating unit (2). Polymer (I) may be a random polymer having repeating unit (1) and repeating unit (2) randomly. Regarding repeating unit (1) and repeating unit (2), the description in [Polymer (II)] is incorporated herein by reference.

[0015] [Polymer (II)] Polymer (II) has an alternating arrangement (A) consisting of repeating unit (1) and repeating unit (2).

[0016] (Alternating arrangement (A)) Alternating arrangement (A) consists of repeating unit (1) and repeating unit (2). That is, alternating arrangement (A) is an arrangement formed by the alternating bonding of repeating unit (1) and repeating unit (2), and the following formula: -[CH2C(-Q 1 )C(=O)R 1 -[CH2C(-Q 2 )C(=O)NHR 2 OH]- [In the formula, Q 1 is a hydrogen atom, a monovalent organic group or a halogen atom, and R1 is -NH(R 11 ) or -N(R 11 )2, where R 11 is, independently at each occurrence, a monovalent organic group having a hydrocarbon group with 4 to 40 carbon atoms, Q 2 is a hydrogen atom, a monovalent organic group or a halogen atom, R 2 is an alkylene group with 1 to 10 carbon atoms.] is represented by

[0017] (Repeating unit (1)) The repeating unit (1) is the following formula: -[CH2C(-Q[[ID=2,8]] 1 )C(=O)R 1 - [wherein, Q 1 is a hydrogen atom, a monovalent organic group or a halogen atom, R 1 is -NH(R 11 ) or -N(R 11 )2, where R 11 is, independently at each occurrence, a monovalent organic group having a hydrocarbon group with 4 to 40 carbon atoms.] is represented by

[0018] Q 1 is a hydrogen atom, a monovalent organic group or a halogen atom. Examples of the monovalent organic group include a cyano group, an aliphatic hydrocarbon group with 1 to 6 carbon atoms (e.g., an alkyl group, an alkenyl group, etc.), and an aromatic group with 5 to 12 carbon atoms, etc. Examples of the halogen atom include fluorine, chlorine, bromine, iodine, etc. Q 1 may be a hydrogen atom, a halogen atom, a methyl group, a cyano group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, for example, a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, a cyano group, preferably a hydrogen atom, a methyl group, a chlorine atom, particularly a hydrogen atom or a methyl group.

[0019] R 1 is -NH(R11 ) or -N(R 11 )2. For example, R 1 may be a combination of -NH(R 11 ) and -N(R 11 )2.

[0020] R 11 is a monovalent organic group having a hydrocarbon group with 4 to 40 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, particularly preferably a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be cyclic, linear, or branched, preferably linear. The number of carbon atoms of the hydrocarbon group may be 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, preferably 8 or more, more preferably 12 or more. The number of carbon atoms of the hydrocarbon group may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, more preferably 25 or less.

[0021] R 11 may contain other groups in addition to the hydrocarbon group with 4 to 40 carbon atoms. Examples of other groups include ether oxygen and amino groups (e.g., secondary or tertiary amino groups). For example, R 11 may form a branched structure from the nitrogen atom.

[0022] R 11 may be combined in two or more (e.g., two, three, four) kinds. By combining two or more R 11 , it may be possible to impart a plurality of properties well. Examples of combinations include combinations of a hydrocarbon group with 12 or more carbon atoms (e.g., a chain alkyl group) as R 11 and a cyclic hydrocarbon-containing group (e.g., a cycloalkyl-containing group, a phenyl group-containing group, etc.). A hydrocarbon group with 12 or more carbon atoms can impart high liquid repellency, and a cyclic hydrocarbon-containing group can impart high heat resistance. When two or more R 11 are used in combination, each R 11 is R 11It may be present in an amount of 10 mol% or more, 20 mol% or more, or 30 mol% or more with respect to the total.

[0023] R 11 The carbon atom ratio of may be 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%, preferably 60% or more. R 11 The carbon atom ratio of may be 100% or less, 95% or less, 90% or less, 85% or less, 80% or less. Here, R 11 The carbon atom ratio of refers to the 11 molar ratio of the amount of carbon atoms in R to the total amount of heteroatoms (atoms other than carbon atoms and hydrogen atoms) in R. R 11 11 When the carbon atom ratio of R is at or above the above lower limit, liquid repellency can be favorably exhibited.

[0024] R 11 The molecular weight of may be 50 or more, 100 or more, 150 or more, 200 or more, 250 or more, or 300 or more. R 11 The molecular weight of may be 750 or less, 600 or less, 500 or less, 400 or less, 300 or less, 200 or less, or 100 or less.

[0025] (Repeating unit (2)) The repeating unit (2) is the following formula: -[CH2C(-Q 2 )C(=O)NHR 2 OH]- [In the formula, Q 2 is a hydrogen atom, a monovalent organic group, or a halogen atom, and R 2 is an alkylene group having 1 to 10 carbon atoms. ] is represented by.

[0026] Q 2is a hydrogen atom, a monovalent organic group or a halogen atom. Examples of the monovalent organic group include a cyano group, an aliphatic hydrocarbon group having 1 to 6 carbon atoms (e.g., an alkyl group, an alkenyl group, etc.), and an aromatic group having 5 to 12 carbon atoms, etc. Examples of the halogen atom include fluorine, chlorine, bromine, iodine, etc. Q 2 may be a hydrogen atom, a halogen atom, a methyl group, a cyano group, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, for example, a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, or a cyano group, preferably a hydrogen atom, a methyl group, a chlorine atom, particularly a hydrogen atom or a methyl group.

[0027] R 2 is an alkylene group having 1 to 10 carbon atoms. The alkylene group may be cyclic, linear or branched, preferably linear. The number of carbon atoms of the alkylene group may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more. The number of carbon atoms of the alkylene group may be 10 or less, 8 or less, 6 or less, 4 or less, 2 or less, for example, 5 or less.

[0028] [Polymer (III)] Polymer (III) has an alternating sequence (E) composed of repeating unit (3) and repeating unit (4).

[0029] (Alternating sequence (E)) The alternating sequence (E) is composed of repeating unit (3) and repeating unit (4). That is, the alternating sequence (E) is a sequence formed by alternately bonding repeating unit (3) and repeating unit (4), and the following formula: -[CH2C(-Q 3 )C(=O)OH]-[CH2C(-Q 4 )C(=O)OR 41 OC(=O)NHR 42 - [In the formula, Q 3 is a hydrogen atom, a monovalent organic group or a halogen atom, Q 4 is a hydrogen atom, a monovalent organic group or a halogen atom, R 41is an alkylene group having 1 to 10 carbon atoms, R 42 is a monovalent organic group having a hydrocarbon group with 4 to 40 carbon atoms.] It is represented by. Each symbol will be described in detail below.

[0030] (Repeating unit (3)) The repeating unit (3) is represented by the following formula: -[CH2C(-Q 3 )C(=O)OH]- [In the formula, Q 3 is a hydrogen atom, a monovalent organic group or a halogen atom.] It is represented by.

[0031] Q 3 is a hydrogen atom, a monovalent organic group or a halogen atom. Examples of the monovalent organic group include a cyano group, an aliphatic hydrocarbon group having 1 to 6 carbon atoms (e.g., an alkyl group, an alkenyl group, etc.), and an aromatic group having 5 to 12 carbon atoms, etc. Examples of the halogen atom include fluorine, chlorine, bromine, iodine, etc. Q 3 may be a hydrogen atom, a halogen atom, a methyl group, a cyano group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, for example, a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, a cyano group, preferably a hydrogen atom, a methyl group, a chlorine atom, particularly a hydrogen atom or a methyl group, and more preferably a methyl group.

[0032] (Repeating unit (4)) The repeating unit (4) is represented by the following formula: -[CH2C(-Q 4 )C(=O)OR 41 OC(=O)NHR 42 - [In the formula, Q 4 is a hydrogen atom, a monovalent organic group or a halogen atom, R 41 is an alkylene group having 1 to 10 carbon atoms, R 42is a monovalent organic group having a hydrocarbon group with 4 to 40 carbon atoms. It is represented by

[0033] Q 4 is a hydrogen atom, a monovalent organic group, or a halogen atom. Examples of the monovalent organic group include a cyano group, an aliphatic hydrocarbon group having 1 to 6 carbon atoms (e.g., an alkyl group, an alkenyl group, etc.), and an aromatic group having 5 to 12 carbon atoms, etc. Examples of the halogen atom include fluorine, chlorine, bromine, iodine, etc. Q 4 may be a hydrogen atom, a halogen atom, a methyl group, a cyano group, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, for example, a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, or a cyano group, preferably a hydrogen atom, a methyl group, a chlorine atom, particularly a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0034] R 41 is an alkylene group having 1 to 10 carbon atoms. The alkylene group may be cyclic, linear, or branched, and is preferably linear. The number of carbon atoms of the alkylene group may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more. The number of carbon atoms of the alkylene group may be 10 or less, 8 or less, 6 or less, 4 or less, 2 or less, for example, 5 or less.

[0035] R 42 is a monovalent organic group having a hydrocarbon group with 4 to 40 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, and particularly preferably a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be cyclic, linear, or branched, and is preferably linear. The number of carbon atoms of the hydrocarbon group may be 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, preferably 8 or more, and more preferably 12 or more. The number of carbon atoms of the hydrocarbon group may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, and more preferably 25 or less.

[0036] R42 may contain other groups in addition to the hydrocarbon group having 4 to 40 carbon atoms. Examples of the other groups include ether oxygen and amino groups (for example, secondary or tertiary amino groups). For example, R 42 may form a branched structure from a nitrogen atom. R 42 As one kind may be used, or two or more kinds may be used in combination.

[0037] R 42 Two or more kinds (for example, two kinds, three kinds, four kinds) may be combined. By combining two or more kinds of R 42 , it may be possible to impart a plurality of properties favorably. Examples of the combination include a combination of an R 42 that is a hydrocarbon group having 12 or more carbon atoms (for example, a chain alkyl group) and a cyclic hydrocarbon-containing group (for example, a cycloalkyl-containing group, a phenyl group-containing group, etc.). A hydrocarbon group having 12 or more carbon atoms can impart high liquid repellency, and a cyclic hydrocarbon-containing group can impart high heat resistance. When two or more kinds of R 42 are used in combination, each R 42 may be present in an amount of 10 mol% or more, 20 mol% or more, or 30 mol% or more based on the total of R 42 .

[0038] R 42 The carbon atom ratio of may be 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%, preferably 60% or more. The carbon atom ratio of R 42 may be 100% or less, 95% or less, 90% or less, 85% or less, 80% or less. Here, the carbon atom ratio of R 42 means the molar ratio of the amount of carbon atoms in R 42 to the total amount of heteroatoms (atoms other than carbon atoms and hydrogen atoms) in R 42 . When the carbon atom ratio of R 42 is at or above the above lower limit, liquid repellency can be favorably exhibited.

[0039] R 42The molecular weight may be 50 or more, 100 or more, 150 or more, 200 or more, 250 or more, or 300 or more. R 42 The molecular weight may be 750 or less, 600 or less, 500 or less, 400 or less, 300 or less, 200 or less, or 100 or less.

[0040] [Other repeating units] The polymer (polymers (I) to (III)) may have other repeating units other than the repeating units (1) to (4) described above. Examples of other repeating units are repeating units derived from hydrocarbon monomers, crosslinkable monomers, halogenated olefin monomers, and / or other monomers.

[0041] (Hydrocarbon monomer) The polymer has the following formula: CH2=C(-Q)-C(=O)-X-R n [In the formula, Q is a hydrogen atom, a monovalent organic group, or a halogen atom, X is at least one selected from the group consisting of a direct bond, -O-, -C(=O)-, -S(=O)2-, -NR’-, -C(OR’)R’-, and -C(OR’)(-)2 (wherein R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms).) X 1 and X is a hydrocarbon group having 1 to 40 carbon atoms 2 and is a 1+n-valent group selected from the group consisting of one or more selected from the group consisting of, R is an aliphatic hydrocarbon group having 6 to 40 carbon atoms, n is 1 to 3.] The polymer may have a repeating unit derived from a hydrocarbon monomer represented by

[0042] Q is a hydrogen atom, a monovalent organic group, or a halogen atom. Examples of the monovalent organic group include a cyano group, an aliphatic hydrocarbon group having 1 to 6 carbon atoms (e.g., an alkyl group, an alkenyl group, etc.), and an aromatic group having 5 to 12 carbon atoms, etc. Examples of the halogen atom include fluorine, chlorine, bromine, iodine, etc. Q may be a hydrogen atom, a halogen atom, a methyl group, a cyano group, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, for example, a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, or a cyano group, preferably a hydrogen atom, a methyl group, a chlorine atom, particularly a hydrogen atom or a methyl group.

[0043] X is composed of at least one selected from the group consisting of a direct bond, -O-, -C(=O)-, -S(=O)2-, -NR’-, -C(OR’)R’-, and -C(OR’)(-)2 (wherein R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms). 1 and a hydrocarbon group having 1 to 40 carbon atoms 2 and is a 1 + n-valent group composed of one or more selected from the group consisting of. n may be 1 to 3, 2 to 3, 1 to 2, 1, 2, or 3.

[0044] X is represented by the following formula: -X 1 -, or, -X 1 -X 2 -X 1 - [wherein X 1 is, independently at each occurrence, -O-, -NR’-, -C(=O)-NR’-, -NR’-C(=O)-, or -NR’-C(=O)-NR’- (R’ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), and X 2 is a hydrocarbon group having 1 to 40 carbon atoms.] may be a group represented by.

[0045] R is a monovalent aliphatic hydrocarbon group having 6 to 40 carbon atoms. R may be cyclic, branched, or linear, preferably branched or linear, and more preferably linear. R is preferably a saturated aliphatic hydrocarbon group (alkyl group).

[0046] The number of carbon atoms of R may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, preferably 10 or more, and more preferably 12 or more. The number of carbon atoms of R may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, and more preferably 25 or less.

[0047] From the viewpoint of liquid repellency, the hydrocarbon monomer may include a hydrocarbon monomer containing an amide group, a urea group, or a urethane group in X. The hydrocarbon monomer may be a combination of a hydrocarbon monomer having an amide group, a urea group, or a urethane group and a hydrocarbon monomer having no amide group, urea group, or urethane group.

[0048] The hydrocarbon monomer may be only a non-cyclic hydrocarbon group-containing monomer, but may also include a cyclic hydrocarbon group-containing monomer. The cyclic hydrocarbon group-containing monomer is a monomer having a cyclic hydrocarbon group, and may be a monomer having one ethylenically unsaturated double bond and a cyclic hydrocarbon group.

[0049] The cyclic hydrocarbon group-containing monomer 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.

[0050] 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 cyclic group, preferably a bridged cyclic group. The cyclic hydrocarbon group may have a chain group (for example, a linear or branched hydrocarbon group).

[0051] The number of carbon atoms in the cyclic hydrocarbon group may be 4 or more, 6 or more, or 8 or more, and may be 30 or less, 26 or less, 22 or less, 18 or less, or 14 or less.

[0052] Specific examples of the cyclic hydrocarbon group include cyclohexyl group, t-butylcyclohexyl group, adamantyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, bornyl group, isobornyl group, norbornyl group, dicyclopentanyl group, dicyclopentenyl group, benzyl group, phenyl group, naphthyl group, 2-t-butylphenyl group, residues obtained by removing one or more hydrogen atoms from these groups (e.g., cyclohexylene group, adamantylene group, phenylene group, naphthylene group, etc.), and groups which are substituents of these.

[0053] Specific examples of the monomer containing a cyclic hydrocarbon group 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, compounds in which these acrylates are substituted with acrylamide, etc. These may be used alone or in combination of two or more.

[0054] Specific examples of the hydrocarbon monomer are as follows. The compounds of the following chemical formulas are acrylic compounds in which the α-position is a hydrogen atom, but the α-position may be another Q, for example, methacrylic compounds in which the α-position is a methyl group and α-chloroacrylic compounds in which the α-position is a chlorine atom, etc. CH2=CHC(=O)OC p H 2p NHC(=O)C q H 2q+1 CH2=CHC(=O)OC2H4NHC(=O)C17 H 35 CH2=CHC(=O)OC2H4NHC(=O)C 15 H 31 CH2=CHC(=O)OC2H4NHC(=O)C 17 H 35 and CH2=CHC(=O)OC2H4NHC(=O)C 15 H 31 and its mixture CH2=CHC(=O)OC q H 2q+1 CH2=CHC(=O)OC 18 H 37 CH2=CHC(=O)OC 16 H 33 CH2=CHC(=O)OC2H4OC(=O)NHC q H 2q+1 CH2=CHC(=O)OC2H4NHC(=O)OC q H 2q+1 CH2=CHC(=O)OC2H4NHC(=O)NHC q H 2q+1 CH2=CHC(=O)OC4H8OC(=O)NHC q H 2q+1 CH2=CHC(=O)OC2H4OC(=O)NHC 18 H 37 CH2=CHC(=O)OC2H4NHC(=O)OC 18 H 37 CH2=CHC(=O)NHC p H 2p OC(=O)NHC q H 2q+1 CH2=CHC(=O)OC p H 2p-1 (NH(C=O)C q H q+1 )(NH(C=O)C q H q+1 ) CH2=CHC(=O)OC p H 2p-1 (NH(C=O)C 17 H 35 )(NH(C=O)C 17 H 35 ) CH2=CHC(=O)OC p H 2p-1 (O(C=O)NHC q H q+1 )(CH2O(C=O)NHC q H q+1 ) CH2=CHC(=O)OCH2CH(O(C=O)NHC 18 H 37 )(CH2O(C=O)NHC 18 H 37 ) [In the above formula, p is 1 to 40 (for example, 1 to 6), and q is 6 to 40 (for example, 12 to 30).]

[0055] (Halogenated olefin monomer) The polymer may have repeating units derived from a halogenated olefin monomer. The halogenated olefin monomer preferably does not have a fluorine atom. The halogenated olefin monomer is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. The halogenated olefin monomer 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 specific examples of the halogenated olefin monomer are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene iodide. Vinyl chloride is preferred because the water repellency (particularly the durability of water repellency) is high. The presence of repeating units derived from the halogenated olefin monomer increases the washing durability provided by the polymer.

[0056] (Crosslinkable monomer) The polymer may have repeating units derived from a crosslinkable monomer. The crosslinkable monomer is a monomer capable of imparting crosslinkability to the polymer and may have at least two selected from the group consisting of a reactive group and an olefinic carbon-carbon double bond. The crosslinkable monomer may be a compound having at least two ethylenically unsaturated double bonds or a compound having at least one ethylenically unsaturated double bond and at least one reactive group.

[0057] The crosslinkable monomer preferably has a (meth)acryl 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.

[0058] Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, a carboxyl group, a carbonyl group, an isocyanate group, and the like.

[0059] Specific examples of the crosslinkable monomer include diacetone (meth)acrylamide, N-methylol (meth)acrylamide, hydroxyethyl (meth)acrylamide, glycidyl (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 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, neopentyl glycol di(meth)acrylate, and the like. These may be used alone or in combination of two or more. These may be used alone or in combination of two or more.

[0060] (Other monomers) The polymer may contain repeating units derived from monomers other than the monomers described above.

[0061] Specific examples of other monomers include, for example, acrylonitrile, alkoxypolyalkylene glycol (meth)acrylate, dimethylaminoethyl (meth)acrylate, organosiloxane-containing (meth)acrylate, vinyl acetate, vinyl alkyl ether, etc. Other monomers are not limited to these examples. These may be used alone or in combination of two or more.

[0062] [Composition of polymer, etc.] The amount of the repeating unit (1) in the polymer may be 5% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight or more, 35% by weight or more, 45% by weight or more, 55% by weight or more, or 65% by weight or more in the polymer, preferably 15% by weight or more. The amount of the repeating unit (1) in the polymer may be 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less.

[0063] The amount of the repeating unit (2) in the polymer may be 5% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight or more, 35% by weight or more, 45% by weight or more, 55% by weight or more, or 65% by weight or more in the polymer, preferably 15% by weight or more. The amount of the repeating unit (2) in the polymer may be 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less.

[0064] The molar ratio of the repeating unit (1) to the repeating unit (2) in the polymer (repeating unit (1) / repeating unit (2)) may be 0.5 or more, 0.75 or more, 0.95 or more. The molar ratio of the repeating unit (1) to the repeating unit (2) in the polymer (repeating unit (1) / repeating unit (2)) may be 2 or less, 1.5 or less, 1.25 or less, 1.05 or less.

[0065] The amount of the alternating sequence (A) possessed by the polymer may be 10% by weight or more, 30% by weight or more, 50% by weight or more, 70% by weight or more, 90% by weight or more in the polymer, and preferably 30% by weight or more. The amount of the alternating sequence (A) possessed by the polymer may be 100% by weight or less, 80% by weight or less, 60% by weight or less, 40% by weight or less, or 20% by weight or less in the polymer.

[0066] The amount of the repeating unit (3) possessed by the polymer may be 5% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight or more, 35% by weight or more, 45% by weight or more, 55% by weight or more, or 65% by weight or more in the polymer. The amount of the repeating unit (3) possessed by the polymer may be 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less in the polymer.

[0067] The amount of the repeating unit (4) possessed by the polymer may be 5% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight or more, 35% by weight or more, 45% by weight or more, 55% by weight or more, or 65% by weight or more in the polymer. The amount of the repeating unit (4) possessed by the polymer may be 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less in the polymer.

[0068] The molar ratio of the repeating unit (3) to the repeating unit (4) (repeating unit (3) / repeating unit (4)) possessed by the polymer may be 0.5 or more, 0.75 or more, 0.95 or more. The molar ratio of the repeating unit (1) to the repeating unit (2) (repeating unit (3) / repeating unit (4)) possessed by the polymer may be 2 or less, 1.5 or less, 1.25 or less, 1.05 or less.

[0069] The amount of the alternating sequence (E) in the polymer may be 10% by weight or more, 30% by weight or more, 50% by weight or more, 70% by weight or more, 90% by weight or more, and is preferably 30% by weight or more. The amount of the alternating sequence (E) in the polymer may be 100% by weight or less, 80% by weight or less, 60% by weight or less, 40% by weight or less, or 20% by weight or less.

[0070] The amount of other repeating units in the polymer may be 10% by weight or more, 30% by weight or more, 50% by weight or more. The amount of other repeating units in the polymer may be 60% by weight or less, 40% by weight or less, or 20% by weight or less.

[0071] The number average molecular weight (Mn) of the polymer may be 500 or more, 1000 or more, 2500 or more, 5000 or more, 10000 or more, 25000 or more, or 50000 or more, and 5000 or more is preferable. The number average molecular weight (Mn) of the polymer may be 1000000 or less, 500000 or less, 250000 or less, 100000 or less, 50000 or less, 25000 or less, or 10000 or less, and 100000 or less is preferable.

[0072] The Mw / Mn of the polymer may be 1 or more, 1.2 or more, 1.5 or more, or 1.7 or more. The Mw / Mn of the polymer may be 5 or less, 4.5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, 2 or less, or 1.5 or less.

[0073] The melting point of the polymer may be 30°C or more, 40°C or more, 60°C or more, 80°C or more, 100°C or more, or 120°C or more, and is preferably 50°C or more, for example 100°C or more. The melting point of the polymer may be 250°C or less, 200°C or less, 150°C or less, 100°C or less, or 50°C or less. The polymer may not have a melting point.

[0074] The glass transition point of the polymer may be 30 °C or higher, 40 °C or higher, 60 °C or higher, 80 °C or higher, 100 °C or higher, or 120 °C or higher, preferably 30 °C or higher, for example 50 °C or higher or 75 °C or higher. The glass transition point of the polymer may be 250 °C or lower, 200 °C or lower, 150 °C or lower, 100 °C or lower, or 50 °C or lower.

[0075] [Method for producing polymer (I)] The method for producing polymer (I) is not limited, and may be produced, for example, by copolymerizing a monomer that induces repeating unit (1) and a monomer that induces repeating unit (2).

[0076] Examples of the monomer that induces repeating unit (1) are represented by the following formula: CH2=C(-Q 1 )C(=O)R 1 [In the formula, Q 1 is a hydrogen atom, a monovalent organic group, or a halogen atom, R 1 is -NH(R 11 ) or -N(R 11 )2, where R 11 is, in each occurrence independently, a monovalent organic group having a hydrocarbon group with 4 to 40 carbon atoms.] is a compound represented by. Details of Q 1 and R 1 are as described above.

[0077] Examples of the monomer that induces repeating unit (2) are represented by the following formula: CH2=C(-Q 2 )C(=O)NHR 2 OH [In the formula, Q 2 is a hydrogen atom, a monovalent organic group, or a halogen atom, R 2 is an alkylene group having 1 to 10 carbon atoms.] is a compound represented by. Details of Q 2 and R 2 are as described above.

[0078] The copolymerization method is not limited, and known polymerization methods can be selected, and the conditions of the polymerization reaction can also be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization.

[0079] In solution polymerization, in the presence of a polymerization initiator, the monomer is dissolved in an organic solvent, and after nitrogen substitution, heating and stirring are carried out at a temperature in the range of 30 to 120 °C for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxy pivalate, diisopropyl peroxydicarbonate, etc. The polymerization initiator is used in the range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, based on 100 parts by weight of the monomer.

[0080] The organic solvent is inert to the monomer and dissolves them. For example, aprotic polar solvents (such as DMSO, DMF), esters (such as esters having 2 to 40 carbon atoms, specifically ethyl acetate, butyl acetate), ketones (such as ketones having 2 to 40 carbon atoms, specifically methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone), and alcohols (such as alcohols having 1 to 40 carbon atoms, specifically ethanol, butanol, isopropyl alcohol) may be used. 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, trichlorotrifluoroethane, etc. The organic solvent is used in the range of 10 to 3000 parts by weight, for example, 50 to 2000 parts by weight, based on 100 parts by weight of the total monomer.

[0081] In emulsion polymerization, a method is adopted in which monomers are emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, they are stirred and polymerized at a temperature in the range of 50 to 80 °C for 1 to 20 hours. As the polymerization initiator, water-soluble ones such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine-dihydrochloride, sodium peroxide, potassium persulfate, ammonium persulfate, etc., and oil-soluble ones such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, etc. are used. The polymerization initiator is used in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomers.

[0082] In order to obtain a polymer aqueous dispersion with excellent storage stability, it is desirable to polymerize the monomers after atomizing them into fine particles in water using an emulsifying device capable of imparting strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. Further, as the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and they are used in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the monomers. It is preferable to use an anionic and / or nonionic and / or cationic emulsifier. When the monomers are not completely compatible, it is preferable to add a compatibilizer that can be sufficiently compatible with these monomers, for example, a water-soluble organic solvent or a low-molecular-weight monomer. By adding the compatibilizer, it is possible to improve the emulsifying property and copolymerizability.

[0083] As the water-soluble organic solvent, the above-described organic solvents may be used. For example, acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, etc. may be mentioned, and it may be used in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight with respect to 100 parts by weight of water. Further, as the low molecular weight monomer, methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc. may be mentioned, and it may be used in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight with respect to 100 parts by weight of the total amount of the monomers.

[0084] In the polymerization, a chain transfer agent may be used. The molecular weight of the polymer can be changed according to the amount of the chain transfer agent used. Examples of the chain transfer agent are mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, thioglycerol (especially, (for example, alkyl mercaptan having 1 to 40 carbon atoms)), inorganic salts such as sodium hypophosphite, sodium bisulfite, etc. The amount of the 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 with respect to 100 parts by weight of the total amount of the monomers.

[0085] [Method for producing polymer (II)] The method for producing polymer (II) is the following formula: CH2=C(-Q 1 )C(=O)-X A -OR 2 NHC(=O)C(-Q 2 )=CH2 [wherein, Q 1 is a hydrogen atom, a monovalent organic group or a halogen atom, X A is a group removable by aminolysis, R 2 is an alkylene group having 1 or more and 10 or less carbon atoms, Q 2 is a hydrogen atom, a monovalent organic group or a halogen atom.] The step of obtaining a precursor (A) by ring-opening polymerization of a divinyl monomer (A) represented by; and said precursor (A) and the following formula: NH2(R 11 ) or NH(R 11 )2 [wherein, R 11 is, in each occurrence, independently, a monovalent organic group having a hydrocarbon group with 4 to 40 carbon atoms.] and a reaction step with an amine compound represented by.

[0086] (The step of obtaining a precursor (A) by ring-opening polymerization of a divinyl monomer (A)) In this step, a precursor (A) is obtained by ring-opening polymerization of a divinyl monomer (A). By using ring-opening polymerization, it becomes possible to obtain a polymer (II) which is an alternating copolymer.

[0087] The divinyl monomer (A) is the following formula: CH2=C(-Q 1 )C(=O)-X A -OR 2 NHC(=O)C(-Q 2 )=CH2 [wherein, Q 1 is a hydrogen atom, a monovalent organic group or a halogen atom, X A is a group removable by aminolysis, R 2 is an alkylene group having 1 to 10 carbon atoms, Q 2 is a hydrogen atom, a monovalent organic group or a halogen atom.] represented by.

[0088] Q 1 、R 2 、and Q 2 are as described in the above explanation.

[0089] X Ais a group removable by aminolysis. Here, aminolysis refers to a reaction in which an ester is cleaved by reacting with an amine. X A is -O-R A may be a group represented by -(C=O)-. Here, R A is an organic group and may be a hydrocarbon group or a derivative thereof. R A may be an aromatic group (e.g., a phenylene group (e.g., 1,2-phenylene group)), for example, an aromatic group having a substituent, and particularly an aromatic group having an electron-withdrawing group (e.g., -CF3, -CCl3, -NO2, -CN, etc.) that activates the aminolysis reaction. R A may have a molecular weight of 150 or less, or 100 or less. R A may have 10 or less, 8 or less, or 6 or less carbon atoms. R A Specific examples of R include 3-trifluoromethyl-1,2-phenylene group, 5-trifluoromethyl-1,2-phenylene group, 3,5-bis(trifluoromethyl)-1,2-phenylene group, 3-trichloromethyl-1,2-phenylene group, 5-trichloromethyl-1,2-phenylene group, 3,5-bis(trichloromethyl)-1,2-phenylene group, 4-nitro-1,2-phenylene group, and the like.

[0090] The method of ring-opening polymerization is not limited, and a known polymerization method can be selected, and the conditions of the polymerization reaction can also be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization. Details of the polymerization method are as described above.

[0091] The precursor (A) is TIFF0007716723000001.tif3457[wherein, Q 1 is a hydrogen atom, a monovalent organic group, or a halogen atom, X A is a group removable by aminolysis, R 2 is an alkylene group having 1 to 10 carbon atoms, Q 2is a hydrogen atom, a monovalent organic group, or a halogen atom. is a polymer having a repeating unit represented by the following formula.

[0092] (Step of reacting precursor (A) with an amine compound) In this step, precursor (A) is reacted with an amine compound. By this reaction, the ester in precursor (A) is cleaved by reacting with the amine, and polymer (II) is obtained.

[0093] The amine compound is represented by the following formula: NH2(R 11 ) or NH(R 11 )2 [In the formula, R 11 is, in each occurrence, independently, a monovalent organic group having a hydrocarbon group with 4 to 40 carbon atoms. is represented by the following formula.

[0094] R 11 is as described in the above explanation.

[0095] The reaction conditions of precursor (A) and the amine compound can be set as appropriate. For example, the reaction may be carried out at 20°C to 80°C for 3 hours to 48 hours.

[0096] Two or more amine compounds may be used so that polymer (II) contains two or more R 11 .

[0097] [Method for producing polymer (III)] The method for producing polymer (III) is represented by the following formula: CH2=C(-Q 3 )C(=O)O-X E -O-R 41 -OC(=O)C(-Q 4 )=CH2 [In the formula, Q 3 is a hydrogen atom, a monovalent organic group, or a halogen atom, and X Eis a group removable by acidolysis, Q 4 is a hydrogen atom, a monovalent organic group or a halogen atom, R 41 is an alkylene group having 1 to 10 carbon atoms.] A step of obtaining a precursor (E1) by cyclopolymerizing a divinyl monomer (E) represented by; Removing X from the precursor (E1) by acidolysis of the precursor (E1) to obtain a precursor (E2); and E The precursor (E2) and The following formula: R 42 -NCO [wherein R 42 is a monovalent organic group having a hydrocarbon group having 4 to 40 carbon atoms.] And reacting with an isocyanate compound represented by.

[0098] (Step of obtaining a precursor (E1) by cyclopolymerizing a divinyl monomer (E)) In this step, the divinyl monomer (E) is cyclopolymerized to obtain a precursor (A). By using cyclopolymerization, it becomes possible to obtain a polymer (III) which is an alternating copolymer.

[0099] The divinyl monomer (E) is The following formula: CH2=C(-Q 3 )C(=O)O-X E -O-R 41 -OC(=O)C(-Q 4 )=CH2 [wherein, Q 3 is a hydrogen atom, a monovalent organic group or a halogen atom, X E is a group removable by acidolysis, Q 4 is a hydrogen atom, a monovalent organic group or a halogen atom, R 41 is an alkylene group having 1 to 10 carbon atoms.] represented by. ​

[0100] Q 3 、Q 4 、and R 41 The details of Q, Q, and R are as described above.

[0101] X E is a group removable by acidolysis. X E is -CHR E - or -C(R E )2-, and may form an acetal structure. Here, R E is an organic group and may be a hydrocarbon group or a derivative thereof. R A may be an aliphatic group, for example, an aliphatic hydrocarbon group, and particularly may be an alkyl group. R E may have a molecular weight of 150 or less, or 100 or less. R E may have 8 or less, 6 or less, 4 or less, 3 or less, 2 or less carbon atoms. R E Specific examples of R include a methyl group, an ethyl group, a propyl group, etc.

[0102] The method of ring-opening polymerization is not limited, and a known polymerization method can be selected, and the conditions of the polymerization reaction can also be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization. The details of the polymerization method are as described above.

[0103] The precursor (E1) is the following formula: TIFF0007716723000002.tif2841[wherein, Q 3 is a hydrogen atom, a monovalent organic group, or a halogen atom, X E is a group removable by acidolysis, Q 4 is a hydrogen atom, a monovalent organic group, or a halogen atom, R 41 is an alkylene group having 1 to 10 carbon atoms.] and is a polymer having a repeating unit represented by

[0104] (Step of removing X from precursor (E1) to obtain precursor (E2)) E In this step, by subjecting precursor (E1) to acid decomposition, X is removed from precursor (E1) to obtain precursor (E2). E

[0105] The conditions for acid decomposition are not limited and can be set as appropriate. For example, it may be reacted at 20 °C to 80 °C for 3 hours to 48 hours.

[0106] Precursor (E2) is the following formula: TIFF0007716723000003.tif3141[wherein Q 3 is a hydrogen atom, a monovalent organic group or a halogen atom, Q 4 is a hydrogen atom, a monovalent organic group or a halogen atom, R 41 is an alkylene group having 1 to 10 carbon atoms.] and is a polymer having a repeating unit represented by

[0107] (Step of reacting precursor (E2) with an isocyanate compound) In this step, precursor (E2) is reacted with an isocyanate compound. By this reaction, the hydroxy group in precursor (E2) reacts with the isocyanate group of the isocyanate compound to obtain polymer (III).

[0108] The isocyanate compound is the following formula: R 42 -NCO [wherein R 42 is a monovalent organic group having a hydrocarbon group with 4 to 40 carbon atoms.] and is represented by

[0109] R 42 For details of which, the description in the above polymer can be incorporated by reference.

[0110] ​​The reaction conditions between the precursor (E2) and the isocyanate compound can be set as appropriate. For example, the reaction may be carried out at 20°C to 80°C for 3 hours to 48 hours.

[0111] The isocyanate compound may use two or more amine compounds so that the polymer (III) contains two or more Rs. 42 It may be used in combination with two or more amine compounds so as to contain the same.

[0112] [Amount of polymer] The amount of the polymer 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 in the release agent. The amount of the polymer 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 in the release agent.

[0113] [Liquid medium] The release agent in the present disclosure may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The release agent may be a dispersion or a solution.

[0114] Examples of the organic solvent include esters (for example, esters having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), ketones (for example, ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone), alcohols (for example, alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (for example, toluene and xylene), and petroleum solvents (for example, alkanes having 5 to 10 carbon atoms, specifically, naphtha, 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 (for example, polyhydric alcohols such as alcohols and glycol solvents, ether forms of polyhydric alcohols (for example, monoether forms), etc.). These may be used alone or in combination of two or more.

[0115] [Amount of liquid medium] The amount of the liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more with respect to 1 part by weight of the polymer. The amount of the liquid medium may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less with respect to 1 part by weight of the polymer.

[0116] The amount of water may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more with respect to 1 part by weight of the polymer. The amount of water may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less with respect to 1 part by weight of the polymer.

[0117] 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, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more with respect to 1 part by weight of the polymer. The amount of the organic solvent may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less with respect to 1 part by weight of the polymer.

[0118] 〔Surfactant〕 The release agent may contain a surfactant. The surfactant may contain one or more surfactants selected from nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0119] [Nonionic surfactant] Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides.

[0120] Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0121] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are C1-C50 (especially C10-C30) alcohols having 1 to 6 (especially 2 to 5) valences (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0122] Examples of ester ethers are compounds obtained by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are C1-C50 (especially C3-C30) alcohols having 1 to 6 (especially 2 to 5) valences (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0123] Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or a dialkanolamine. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 1 to 3 amino groups and 1 to 5 hydroxyl groups and having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0124] The polyhydric alcohol may be a C10-C30 alcohol having 2 to 5 valences. The amine oxide may be an oxide of an amine (secondary amine or preferably tertiary amine) (e.g., having 5 to 50 carbon atoms).

[0125] The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms of 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.

[0126] 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 portion and the polyalkylene glycol portion is polyoxyethylene (POE) or polyoxypropylene (POP) or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Also, the nonionic surfactant preferably has a structure that does not contain an aromatic group due to environmental problems (biodegradability, environmental hormones, etc.).

[0127] The nonionic surfactant has the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [wherein, R 1 is an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms or an acyl group, R 2 Each of them is independently the same or different and is an alkylene group having 3 or more carbon atoms (for example, 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 of 2 or more. q is 0 or a number of 1 or more.] It may be a compound represented by.

[0128] R 1 is preferably 8 to 20, particularly 10 to 18 carbon atoms. R 1 Preferred specific examples of include lauryl group, tridecyl group, oleyl group. R 2 Examples of are propylene group, 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) in the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, a styrene chain, etc. Among them, an oxypropylene chain is preferred.

[0129] Specific examples of the nonionic surfactant include condensation products with ethylene oxide and hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkane (C 12 -C 16 ) thiol, sorbitan monofatty acid (C7-C 19 ) or alkyl (C 12 -C 18 ) amine, etc.

[0130] 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-lipophilic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. Examples of the compound having an HLB of less than 15 are sorbitan fatty acid esters. Examples of the compound having an HLB of 15 or more are polyoxyethylene alkyl ethers. 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 a single kind or a mixture of two or more kinds.

[0131] [Cationic surfactant] The cationic surfactant is preferably a compound having no amide group.

[0132] The cationic surfactant may be an amine salt, a quaternary ammonium salt, or an oxyethylene-added ammonium salt. Specific examples of the cationic surfactant include, but are not particularly limited to, amine salt type surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, etc., quaternary ammonium salt type surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, etc.

[0133] Preferred examples of the cationic surfactant are R 21 -N + (-R 22 )(-R 23 )(-R 24 )X - [wherein, R 21 , R22 and R 23 and R 24 are hydrocarbon groups having 1 to 40 carbon atoms, X is an anionic group.] is a compound of. R 21 and R 22 and R 23 and -R 24 Specific examples of are alkyl groups (for example, methyl group, butyl group, stearyl group, palmitoyl group). Specific examples of X are halogen (for example, chlorine), acid (for example, hydrochloric acid, acetic acid). The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl having 4 to 40 carbon atoms).

[0134] The cationic surfactant is preferably an ammonium salt. The cationic surfactant has the formula: R 1 p -N + R 2 q X - [wherein R 1 is a linear and / or branched aliphatic (saturated and / or unsaturated) group having 12 or more carbon atoms (for example, C 12 ~C 50 ), R 2 is H or an alkyl group having 1 to 4 carbon atoms, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, especially 3) to 50) (CH3 and C2H5 are particularly preferred), X is a halogen atom (for example,), a fatty acid base having 1 to 4 carbon atoms, p is 1 or 2, q is 2 or 3, and p + q = 4.] may be an ammonium salt represented by. The carbon number of R 1 may be 12 to 50, for example, 12 to 30.

[0135] 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.

[0136] [Anionic surfactant] Examples of anionic surfactants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonated fatty acid salts, N-acyl amino acid type surfactants, phosphoric acid mono- or diester type surfactants, and sulfosuccinic acid esters.

[0137] [Amphoteric surfactant] Examples of amphoteric surfactants include alanines, imidazolinium betaines, amide betaines, betaine acetate, etc. Specifically, lauryl betaine, stearyl betaine, lauryl carboxymethylhydroxyethylimidazolinium betaine, lauryldimethylaminoacetate betaine, fatty acid amide propyldimethylaminoacetate betaine, etc. can be mentioned.

[0138] The surfactant may be one or a combination of two or more of nonionic surfactants, cationic surfactants, and amphoteric surfactants.

[0139] [Amount of surfactant] The amount of the surfactant may be 0.01 part by weight or more, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more with respect to 100 parts by weight of the polymer. The amount of the surfactant may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less with respect to 100 parts by weight of the polymer. may be.

[0140] [Silicone] The water repellent agent in the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, in addition to good water repellency, it can also have good texture and durability.

[0141] As the silicone, known silicones can be used. Examples of the silicone include polydimethylsiloxane, modified silicones (amino-modified, epoxy-modified silicone, carboxy-modified silicone, methylhydrogen silicone, etc.). The silicone may be a silicone wax having a wax-like property. These may be used alone or in combination of two or more.

[0142] The weight average molecular weight of the silicone may be 1000 or more, 10000 or more, or 50000 or more. The weight average molecular weight of the silicone may be 500000 or less, 2500000 or less, 100000 or less, or 50000 or less.

[0143] [Amount of silicone] The amount of silicone may be 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more with respect to 100 parts by weight of the polymer. The amount of silicone may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less with respect to 100 parts by weight of the polymer.

[0144] 〔Wax〕 The repellent in the present disclosure may contain wax. By containing wax, liquid repellency can be favorably imparted to the substrate.

[0145] Examples of wax include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (such as polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, silicone wax, animal and plant wax, and mineral wax. Paraffin wax is preferred. Specific examples of the compounds constituting the wax are normal alkanes (for example, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane), normal alkenes (for example, 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane). The carbon number of the compounds 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, 300 to 1000. These may be used alone or in combination of two or more.

[0146] 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.

[0147] [Amount of wax] The amount of wax may be 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more with respect to 100 parts by weight of the polymer. The amount of wax may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less with respect to 100 parts by weight of the polymer.

[0148] [Organic acid] The release agent may contain an organic acid. Known organic acids can be used. Preferred examples of the organic acid include carboxylic acids, sulfonic acids, sulfinic acids, etc., and carboxylic acids are particularly preferred. Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., and formic acid or acetic acid is particularly preferred. In the present disclosure, one kind of organic acid may be used, or two or more kinds may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0149] [Amount of organic acid] The amount of the organic acid may be 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more with respect to 100 parts by weight of the polymer. The amount of the organic acid may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less with respect to 100 parts by weight of the polymer. The amount of the organic acid may be adjusted so that the pH of the release agent is 3 to 10, for example, 5 to 9, particularly 6 to 8. The release agent may be acidic (pH 7 or less, for example, 6 or less).

[0150] 〔Curing agent〕 The release agent may contain a curing agent (an active hydrogen-reactive compound or an active hydrogen-containing compound).

[0151] The curing agent (crosslinking agent) in the release agent can cure the polymer well. 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 group of the polymer. Examples of the active hydrogen-reactive compound are isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of the active hydrogen-containing compound are hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0152] The hardener may contain an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound acts as a crosslinking agent. Examples of the polyisocyanate compound include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (for example, it may be a blocked polyisocyanate compound). The blocked isocyanate compound is a compound in which the isocyanate group of the isocyanate compound is masked with a blocking agent to suppress the reaction.

[0153] Examples of the aliphatic polyisocyanate include aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethyl caproate, and lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane and other aliphatic triisocyanates. These may be used alone or in combination of two or more.

[0154] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates are 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.

[0155] Examples of aromatic aliphatic polyisocyanates are aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of aromatic aliphatic polyisocyanates are 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.

[0156] Examples of aromatic polyisocyanates are aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates are 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, etc. These may be used alone or in combination of two or more.

[0157] Derivatives of polyisocyanates include, for example, various derivatives such as dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, uretoimines, isocyanurates, iminooxadiazinediones, etc. of the above-mentioned polyisocyanate compounds. These may be used alone or in combination of two or more.

[0158] 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 obtained by blocking the isocyanate groups of the polyisocyanate compound with a blocking agent. It is preferable to use the blocked polyisocyanate compound because it is relatively stable in solution and can be used in the same solution as the defoaming agent.

[0159] The blocking agent blocks free isocyanate groups. The blocked polyisocyanate compound can regenerate isocyanate groups and react easily with hydroxyl groups by heating, for example, to 100 °C or higher, for example, 130 °C or higher. Examples of the blocking agent are phenolic compounds, lactam compounds, aliphatic alcohol compounds, oxime compounds, etc. The polyisocyanate compound can be used alone or in combination of two or more.

[0160] The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound are epoxy compounds having a polyoxyalkylene group, for example, polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether, etc. The chloromethyl group-containing compound is a compound having a chloromethyl group. Examples of the chloromethyl group-containing compound are chloromethylpolystyrene, etc. The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound are (poly)acrylic acid, (poly)methacrylic acid, etc.

[0161] Specific examples of the ketone group-containing compound include (poly) diacetone acrylamide, diacetone alcohol, etc. Specific examples of the hydrazide compound include hydrazine, carbohydrazide, adipic acid hydrazide, etc. Specific examples of the melamine compound include melamine resin, methyl etherified melamine resin, etc.

[0162] [Amount of curing agent] The amount of the curing agent may be 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more with respect to 100 parts by weight of the polymer. The amount of the curing agent may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less with respect to 100 parts by weight of the polymer.

[0163] [Other components] The release agent may contain other components other than the above components. Examples of other components include polysaccharides, paper strength enhancers, flocculants, yield improvers, coagulants, binder resins, anti-slip agents, sizing agents, paper strength enhancers, fillers, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above-mentioned components, other components such as other water-repellent and / or oil-repellent agents, dispersants, hand modifiers, softeners, flame retardants, paint fixatives, anti-wrinkle agents, drying rate adjusters, crosslinking agents, film-forming aids, compatibilizers, anti-freezing agents, viscosity adjusters, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage preventers, anti-washing wrinkle agents, shape retainers, drape retainers, ironing property improvers, brighteners, whitening agents, fabric softening clay, migration inhibitors such as polyvinylpyrrolidone, polymer dispersants, soil release agents, scum dispersants, fluorescent brighteners such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Ciba Speciality Chemicals' Tinopal CBS-X), dye fixatives, anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine, stain removers, enzymes such as cellulase, amylase, protease, lipase, keratinase, etc. as fiber surface modifiers, anti-foaming agents, silk protein powder, their surface modified products or emulsion dispersions (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk solution (Kamawata), Silkgen G Soluble S (Ichimaru Pharcos)) that can impart the texture and functions of silk such as water absorption and release properties, anti-pollution agents (e.g., nonionic polymer compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by Gohou Chemical Industry Co., Ltd.), SRC-1 manufactured by Clariant Japan, etc.) can be blended. These may be used alone or in combination of two or more.

[0164] [Polysaccharides] Examples of polysaccharides include starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, and pullulan, etc. The polysaccharides may be substituted modified polysaccharides, particularly modified polysaccharides into which hydroxyl groups or cationic groups are introduced.

[0165] [Paper strength enhancer, aggregating agent, yield improver or coagulant] Examples of paper strength enhancers, flocculants, yield improvers or coagulants include styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide-based polymers, polyamine-based polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichloride and polyalkylene polyamines, dicyandiamide-formalin condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers, etc.

[0166] [Sizing agent] Examples of sizing agents include cellulose-reactive sizing agents, such as rosin-based sizing agents like rosin soap, rosin-based emulsions / dispersions, cellulose-reactive sizing agents, such as emulsions / dispersions of acid anhydrides like alkyl and alkenyl succinic anhydrides (ASA), alkenyl and alkyl ketene dimers (AKD) and multimers, and anionic, cationic and amphoteric polymers of ethylenically unsaturated monomers, such as copolymers of styrene and acrylate.

[0167] [Antistatic agent] Examples of antistatic agents include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, primary, secondary and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate esters, phosphonates, phosphate esters; amphoteric antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, alanine and its derivatives; nonionic antistatic agents such as amino alcohols and their derivatives, glycerin and its derivatives, polyethylene glycol and its derivatives, etc. Ion conductive polymers obtained by polymerizing or copolymerizing monomers having these cationic, anionic and zwitterionic ion conductive groups may also be used. These may be used alone or in combination of two or more.

[0168] Antiseptic Antiseptics can mainly be used to enhance the antiseptic power and bactericidal power and maintain the antiseptic property during long-term storage. Examples of antiseptics include isothiazolone-based organic sulfur compounds, benzisothiazolone-based organic sulfur compounds, benzoic acids, 2-bromo-2-nitro-1,3-propanediol, and the like.

[0169] Ultraviolet absorber An ultraviolet absorber is a drug having an effect of protecting against ultraviolet rays, and is a component that absorbs ultraviolet rays and converts them into infrared rays, visible light, etc. and emits them. Examples of ultraviolet absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole-based compounds, 4-t-butyl-4'-methoxybenzoylmethane, and the like.

[0170] Antibacterial agent An antibacterial agent is a component having an effect of suppressing the growth of bacteria on fibers and further suppressing the generation of unpleasant odors derived from decomposition products of microorganisms. Examples of antibacterial agents include cationic bactericides such as quaternary ammonium salts, zinc bis-(2-pyridylthio-1-oxide), polyhexamethylene biguanide hydrochloride, 8-hydroxyquinoline, polylysine, and the like.

[0171] Deodorant Examples of deodorants include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, aminocarboxylic acid-based metal complexes (zinc complex of methylglycine diacetic acid trisodium described in WO2012 / 090580), and the like.

[0172] Amount of other components The amount of each or the total amount of other components may be 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more with respect to 100 parts by weight of the polymer. The amount of each or the total amount of other components may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less with respect to 100 parts by weight of the polymer.

[0173] <Method for manufacturing a treated substrate> The method for manufacturing a product treated with a water repellent in the present disclosure includes a treatment step of treating a substrate with the water repellent described above.

[0174] "Treatment" means applying a water repellent to a substrate by dipping, spraying, coating, or the like. By the treatment, the polymer, which is the active ingredient of the water repellent, penetrates into the interior of the substrate and / or adheres to the surface of the substrate.

[0175] [Substrate] The substrate to be treated with the water repellent in the present disclosure is not limited, but is preferably a fiber product or a paper product.

[0176] Examples of the substrate of the fiber product include animal and plant natural fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber, or a mixed fiber thereof. The fiber products include woven fabrics, knitted fabrics, and non-woven fabrics, cloth in the form of clothing, and carpets, and the fibers, yarns, and intermediate fiber products (for example, sliver or roving, etc.) in the state before being made into cloth may be treated.

[0177] Examples of the base material of the paper product include paper made from bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, groundwood pulp, bleached or unbleached high-yield pulp such as mechanical pulp or thermomechanical pulp, waste paper pulp such as waste newspaper, waste magazine, corrugated cardboard waste paper or deinked waste paper, paper containers made of paper, paper molded articles, etc. Specific examples of the paper product include paper for food packaging, base paper for gypsum board, base paper for coating, medium paper, general liner and core, neutral pure white roll paper, neutral liner, rust-proof liner and metal laminated paper, kraft paper, neutral printing and writing paper, neutral base paper for coating, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, mold paper (mold container), etc.

[0178] The base material treated with the repellent of the present disclosure is not limited to fiber products or paper products, and other examples include stone, filters (e.g., electrostatic filters), dust masks, parts of fuel cells (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, coated surfaces, and plaster, etc.

[0179] [Treatment method] The water repellent of the present disclosure can be applied to a substrate by a conventionally known method as a treatment agent (especially a surface treatment agent). As a treatment method, the water repellent in the present disclosure can be dispersed and diluted in an organic solvent or water if necessary, and then adhered to the surface of the substrate and dried by a known method such as dip coating, spray coating, foam coating, etc. After drying, a fiber product with the solid component in the water repellent adhered thereto can be obtained. Further, if necessary, it may be applied together with a suitable crosslinking agent and cured. To the water repellent of the present disclosure, if necessary, further, a water and / or oil repellent, an anti-slip agent, an antistatic agent, a handle modifier, a softener, an antibacterial agent, a flame retardant, a paint fixing agent, an anti-wrinkle agent, a drying rate adjuster, a crosslinking agent, a film-forming aid, a compatibilizer, an antifreezing agent, a viscosity adjuster, an ultraviolet absorber, an antioxidant, a pH adjuster, an insect repellent, an antifoaming agent, and other various additives can also be used in combination. Examples of the various additives may be the same as those described as "other components" in the above water repellent composition. The concentration of the water repellent in the treatment agent in contact with the substrate may be appropriately changed depending on the application, but may be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0180] The water repellent can be applied to the substrate by any of the methods known for treating the substrate with a liquid. The substrate may be immersed in the water repellent, or a solution may be adhered or sprayed onto the substrate. The treated substrate is preferably dried and cured by heating in order to exhibit water repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In the present disclosure, good performance can be obtained even with low-temperature heating (for example, 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. When the fiber product is paper, it may be coated on the paper, or a solution may be adhered or sprayed onto the paper, or it may be treated by mixing with a pulp slurry before papermaking. The treatment may be an external addition treatment or an internal addition treatment. Alternatively, the water repellent may be applied to the fiber product by a cleaning method, for example, applied to the fiber product in a washing application or a dry cleaning method, etc.

[0181] [Treatment of Paper] Examples of the paper substrate include paper, containers made of paper, and molded articles made of paper (e.g., pulp moldings).

[0182] Paper can be manufactured by a conventionally known papermaking method. An internal sizing method of adding a sizing agent to the pulp slurry before papermaking or an external sizing method of applying a sizing agent to the paper after papermaking can be used.

[0183] The internal sizing method may mean a method of adding a sizing agent to the pulp slurry before papermaking. As the internal sizing method, it may include one or more of the steps of adding a sizing agent to the pulp slurry and stirring and mixing, suction-dehydrating the pulp composition prepared in the step through a reticulate body of a predetermined shape to deposit the pulp composition to form an intermediate pulp molding, and molding and drying the intermediate pulp molding with a heated mold to obtain paper, a container made of paper, or a molded article made of paper, but is not limited thereto. The treated paper may be optionally heat-treated depending on the properties of the paper after simple drying at room temperature or high temperature. The temperature of the heat treatment may be 150 °C or higher, 180 °C or higher, or 210 °C or higher, and may be 300 °C or lower, 250 °C or lower, or 200 °C or lower, and particularly may be 80 °C to 180 °C. By performing the heat treatment within such a temperature range, excellent oil resistance, water resistance, etc. can be exhibited.

[0184] The size press of the external sizing method can also be classified as follows by the coating method. One coating method is a so-called pond-type two-roll size press in which a coating liquid (size liquid) is supplied to a nip portion formed by passing paper between two rubber rolls to create a coating liquid reservoir called a pond, and the size liquid is applied to both sides of the paper by passing the paper through this coating liquid reservoir. Other coating methods are a gate roll type in which the size liquid is applied by a surface transfer type, and a rod metering size press. In the pond-type two-roll size press, the size liquid easily penetrates into the paper, and in the surface transfer type, the size liquid components tend to remain on the surface of the paper. The surface transfer type has a coating layer that tends to remain on the surface of the paper compared to the pond-type two-roll size press, and more coating layers are formed on the surface than in the pond-type two-roll size press. In the present disclosure, even when the former pond-type two-roll size press is used, performance can be imparted to the paper. The paper treated in this way can show excellent oil resistance and water resistance, etc., by undergoing a heat treatment that can optionally take a temperature range of up to 300 °C, for example up to 200 °C, particularly 80 °C to 180 °C, depending on the properties of the paper, after simple drying at room temperature or high temperature.

[0185] The present disclosure can be used in gypsum board base paper, coated base paper, medium paper, general liner and core, neutral pure white roll paper, neutral liner, rust-proof liner and metal laminated paper, kraft paper, etc. It can also be used in 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.

[0186] As the pulp raw material, bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, groundwood pulp, mechanical pulp or thermomechanical pulp, etc. Any of bleached or unbleached high-yield pulp, waste paper pulp such as newspaper waste paper, magazine waste paper, corrugated waste paper or deinked waste paper can be used. Mixtures of the above pulp raw materials and synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, polyvinyl alcohol, etc. can also be used.

[0187] The water resistance of paper can be improved by adding a sizing agent. Examples of sizing agents are cationic sizing agents, anionic sizing agents, rosin sizing agents (e.g., acidic rosin sizing agents, neutral rosin sizing agents). The amount of the sizing agent may be 0.01 to 5% by weight based on the pulp.

[0188] If necessary, for paper, as papermaking chemicals used to a normal extent, additives used in the production of paper such as starch, modified starch, carboxymethyl cellulose, paper strength enhancers such as polyamide polyamine-epichlorohydrin resin, flocculants, fixing agents, yield improvers, dyes, fluorescent dyes, slime control agents, defoamers, etc. can be used. For example, starch or modified starch may be used. If necessary, using starch, polyvinyl alcohol, dyes, coating colors, anti-slip agents, etc., a water repellent can be applied to the paper by a size press, a gate roll coater, a blade coater, a calender, etc.

[0189] In external addition, the amount of the liquid repellent compound contained in the coating layer is 0.01 to 2.0 g / m 2 、 particularly preferably 0.1 to 1.0 g / m 2 . The coating layer may be formed by a water repellent and starch and / or modified starch. The solid content of the paper water repellent in the coating layer is preferably 2 g / m 2 or less. In internal addition, it is preferable to mix the water repellent with the pulp such that the amount of the water repellent is 0.01 to 50 parts by weight or 0.01 to 30 parts by weight, for example 0.01 to 10 parts by weight, particularly 0.2 to 5.0 parts by weight, based on 100 parts by weight of the pulp forming the paper.

[0190] In external addition, by storing a treatment liquid between rolls and passing the base paper through the treatment liquid between the rolls at an arbitrary roll speed and nip pressure, using a so-called pond type two-roll size press treatment, oil resistance can also be imparted to the paper.

[0191] In the external addition treatment, the paper base material may contain additives such as sizing agents, paper strength enhancers, flocculants, retention agents or coagulants. The additives may be nonionic, cationic, anionic or amphoteric. The ionic charge density of the additives is -10,000 to 10,000 μeq / g, preferably -4,000 to 8,000 μeq / g, and more preferably -1,000 to 7,000 μeq / g. Additives (such as solid components or active ingredients) such as sizing agents, paper strength enhancers, flocculants, retention agents or coagulants can generally be used in an amount of 0.1 to 10% by weight (for example, 0.2 to 5.0% by weight) based on the pulp. In the case of a paper base material containing a cationic additive (for example, a sizing agent, a paper strength enhancer, a flocculant, a retention agent or a coagulant), the repellent is preferably anionic.

[0192] In the internal addition treatment, it is preferable to form paper from a pulp slurry having a pulp concentration of 0.5 to 5.0% by weight (for example, 2.5 to 4.0% by weight). Additives (such as sizing agents, paper strength enhancers, flocculants, retention agents or coagulants) and drainage aid compounds can be added to the pulp slurry. Examples of the additives (such as sizing agents, paper strength enhancers, flocculants, retention agents or coagulants) include alkyl ketene dimers, alkenyl succinic anhydrides, styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimines, melamine-formaldehyde polymers, polyamideamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichloride and polyalkylene polyamines, dicyandiamide-formalin condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0193] [Pretreatment of Fiber Products] The fiber product may be pretreated before being treated with the repellent of the present disclosure. By performing the pretreatment of the fiber product, excellent fastness can be imparted to the fiber product after being treated with the repellent.

[0194] Examples of the pretreatment of textile products include cationization treatment by reaction with a reactive quaternary ammonium salt, anionic treatment such as sulfonation, carboxylation, phosphorylation, etc., acetylation treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, polymer coating treatment, etc. after anionic treatment.

[0195] As a method for pretreating textile products, although not limited thereto, the textile products can be pretreated by a conventionally known method. If necessary, the pretreatment liquid can be dispersed and diluted in an organic solvent or water, and attached to the surface of the textile products by a known method such as dip coating, spray coating, foam coating, etc., and then dried. The pH and temperature of the pretreatment liquid may be adjusted according to the required degree of treatment. As an example of the method for pretreating textile products, the method for pretreating textile products with a hydrocarbon-based water repellent will be described in detail.

[0196] The pretreatment method of the textile product is to introduce -SO3M 1 (wherein M 1 represents a monovalent cation), a monovalent group represented by -COOM 2 (wherein M 2 represents a monovalent cation), and -O-P(O)(OX 1 )(OX 2 (wherein X 1 and X 2 each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms)), at least one functional group selected from the group consisting of monovalent groups (hereinafter sometimes referred to as "specific functional groups").

[0197] Examples of M 1 include H, K, Na, or an ammonium ion which may have a substituent. Examples of M 2 include H, K, Na, or an ammonium ion which may have a substituent. When X 1 or X 2 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.

[0198] The fiber containing the specific functional group (hereinafter, may also be referred to as "functional group-containing fiber") can be prepared, for example, by the following method. (i) A compound having the specific functional group is attached to the fiber material. Note that the attachment of the compound may be in a state where a part of the compound and a part of the fiber are chemically bonded as long as a sufficient amount of the specific functional group remains. (ii) Prepare a fiber in which the specific functional group is directly introduced into the material constituting the fiber.

[0199] In the case of (i), for example, a functional group-containing fiber can be obtained by a functional group introduction step of treating the fiber material with a pretreatment liquid containing one or more compounds having the specific functional group.

[0200] The material of the fiber material is not particularly limited, and examples include natural fibers such as cotton, hemp, 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 form such as fiber (tow, sliver, etc.), yarn, knitted fabric (including interlaced knitting), woven fabric (including interlacing), and non-woven fabric.

[0201] In the present embodiment, from the viewpoint of improving the water repellency of the obtained fiber product, it is preferable to use a fiber material containing polyamide and polyester as materials, and particularly, nylon such as nylon 6 and nylon 6,6, polyester such as polyethylene terephthalate (PET), polytrimethyl terephthalate, and polylactic acid, and mixed fibers containing these are preferably used.

[0202] The above -SO3M 1 As the compound having, a phenolic polymer can be used. Examples of such a phenolic polymer include those containing at least one compound represented by the following general formula.

[0203] TIFF0007716723000004.tif4678[wherein, X 2 is -SO3M 3 (wherein, M 3 represents a monovalent cation) or a group represented by the following general formula, and n is an integer of 20 to 3000.)

[0204] TIFF0007716723000005.tif2661[wherein, M 4 represents a monovalent cation.)

[0205] Said M 3 includes H, K, Na or an ammonium ion which may have a substituent.)

[0206] Said M 4 includes H, K, Na or an ammonium ion which may have a substituent.)

[0207] 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.)

[0208] Examples of the compound having said -COOM 2 include polycarboxylic acid-based polymers.)

[0209] Examples of the polycarboxylic acid-based polymer include polymers synthesized by a conventionally known radical polymerization method using, for example, acrylic acid, methacrylic acid, maleic acid, etc. as monomers, or commercially available products can be used.)

[0210] As a method for producing a polycarboxylic acid polymer, for example, a method of adding a radical polymerization initiator to an aqueous solution of the above monomer and / or its salt and heating and reacting at 30 to 150°C for 2 to 5 hours can be mentioned. At this time, alcohols such as methanol, ethanol, isopropyl alcohol, etc. or aqueous solvents such as acetone may be added to the aqueous solution of the above monomer and / or its salt. Examples of the radical polymerization initiator include persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate, etc., redox polymerization initiators by combinations of persulfates and sodium bisulfite, etc., hydrogen peroxide, water-soluble azo polymerization initiators, etc. These radical polymerization initiators may be used alone or in combination of two or more. Further, during radical polymerization, a chain transfer agent (for example, octyl thioglycolate) may be added for the purpose of adjusting the degree of polymerization.

[0211] In radical polymerization, monomers copolymerizable with the above monomer can be used in addition to the above monomer. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, vinyl acetate, etc., acrylamide, acrylates, methacrylates, etc. Acrylates and methacrylates preferably 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, propyl methacrylate, etc. These copolymerizable monomers may be used alone or in combination of two or more.

[0212] The carboxyl group in the polycarboxylic acid polymer may be free or neutralized by an alkali metal, an amine compound, etc. Examples of the alkali metal include sodium, potassium, lithium, etc., and examples of the amine compound include ammonia, monoethanolamine, diethanolamine, triethanolamine, etc.

[0213] From the viewpoint of achieving good water repellency of the resulting fiber product, 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.

[0214] As the polycarboxylic acid polymer, commercially available products such as "Neocrystar 770" (trade name, manufactured by Nikkawa Chemical Co., Ltd.) and "Cellopol PC-300" (trade name, manufactured by Sanyo Chemical Industries, Ltd.) can be used.

[0215] Examples of the compound having -O-P(O)(OX 1 )(OX 2 ) include, for example, phosphate ester compounds represented by the following general formula. TIFF0007716723000006.tif3243[In the formula, X 1 or X 2 has the same meaning as described above, and X 3 represents an alkyl group having 1 to 22 carbon atoms.]

[0216] As the phosphate ester compound, a phosphate monoester, diester, and triester in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, and mixtures thereof can be used.

[0217] From the viewpoint of achieving good water repellency of the resulting fiber product, it is preferable to use lauryl phosphate ester and decyl phosphate ester.

[0218] As the phosphate ester compound, commercially available products such as "Phosphanol ML-200" (trade name, manufactured by Toho Chemical Industry Co., Ltd.) can be used.

[0219] The pretreatment liquid containing one or more of the above-mentioned compounds having specific functional groups can be, for example, an aqueous solution of the above-mentioned compounds. Further, the pretreatment liquid may contain an acid, an alkali, a surfactant, a chelating agent, etc.

[0220] Examples of the method for treating the fiber material with the above pretreatment liquid include padding treatment, dipping treatment, spraying treatment, and coating treatment. Examples of the padding treatment include the method using a padding apparatus described on pages 396 to 397 of the Fiber Dyeing and Finishing Dictionary (published in 1963 by Nikkanshimbunsha) and pages 256 to 260 of Color Dyeing Chemistry III (published in 1975 by Jikkyo Shuppan Co., Ltd.). Examples of the coating treatment include the method using a coating machine described on pages 473 to 477 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Sen'i Shuppan Co., Ltd.). Examples of the dipping treatment include the method using a batch dyeing machine described on pages 196 to 247 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Sen'i Shuppan Co., Ltd.), and a liquid flow dyeing machine, an air flow dyeing machine, a drum dyeing machine, a winch dyeing machine, a washer dyeing machine, a cheese dyeing machine, etc. can be used. Examples of the spraying treatment include an air spray that atomizes the treatment liquid with compressed air and blows it, and a method using an air spray with a hydraulic atomization method. The treatment conditions such as the concentration of the treatment liquid and the heat treatment after application can be appropriately adjusted in consideration of various conditions such as the purpose and performance. When the pretreatment liquid contains water, it is preferably dried to remove the water after adhering to the fiber material. The drying method is not particularly limited, and either a dry heat method or a wet heat method may be used. The drying temperature is not particularly limited either, but for example, it may be dried at room temperature to 200°C for 10 seconds to several days. If necessary, heat treatment may be performed at a temperature of 100 to 180°C for about 10 seconds to 5 minutes after drying.

[0221] When the fiber material is to be dyed, the treatment with the pretreatment liquid may be carried out before dyeing or in the same bath as dyeing. However, when performing reduction soaping, since the compound having the above specific functional group adsorbed in the process (for example, a phenolic polymer compound, etc.) may fall off, it is preferably carried out after reduction soaping after dyeing.

[0222] The treatment temperature in the dipping treatment can be 60 to 130°C. The treatment time can be 5 to 60 minutes.

[0223] In the functional group introduction step using the pretreatment liquid, it is preferable to perform the treatment in an amount such that the adhesion amount of the compound having the specific functional group is 1.0 to 7.0 parts by weight with respect to 100 parts by weight of the fiber material. When it is within this range, both durable water repellency and texture can be achieved at a high level.

[0224] The pretreatment liquid preferably has its pH adjusted to 3 to 5. For pH adjustment, pH adjusters such as acetic acid and malic acid can be used.

[0225] In the pretreatment liquid, a salt can also be used in combination in order to effectively adsorb the compound having the specific functional group to the fiber material by the salting-out effect. Examples of the salt that can be used include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate.

[0226] In the functional group introduction step using the pretreatment liquid, it is preferable to remove the compound having the specific functional group that has been treated excessively. Examples of the removal method include the method by water washing. By performing sufficient removal, it is possible to suppress the inhibition of the expression of water repellency in the subsequent water repellent treatment, and in addition, the texture of the obtained fiber product becomes good. Further, the obtained functional group-containing fiber is preferably dried sufficiently before being brought into contact with the hydrocarbon-based water repellent.

[0227] (ii) Examples of the fiber in which the specific functional group is directly introduced into the material constituting the fiber include cation-dyeable polyester (CD-PET).

[0228] From the viewpoint of good water repellency of the obtained fiber product, the zeta potential of the surface of the functional group-containing fiber is preferably -100 to -0.1 mV, and more preferably -50 to -1 mV. The zeta potential of the surface of the fiber can be measured, for example, with a zeta potential / particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0229] Although the embodiments have been described above, it will be understood that various changes in form and detail can be made without departing from the spirit and scope of the claims.

Example

[0230] Hereinafter, the present disclosure will be described in detail with reference to examples, but the present disclosure is not limited to these examples.

[0231] <Test method> The test procedure is as follows.

[0232] 〔Number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw / Mn)〕 The number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) were determined by gel permeation chromatography (GPC). For GPC, tetrahydrofuran or DMF was used as the eluent, LF-404 and KF-805L manufactured by Shodex were used as columns, and the molecular weight and the like were calculated in terms of PMMA.

[0233] 〔Composition of copolymer by NMR (nuclear magnetic resonance method)〕 For 1H-NMR (nuclear magnetic resonance method) measurement, deuterated chloroform was used as the solvent.

[0234] 〔Measurement of thermal physical properties by differential scanning calorimetry (DSC)〕 The melting point of the polymer was calculated by differential scanning calorimetry (DSC). For DSC measurement, after cooling to -20°C under a nitrogen atmosphere, the temperature was raised to 180°C at a rate of 10°C / min, then cooled again to -20°C, and the melting point observed during the subsequent heating process to 180°C at a rate of 10°C / min was measured. For polymers showing multiple melting peaks, the peak with the largest heat of fusion derived from the melting of the long-chain alkyl was taken as the melting point. The glass transition point (glass transition temperature) was determined as the temperature indicated by the midpoint of the intersection of the extension lines of the respective baselines before and after the secondary transition of the DSC curve and the tangent line at the inflection point of the DSC curve.

[0235] 〔Measurement of static contact angle〕 A chloroform solution of the polymer (solid content concentration: 1.0%) was spin-coated onto a silicon wafer substrate and heated at 120 °C for 15 minutes to form a coating film. 2 μL of water or hexadecane (n-HD) was dropped onto this coating film, and the static contact angle 1 second after droplet deposition was measured using an automatic contact angle meter (DropMaster 701 manufactured by Kyowa Interface Science Co., Ltd.).

[0236] 〔Adhesion〕 A chloroform solution of the polymer (solid content concentration: 5.0%) was bar-coated onto a polyester film (Lumirror manufactured by Toray Industries, Inc.) with a thickness of 250 μm and heated at 80 °C for 20 minutes to form a coating film. Cut marks in a grid pattern at 1-mm intervals were made in the coating film with a cutter knife, and after attaching cellophane tape and then peeling it off, those with a peeling area of 0 to 15% were evaluated as ○, those with a peeling area of 15 to 50% were evaluated as △, and those with a peeling area of 50% or more were evaluated as ×.

[0237] 〔Water repellency test〕 A treatment liquid with a solid content concentration of 1.5% was prepared using chloroform as a solvent. A polyester cloth (PET) was immersed in this test solution and then passed through a mangle, and the water repellency was evaluated using the heat-treated test cloth. The test was carried out according to the spray method of JIS-L-1092 (AATCC-22), and the water repellency of the treated cloth was evaluated as ○×. ○: Does not show wetting ×: Shows wetting overall

[0238] 〔Production of paper plates〕 Using wood pulp slurry, paper plates (untreated) weighing 10 g were produced with an automatic mold forming machine.

[0239] 〔Water and oil resistance test〕 A treatment liquid with a solid content concentration of 10% was prepared using chloroform as a solvent. The paper plate was immersed in this test solution, and then 100 mL of water or corn oil was poured into the heat-treated test plate. The water resistance and oil resistance were evaluated as ○× based on the presence or absence of penetration of water or oil. ○: No penetration on the back side ×: Penetration throughout the back side

[0240] <Production Example> The synthesis and cyclopolymerization of divinyl monomers were carried out according to the following procedures.

[0241] 〔Production Example 1: Synthesis of Divinyl Monomer 1〕 To a 32113 reactor, 4-(Trifluoromethyl)salicylic acid (250 g), N-(2-Hydroxyrthyl)acrylamide (167 g), 4-Dimethylaminopyridine (37 g), and dichloromethane (2.1 L) were added, and the mixture was stirred at room temperature for 1.5 hours. After cooling to 0 °C, 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide Hydrochloride (278 g) was added, and the mixture was stirred for 3 hours and then stirred overnight at room temperature. After completion of the reaction, it was quenched with a citric acid methanol solution, separated by liquid-liquid extraction, and purified by column chromatography to obtain 2-Acrylamidoethyl 4-(trifluoromethyl)salicylate (272 g) in a yield of 74%. To a 30106 reactor, 2-Acrylamidoethyl 4-(trifluoromethyl)salicylate (101 g) and tetrahydrofuran (1.4 L) were added. While stirring at 0 °C, acryloyl chloride (28 mL) and triethylamine (51 mL) were added, and the mixture was stirred for 4 hours. After completion of the reaction, it was quenched with methanol, filtered, and purified by column chromatography to obtain Divinyl Monomer 1 (93 g) in a yield of 78%.

[0242] 〔Production Example 2: Synthesis of Divinyl Monomer 2〕 To a 1572 reactor, ethylene glycol monovinyl ether (196 g), triethylamine (101 g), and dichloromethane (1.9 L) were added. While stirring at 0 °C, acryloyl chloride (168 g) was added dropwise, and the mixture was further stirred at room temperature. After completion of the reaction, it was quenched with water, separated by liquid-liquid extraction, and purified by column chromatography to obtain 2-(vinyloxy)ethyl acrylate (124 g) in a yield of 47%. To the reactor, methacrylic acid (271 g), 2-(vinyloxy)ethyl acrylate (124 g), and dichloromethane (1.1 L) were added, and the mixture was heated and stirred at 60 °C for 86 hours. After completion of the reaction, an aqueous 5% sodium hydrogen carbonate solution was added, followed by liquid separation and purification by column chromatography to obtain divinyl monomer 2 (189 g) in a yield of 95%.

[0243] [Production Example 3: Cyclopolymerization of Divinyl Monomer 1] To the reactor, divinyl monomer 1 (715.7 mg), AIBN (7.2 mg), and DME (19.7 mL) were added under an argon atmosphere, and the mixture was heated and stirred at 60 °C for 6 hours. Then, it was cooled to -78 °C to stop the reaction. The consumption rates of the two vinyl groups (acrylate; A, acrylamide; Am) were both 88% as determined by 1H-NMR (CDCl3). From SEC, the number average molecular weight (Mn) was 10300 and the molecular weight distribution (Mw / Mn) was 2.49.

[0244] [Production Example 4: Cyclopolymerization of Divinyl Monomer 2] To the reactor, divinyl monomer 2 (6.85 g), AIBN (0.02 eq.), and toluene (300 mL) were added under an argon atmosphere, and the mixture was heated and stirred at 60 °C for 4 hours. Then, it was cooled to -78 °C to stop the reaction. The consumption rates of the two vinyl groups (methacrylate; M, acrylate; A) were both 82% as determined by 1H-NMR (CDCl3). From SEC, the number average molecular weight (Mn) was 25300 and the molecular weight distribution (Mw / Mn) was 3.04.

[0245] [Production Example 5: Scale-up of Cyclopolymerization of Divinyl Monomer 1] To the reactor, 2.5 g of divinyl monomer 1, 23 mg of AIBN, and 70 mL of DME were added under an argon atmosphere. After heating and stirring at 60 °C for 6 hours, the reaction was cooled to -78 °C to stop the reaction. From SEC, the number average molecular weight (Mn) was 7400 and the molecular weight distribution (Mw / Mn) was 2.31.

[0246] <Examples and Comparative Examples> Polymers were synthesized according to the following procedures. The above tests were conducted using the obtained polymers.

[0247] 〔Example 1: Alternating copolymer 1 (conversion with C12 amine)〕 To the reactor, 5 mL of the polymerization solution of Production Example 3 (0.5 mmol of monomer unit) and dodecylamine (10 eq.) were added. After stirring overnight at room temperature, it was purified by methanol dialysis. From SEC, the number average molecular weight (Mn) was 10400 and the molecular weight distribution (Mw / Mn) was 1.85.

[0248] 〔Example 2〕 The reaction was carried out in the same manner as in Example 1 except that the amine was changed to octadecylamine and the reaction temperature was changed to 80 °C.

[0249] 〔Example 3〕 The reaction was carried out in the same manner as in Example 1 except that the amine was changed to n-octylamine.

[0250] 〔Example 4〕 The reaction was carried out in the same manner as in Example 1 except that the amine was changed to 2-ethylhexylamine.

[0251] 〔Example 5〕 The reaction was carried out in the same manner as in Example 1 except that the amine was changed to cyclooctylamine.

[0252] 〔Example 6〕 The reaction was carried out in the same manner as in Example 1, except that the amine was changed to 3-(dibutylamino)propylamine.

[0253] Example 7 To the reactor were added the polymerization solution of Production Example 3 (5 mL; 0.5 mmol of monomer unit) and 4-tBu-benzylamine (10 eq.), and the mixture was stirred overnight at room temperature to convert one side chain. Further, to complete the conversion to a hydroxyethyl group, n-butylamine (5 eq.) was added, and the mixture was stirred overnight at room temperature and then purified by methanol dialysis. From SEC, the number average molecular weight (Mn) was 10300 and the molecular weight distribution (Mw / Mn) was 2.09.

[0254] Example 8: Random copolymer 1 To the reactor were added N-dodecylacrylamide (166 mg), N-hydroxyethylacrylamide (80 mg), AIBN (2.3 mg), and DMF (7 mL) under an argon atmosphere, and the mixture was heated and stirred at 60 °C for 48 hours and then cooled to -78 °C to stop the reaction. From SEC, the number average molecular weight (Mn) was 5500 and the molecular weight distribution (Mw / Mn) was 1.71. From 1H-NMR (CDCl3), it was confirmed that it was a random copolymer with a composition ratio of 1:1.

[0255] Example 9 The reaction was carried out in the same manner as in Example 8, except that N-dodecylacrylamide was changed to N-octylacrylamide.

[0256] Example 10 The reaction was carried out in the same manner as in Example 8, except that N-dodecylacrylamide was changed to N-(2-ethylhexyl)acrylamide.

[0257] Example 11 The reaction was carried out in the same manner as in Example 8, except that N-dodecylacrylamide was changed to N-cyclooctylacrylamide.

[0258] 〔Example 12: Alternating copolymer 2 (Cleavage with TFA, conversion with C18 isocyanate)〕 To a 35153 reactor, cyclic polymer 2 (0.18 g), THF (20 mL), trifluoroacetic acid (1 mL), and water (0.5 mL) were added, and the mixture was stirred at 30 °C for 24 hours. After completion of the reaction, the solvent was distilled off, and the product was purified by reprecipitation with diethyl ether to obtain an intermediate polymer. To the intermediate polymer (0.18 g), octadecyl isocyanate (1.05 eq.), DMSO (5 mL), and THF (5 mL) were added, and the mixture was stirred overnight at room temperature and then purified by dialysis with methanol. From SEC, the number-average molecular weight (Mn) was 15100 and the molecular weight distribution (Mw / Mn) was 3.11.

[0259] 〔Example 13〕 The reaction was carried out in the same manner as in Example 12, except that dodecyl isocyanate was used instead of octadecyl isocyanate and the solvent was changed to THF only.

[0260] 〔Example 14: Synthesis of alternating copolymer by two amines (conversion with C12 amine and cyclooctylamine)〕 To a 41153 reactor, cyclooctylamine 0.89 g (7 mmol, 5 eq.) / dodecylamine 1.30 g (7 mmol, 5 eq.) was added to the polymerization solution of Production Example 3 (14 mL; 1.4 mmol of monomer unit), and the mixture was stirred at room temperature for 24 hours. Subsequently, the reaction solution was placed in a Spectra / Por 7 dialysis membrane and dialyzed in methanol (2.0 L). Methanol was replaced every about 5 hours, and this was carried out 4 times. The obtained white suspension was concentrated under reduced pressure to obtain 0.25 g of an amorphous solid alternating polymer. From NMR analysis, the introduction ratio (molar ratio) of cyclooctylamine and dodecylamine was 1:3.25. From SEC, the number-average molecular weight (Mn) was 8613 and the molecular weight distribution (Mw / Mn) was 1.38.

[0261] [Example 15: Scale-up of the synthesis of an alternating copolymer (conversion with C12 amine and cyclooctylamine)] The scale-up of Example 14 was carried out. To the reactor, 4.45 g (35 mmol, 5 eq.) of cyclooctylamine / 6.48 g (35 mmol, 5 eq.) of dodecylamine was added to the polymerization solution of Production Example 3 (70 mL; 7 mmol of monomer units), and the mixture was stirred at room temperature for 24 hours. Post-treatment was carried out in the same manner as in Example 14 to obtain 1.7 g of an amorphous solid alternating polymer. From NMR analysis, the introduction ratio of amines was cyclooctylamine / dodecylamine = 1:21.03. From SEC, the number average molecular weight (Mn) was 10514, and the molecular weight distribution (Mw / Mn) was 1.48. As a result of the scale-up, the introduction rate of cyclooctylamine was significantly reduced.

[0262] [Comparative Example 1: Random copolymer 2] TIFF0007716723000018.tif30143 To the reactor, tBuMA (0.41 mL), C18URA (1.03 g), AIBN (8.6 mg), and 1,4-dioxane (5.2 mL) were added under an argon atmosphere, and the mixture was heated and stirred at 60 °C for 22 hours, then cooled to -78 °C to stop the reaction. The consumption rates of the two vinyl groups (methacrylate; M, acrylate; A) were M: 99% and A: 95% from 1H-NMR (CDCl3). From SEC, the number average molecular weight (Mn) was 27400, and the molecular weight distribution (Mw / Mn) was 3.95. It was purified by methanol reprecipitation, and it was confirmed from 1H-NMR (CDCl3) that it was a random copolymer with a composition ratio of 1:1. To the reactor, HCl (100 eq.) and 1,4-dioxane (200 mL) were added with respect to the tBuMA unit concentration of the copolymer being 2 mmol, and the mixture was heated and stirred at 90 °C for 12 hours. After completion of the reaction, the solvent was distilled off, and it was confirmed from 1H-NMR (CDCl3) that it was random copolymer 2 in which the tBu group was deprotected.

[0263] [Comparative Example 2] The reaction was carried out in the same manner as in Comparative Example 1, except that C18URA was changed to C12URA.

[0264] [Comparative Example 3] Homopolymer 1 TIFF0007716723000019.tif2057 N-Dodecylacrylamide (4.79 g), AIBN (32.8 mg), and THF (5.2 mL) were added to a reactor under an argon atmosphere, heated and stirred at 60 °C for 3 hours, and then cooled to -78 °C to stop the reaction. From SEC, the number average molecular weight (Mn) was 27,200 and the molecular weight distribution (Mw / Mn) was 1.97.

[0265] [Comparative Example 4] The reaction was carried out in the same manner as in Comparative Example 3, except that N-dodecylacrylamide was changed to N-cyclooctylacrylamide.

[0266] [Results] The results are summarized in the following table.

[0267] [Table 1] (Static contact angle test (water)) JPEG0007716723000020.jpg86154

[0268] [Table 2] (Static contact angle test (n-HD)) JPEG0007716723000021.jpg43151

[0269] [Table 3] (Adhesion test) JPEG0007716723000022.jpg26154

[0270] [Table 4] (Water repellency test (textile)) JPEG0007716723000023.jpg48153

[0271] [Table 5] (Static contact angle test (water and n-HD)) JPEG0007716723000024.jpg32150

[0272] [Table 6] (Water- and oil-resistant test (paper)) TIFF0007716723000025.tif24154

[0273] [Abbreviation] The meanings of the abbreviations are as follows. HEAAm: N-(2-hydroxyethyl)acrylamide DAAm: N-dodecylacrylamide ODAAm: N-octadecylacrylamide OAAm: N-octylacrylamide EHAAm: N-(2-ethylhexyl)acrylamide CyOAAm: N-cyclooctylacrylamide DBAPAAm: N-(3-(dibutylamino)propyl)acrylamide tBuBnAAm: N-(4-(t-butyl)benzyl)acrylamide MAA: Methacrylic acid C18URA: 2-((octadecylcarbamoyl)oxy)ethyl acrylate C12URA: 2-((dodecylcarbamoyl)oxy)ethyl acrylate C12 amine: N-dodecylamine CyONH2: N-cyclooctylamine

Claims

1. A polymer which is the polymer (III) defined below. (III) The following formula: -[CH ２ C(-Q ３ )C(=O)OH] - [In the formula, Q ３ is a hydrogen atom, a monovalent organic group, or a halogen atom. the repeating unit (3) represented by and the following formula: - [CH ２ C(-Q ４ )C(=O)OR ４１ OC(=O)NHR ４２ - [In the formula, Q ４ is a hydrogen atom, a monovalent organic group or a halogen atom, R ４１ is an alkylene group having 1 to 10 carbon atoms, R ４２ is a monovalent organic group having a hydrocarbon group with 4 to 40 carbon atoms. the repeating unit (4) represented by and a polymer having an alternating sequence (E) composed of

2. The polymer according to claim 1, wherein the amount of the alternating sequence (E) is 30% by weight or more in the polymer.

3. A water-repellent agent containing a polymer which is the polymer (III) defined below. (III) The following formula: - [CH ２ C(-Q ３ )C(=O)OH] - [In the formula, Q ３ is a hydrogen atom, a monovalent organic group or a halogen atom. the repeating unit (3) represented by and the following formula: - [CH ２ C(-Q ４ )C(=O)OR ４１ OC(=O)NHR ４２ - [In the formula, Q ４ is a hydrogen atom, a monovalent organic group or a halogen atom, R ４１ is an alkylene group having 1 to 10 carbon atoms, R ４２ is a monovalent organic group having a hydrocarbon group with 4 to 40 carbon atoms. the repeating unit (4) represented by and a polymer having an alternating sequence (E) composed of

4. The water-repellent agent according to claim 3, wherein the amount of the alternating sequence (E) is 30% by weight or more in the polymer.

5. The water-repellent agent according to claim 3, which contains a liquid medium that is water, an organic solvent, or a mixture of water and an organic solvent.

6. The water-repellent agent according to claim 3, which is for fibers or paper.

7. A substrate to which the polymer in the water-repellent agent according to any one of claims 3 to 6 is adhered.

8. A method for manufacturing a treated substrate, which includes applying the water-repellent agent according to any one of claims 3 to 6 to a substrate.

9. A method for manufacturing a polymer (III), comprising: the following formula: CH ２ =C(-Q ３ )C(=O)O-X Ｅ -O-R ４１ -OC(=O)C(-Q ４ )=CH ２ [In the formula, Q ３ is a hydrogen atom, a monovalent organic group or a halogen atom, X Ｅ is a group removable by acid decomposition and is a group represented by -CHRE- or -C(RE)2- RE is a hydrocarbon group or a derivative thereof, Q ４ is a hydrogen atom, a monovalent organic group, or a halogen atom, R ４１ is an alkylene group having 1 to 10 carbon atoms. a step of obtaining a precursor (E1) by cyclopolymerizing a divinyl monomer (E) represented by A step of removing X from the precursor (E1) by acid-decomposing the precursor (E1) to obtain a precursor (E2); and Ｅ ​ the precursor (E2) and the following formula: R ４２ -NCO [wherein, R ４２ is a monovalent organic group having a hydrocarbon group with 4 to 40 carbon atoms. ] and reacting with an isocyanate compound represented by wherein the polymer (III) is the following formula: - [CH ２ C(-Q ３ )C(=O)OH] - [In the formula, Q ３ is a hydrogen atom, a monovalent organic group or a halogen atom. the repeating unit (3) represented by and the following formula: - [CH ２ C(-Q ４ )C(=O)OR ４１ OC(=O)NHR ４２ - [In the formula, Q ４ is a hydrogen atom, a monovalent organic group or a halogen atom, R ４１ is an alkylene group having 1 to 10 carbon atoms, R ４２ is a monovalent organic group having a hydrocarbon group with 4 to 40 carbon atoms. the repeating unit (4) represented by and a method for manufacturing a polymer (III) having an alternating sequence (E) composed of

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