JP7535277B2 - Repellent - Google Patents

Description

This disclosure relates to repellents.

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

Kametani, Yuki, et al. Angewandte Chemie International Edition 59.13 (2020): 5193-5201.

Non-Patent Document 1 does not describe or suggest the application of polymers to repellent applications. In addition, Non-Patent Document 1 only discloses an alternating copolymer consisting of only acrylamide units, and does not describe or suggest polymers having acrylate units. The purpose of this disclosure is to provide a new repellent or a new polymer that can be used for repellent applications.

The present disclosure includes the following aspects:
[Item 1]
A repellent comprising a polymer selected from polymers (I) to (III) defined below.
(I) A compound of the following formula:
-[CH ₂ C(-Q ¹ )C(=O)R ¹ ]-
[Wherein,
^Q1 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 , in each occurrence, is independently a monovalent organic group having a hydrocarbon group having from 4 to 40 carbon atoms.
and a repeating unit (1) represented by the following formula:
-[CH ₂ C(-Q ² )C(=O)NHR ² OH]-
[Wherein,
^Q2 is a hydrogen atom, a monovalent organic group or a halogen atom;
^R2 is an alkylene group having 1 to 10 carbon atoms.
A polymer having a repeating unit (2) represented by the following formula:
(II) A polymer having an alternating sequence (A) consisting of the repeating unit (1) and the repeating unit (2).
(III) a compound represented by the following formula:
-[CH ₂ C(-Q ³ )C(=O)OH]-
[Wherein,
^Q3 is a hydrogen atom, a monovalent organic group, or a halogen atom.
and a repeating unit (3) represented by the following formula:
-[CH ₂ C(-Q ⁴ )C(=O)OR ⁴¹ OC(=O)NHR ⁴² ]-
[Wherein,
^Q4 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 a repeating unit (4) represented by the following alternating sequence (E).
[Item 2]
Item 2. The repellent according to item 1, comprising a polymer (II).
[Item 3]
Item 3. The repellent according to item 1 or 2, comprising a polymer (III).
[Item 4]
Item 4. The repellent according to any one of Items 1 to 3, wherein the amount of the repeating unit (1) in the polymer is 15% by weight or more, and the amount of the repeating unit (2) in the polymer is 15% by weight or more; or the amount of the alternating sequence (A) and/or the alternating sequence (E) in the polymer is 30% by weight or more.
[Item 5]
Item 5. The repellent according to any one of items 1 to 4, comprising a liquid medium which is water, an organic solvent, or a mixture of water and an organic solvent.
[Item 6]
Item 6. The repellent according to any one of items 1 to 5, which is for fibers or paper.
[Item 7]
Item 7. A substrate to which the polymer in the repellent according to any one of items 1 to 6 is attached.
[Item 8]
Item 7. A method for producing a treated substrate, comprising applying the 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) a compound of the following formula:
-[CH ₂ C(-Q ¹ )C(=O)R ¹ ]-
[Wherein,
^Q1 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 , in each occurrence, is independently a monovalent organic group having a hydrocarbon group having from 4 to 40 carbon atoms.
and a repeating unit (1) represented by the following formula:
-[CH ₂ C(-Q ² )C(=O)NHR ² OH]-
[Wherein,
^Q2 is a hydrogen atom, a monovalent organic group or a halogen atom;
^R2 is an alkylene group having 1 to 10 carbon atoms.
and (2) an alternating sequence (A) represented by the following repeating unit:
The repeating unit (1) comprises two or more types of R ¹¹ .
(III) a compound represented by the following formula:
-[CH ₂ C(-Q ³ )C(=O)OH]-
[Wherein,
^Q3 is a hydrogen atom, a monovalent organic group, or a halogen atom.
and a repeating unit (3) represented by the following formula:
-[CH ₂ C(-Q ⁴ )C(=O)OR ⁴¹ OC(=O)NHR ⁴² ]-
[Wherein,
^Q4 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 a repeating unit (4) represented by the following alternating sequence (E).
[Item 10]
Item 10. The polymer according to item 9, which is polymer (II).
[Item 11]
Item 10. The polymer according to item 9, which is polymer (III).
[Item 12]
Item 12. The polymer according to any one of items 9 to 11, wherein the amount of the alternating sequence (A) and/or the alternating sequence (E) is 30% by weight or more in the polymer.
[Item 13]
A method for producing polymer (II), comprising the steps of:
The following formula:
CH ₂ =C(-Q ¹ )C(=O)-X ^A -OR ² NHC(=O)C(-Q ² )=CH ₂
[Wherein,
^Q1 is a hydrogen atom, a monovalent organic group or a halogen atom;
^XA is a group removable by aminolysis;
^R2 is an alkylene group having 1 to 10 carbon atoms;
^Q2 is a hydrogen atom, a monovalent organic group, or a halogen atom.
to obtain a precursor (A) by cyclopolymerizing the precursor (A) and a divinyl monomer represented by the following formula:
_NH2 ( ^R11 ) or NH( ^R11 ) ₂
[In the formula, R ¹¹ is independently in each occurrence a monovalent organic group having a hydrocarbon group having 4 to 40 carbon atoms.]
With an amine compound represented by the formula
The polymer (II) has the following formula:
-[CH ₂ C(-Q ¹ )C(=O)R ¹ ]-
[Wherein,
^Q1 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 , in each occurrence, is independently a monovalent organic group having a hydrocarbon group having from 4 to 40 carbon atoms.
and a repeating unit (1) represented by the following formula:
-[CH ₂ C(-Q ² )C(=O)NHR ² OH]-
[Wherein,
^Q2 is a hydrogen atom, a monovalent organic group or a halogen atom;
^R2 is an alkylene group having 1 to 10 carbon atoms.
and an alternating sequence (A) consisting of a repeating unit (2) represented by
The method for producing a polymer (II), wherein the repeating unit (1) contains two or more types of R ¹¹ .
[Item 14]
A method for producing polymer (III), comprising the steps of:
The following formula:
CH ₂ =C(-Q ³ )C(=O)OX ^E -OR ⁴¹ -OC(=O)C(-Q ⁴ )=CH ₂
[Wherein,
^Q3 is a hydrogen atom, a monovalent organic group or a halogen atom;
^XE is a group removable by acidolysis,
^Q4 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 cyclopolymerizing a divinyl monomer (E) represented by the formula:
A step of removing ^XE from the precursor (E1) by acid decomposition to obtain a precursor (E2); and a step of reacting the precursor (E2) with a compound represented by the following formula:
^R42 -NCO
[In the formula, R ⁴² is a monovalent organic group having a hydrocarbon group having 4 to 40 carbon atoms.]
With an isocyanate compound represented by the formula:
The polymer (III) has the following formula:
-[CH ₂ C(-Q ³ )C(=O)OH]-
[Wherein,
^Q3 is a hydrogen atom, a monovalent organic group, or a halogen atom.
and a repeating unit (3) represented by the following formula:
-[CH ₂ C(-Q ⁴ )C(=O)OR ⁴¹ OC(=O)NHR ⁴² ]-
[Wherein,
^Q4 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 a repeating unit (4) represented by the following formula (E):

The present disclosure provides a new repellent or a new polymer that can be used for repellent applications.

<Definition of terms>
As used herein, the term "n-valent group" refers to a group having n bonds, i.e., a group that forms n bonds. The term "n-valent organic group" refers to 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 a hydrocarbon group refers to a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the end of the hydrocarbon group or in the molecular chain.

As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, and resulting from the elimination of a hydrogen atom from a hydrocarbon. Such hydrocarbon groups are not particularly limited, but include _C1-20 hydrocarbon groups, for example, aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and the like. The above-mentioned "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. In addition, the hydrocarbon group may contain one or more ring structures. The hydrocarbon group may be substituted with one or more substituents.

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

<Repellent>
The repellent in the present disclosure provides liquid repellency to a substrate (e.g., a fiber substrate, a paper substrate, etc.) and can function as at least one selected from the group consisting of a water repellent, an oil repellent, an oil-resistant agent, and a water-resistant agent. In the polymer in the repellent, the coexistence of a hydrogen bond site such as an amide group and a hydrocarbon group can improve the liquid repellency. In the polymer in the present disclosure, the hydrogen bond sites such as amide groups are alternately arranged, which makes it easier to form a phase separation structure than a random arrangement, and the liquid repellency of the alternating copolymer can be improved. Furthermore, in the polymer in the present disclosure, the hydrogen bond sites such as amide groups are alternately arranged, which suppresses molecular motion and suppresses the decrease in liquid repellency due to temperature.

The repellent agent in the present disclosure may not contain any of the compounds selected from the group consisting of compounds having a fluoroalkyl group with 8 or more carbon atoms, compounds having a perfluoroalkyl group with 8 or more carbon atoms, compounds having a fluoroalkyl group with 4 or more carbon atoms, compounds having a perfluoroalkyl group with 4 or more carbon atoms, compounds having a perfluoroalkyl group, compounds having a fluoroalkyl group, and compounds having a fluorine atom. The repellent agent in the present disclosure can impart liquid repellency to the substrate even if it does not contain these fluorine compounds.

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

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

[Polymer (I)]
The polymer (I) has a repeating unit (1) and a repeating unit (2). The polymer (I) may be a random polymer having the repeating unit (1) and the repeating unit (2) arranged randomly. The explanation of the repeating unit (1) and the repeating unit (2) is incorporated in the description of the polymer (II).

[Polymer (II)]
The polymer (II) has an alternating sequence (A) consisting of repeating units (1) and repeating units (2).

(Alternating Sequence (A))
The alternating sequence (A) is composed of a repeating unit (1) and a repeating unit (2). That is, the alternating sequence (A) is a sequence formed by alternately bonding the repeating unit (1) and the repeating unit (2), and is represented by the following formula:
-[CH ₂ C(-Q ¹ )C(=O)R ¹ ]-[CH ₂ C(-Q ² )C(=O)NHR ² OH]-
[Wherein,
^Q1 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 in each occurrence a monovalent organic group having a hydrocarbon group having from 4 to 40 carbon atoms;
^Q2 is a hydrogen atom, a monovalent organic group or a halogen atom;
^R2 is an alkylene group having 1 to 10 carbon atoms.
It is expressed as:

(Repeating unit (1))
The repeating unit (1) is
The following formula:
-[CH ₂ C(-Q ¹ )C(=O)R ¹ ]-
[Wherein,
^Q1 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 , in each occurrence, is independently a monovalent organic group having a hydrocarbon group having from 4 to 40 carbon atoms.
It is expressed as:

^Q1 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. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. ^Q1 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, and is, for example, a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, or a cyano group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom, and in particular a hydrogen atom or a methyl group.

R ¹ is -NH(R ¹¹ ) or -N(R ¹¹ ) _2. For example, R ¹ may be a combination of -NH(R ¹¹ ) and -N(R ¹¹ ) ₂ .

R ¹¹ is a monovalent organic group having a hydrocarbon group having 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, preferably linear. The number of carbon atoms in 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 in 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.

R ¹¹ may contain other groups in addition to the hydrocarbon group having 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 a nitrogen atom.

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

The carbon atom ratio of R ¹¹ may be 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%, and is preferably 60% or more. The carbon atom ratio of R ¹¹ may be 100% or less, 95% or less, 90% or less, 85% or less, or 80% or less. Here, the carbon atom ratio of R ¹¹ is the molar ratio of the amount of carbon atoms in R ¹¹ to the total amount of heteroatoms (atoms other than carbon atoms and hydrogen atoms) in R ^11. When the carbon atom ratio of R ¹¹ is equal to or greater than the above lower limit, liquid repellency can be well expressed.

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

(Repeating unit (2))
The repeating unit (2) is
The following formula:
-[CH ₂ C(-Q ² )C(=O)NHR ² OH]-
[Wherein,
^Q2 is a hydrogen atom, a monovalent organic group or a halogen atom;
^R2 is an alkylene group having 1 to 10 carbon atoms.
It is expressed as:

^Q2 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. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. ^Q2 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, and is, for example, a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, or a cyano group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom, and in particular a hydrogen atom or a methyl group.

^R2 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 in 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 in the alkylene group may be 10 or less, 8 or less, 6 or less, 4 or less, or 2 or less, for example, 5 or less.

[Polymer (III)]
The polymer (III) has an alternating sequence (E) consisting of repeating units (3) and repeating units (4).

(Alternating Sequence (E))
The alternating sequence (E) is composed of a repeating unit (3) and a repeating unit (4). That is, the alternating sequence (E) is a sequence formed by alternately bonding the repeating unit (3) and the repeating unit (4), and is represented by the following formula:
-[CH ₂ C(-Q ³ )C(=O)OH]-[CH ₂ C(-Q ⁴ )C(=O)OR ⁴¹ OC(=O)NHR ⁴² ]-
[In the formula, ^Q3 is a hydrogen atom, a monovalent organic group or a halogen atom,
^Q4 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.
Each symbol is explained in detail below.

(Repeating unit (3))
The repeating unit (3) has the following formula:
-[CH ₂ C(-Q ³ )C(=O)OH]-
[Wherein,
^Q3 is a hydrogen atom, a monovalent organic group, or a halogen atom.
It is expressed as:

^Q3 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. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. ^Q3 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, and is, 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, or a chlorine atom, particularly preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

(Repeating unit (4))
The repeating unit (4) has the following formula:
-[CH ₂ C(-Q ⁴ )C(=O)OR ⁴¹ OC(=O)NHR ⁴² ]-
[Wherein,
^Q4 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.
It is expressed as:

^Q4 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. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. ^Q4 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, and is, 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, or a chlorine atom, particularly preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

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 in 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 in the alkylene group may be 10 or less, 8 or less, 6 or less, 4 or less, or 2 or less, for example, 5 or less.

R ⁴² is a monovalent organic group having a hydrocarbon group having 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 in 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 in 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.

R ⁴² may contain other groups in addition to the hydrocarbon group having 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 ⁴² may form a branched structure from a nitrogen atom. As ^{R 42} , one type may be used, or two or more types may be used in combination.

Two or more types of R ⁴² (e.g., two, three, or four types) may be combined. By combining two or more types of R ⁴² , it may be possible to impart a plurality of properties well. An example of a combination is a combination of R ⁴² , which is a hydrocarbon group having 12 or more carbon atoms (e.g., a chain alkyl group), and a cyclic hydrocarbon-containing group (e.g., a cycloalkyl-containing group, a phenyl-containing group, etc.). The hydrocarbon group having 12 or more carbon atoms can impart high liquid repellency, and the cyclic hydrocarbon-containing group can impart high heat resistance. When two or more types 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 of the total of R ⁴² .

The carbon atom ratio of R ⁴² may be 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%, and is 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, or 80% or less. Here, the carbon atom ratio of R ⁴² is 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 equal to or more than the above lower limit, liquid repellency can be well expressed.

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

[Other repeating units]
The polymers (polymers (I) to (III)) may have other repeating units in addition to the repeating units (1) to (4) described above. Examples of the other repeating units include repeating units derived from a hydrocarbon monomer, a crosslinkable monomer, a halogenated olefin monomer, and/or other monomers.

(Hydrocarbon monomer)
The polymer has the formula:
CH ₂ =C(-Q)-C(=O)-X-R _n
[Wherein,
Q is a hydrogen atom, a monovalent organic group or a halogen atom;
X is at least one member 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 in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms);
^X2 is a hydrocarbon group having 1 to 40 carbon atoms;
is a 1+n valent 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 copolymer may be a polymer having a repeating unit derived from a hydrocarbon monomer represented by the following formula:

Q is a hydrogen atom, a monovalent organic group, or a halogen atom. Examples of monovalent organic groups 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. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. 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, and is, for example, a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, or a cyano group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom, and particularly preferably a hydrogen atom or a methyl group.

X is at least one member 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 in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms);
^X2 is a hydrocarbon group having 1 to 40 carbon atoms;
It is a 1+n valent group consisting of one or more selected from the group consisting of:

X is represented by the following formula:
-X ¹ - or -X ¹ -X ² -X ¹ -
[Wherein,
X ¹ , in each occurrence, is independently -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.]
It may be a group represented by the following formula:

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).

The number of carbon atoms in 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 in 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.

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 not having an amide group, a urea group, or a urethane group.

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.

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

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

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.

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

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

Specific examples of the hydrocarbon monomer are as follows: The compound of the following chemical formula is an acrylic compound in which the α-position is a hydrogen atom, but the α-position may be other Q, for example, a methacryl compound in which the α-position is a methyl group, an α-chloroacrylic compound in which the α-position is a chlorine atom, etc.
CH ₂ =CHC(=O)OC _p H _2p NHC(=O)C _q H _2q+1
CH2 =CHC( ₌ O) _OC2H4NHC (=O _{) C17H35
CH2} =CHC( ₌ O) _OC2H4NHC (=O _{) C15H31}
Mixture of CH ₂ ═CHC(═O)OC ₂ H ₄ NHC(═O)C ₁₇ H ₃₅ and CH ₂ ═CHC(═O)OC ₂ H ₄ NHC(═O)C ₁₅ H ₃₁ CH ₂ ═CHC(═O)OC _q H _2q+1
CH2 =CHC(= _O ) _OC18H37
CH2 =CHC(= _O ) _OC16H33
CH ₂ =CHC(=O)OC ₂ H ₄ OC(=O)NHC _q H _2q+1
CH2 =CHC( ₌ O) _OC2H4NHC ( ₌ O) _OCqH2q+1
CH ₂ =CHC(=O)OC ₂ H ₄ NHC(=O)NHC _q H _2q+1
CH ₂ =CHC(=O)OC ₄ H ₈ OC(=O)NHC _q H _2q+1
CH2 =CHC(=O) _OC2H4OC ( ₌ O _{) NHC18H37
CH2} =CHC(=O) _OC2H4NHC ( ₌ O _{) OC18H37}
CH ₂ =CHC(=O)NHC _p H _2p OC(=O)NHC _q H _2q+1
CH ₂ =CHC(=O)OC _p H _2p-1 (NH(C=O)C _q H _q+1 ) (NH(C=O)C _q H _q+1 )
CH ₂ =CHC(=O)OC _p H _2p-1 (NH(C=O)C ₁₇ H ₃₅ )(NH(C=O)C ₁₇ H ₃₅ )
CH ₂ =CHC(=O)OC _p H _2p-1 (O(C=O)NHC _q H _q+1 ) (CH ₂ O(C=O)NHC _q H _q+1 )
_CH2 =CHC(=O) _OCH2CH (O(C=O) _NHC18H37 )( _CH2O (C=O _{) NHC18H37 )}
[In the above formula, p is 1 to 40 (e.g., 1 to 6), and q is 6 to 40 (e.g., 12 to 30).]

(Halogenated Olefin Monomers)
The polymer may have a repeating unit 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, bromine 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 having 1 to 5 chlorine atoms. Preferred specific examples of the halogenated olefin monomer are vinyl halides, such as vinyl chloride, vinyl bromide, vinyl iodide, and vinylidene halides, such as vinylidene chloride, vinylidene bromide, and vinylidene iodide. Vinyl chloride is preferred because it enhances water repellency (particularly durability of water repellency). The presence of the repeating unit derived from the halogenated olefin monomer enhances the washing durability of the polymer.

(Cross-linking monomer)
The polymer may have repeat 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.

The crosslinkable 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.

Examples of reactive groups include hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, carbonyl groups, isocyanate groups, etc.

Specific examples of crosslinkable monomers 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, etc. These may be used alone or in combination of two or more. These may be used alone or in combination of two or more.

(Other monomers)
The polymer may contain repeat units derived from monomers other than those mentioned above.

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

[Polymer composition, etc.]
The amount of 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, preferably 15% by weight or more. The amount of 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, or 30% by weight or less.

The amount of repeating units (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, preferably 15% by weight or more. The amount of repeating units (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, or 30% by weight or less.

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

The amount of alternating sequence (A) 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 alternating sequence (A) 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.

The amount of repeating units (3) 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. The amount of repeating units (3) 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, or 30% by weight or less.

The amount of repeating unit (4) 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. The amount of repeating unit (4) 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, or 30% by weight or less.

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

The amount of 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 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.

The amount of other repeating units in the polymer may be 10% by weight or more, 30% by weight or more, or 50% by weight or more in the polymer. 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 in the polymer.

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 is preferably 5000 or more. The number average molecular weight (Mn) of the polymer may be 1,000,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 25,000 or less, or 10,000 or less, and is preferably 100,000 or less.

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.

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 have no melting point.

The glass transition temperature 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 30°C or more, for example 50°C or more or 75°C or more. The glass transition temperature 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.

[Method for producing polymer (I)]
The method for producing the polymer (I) is not limited, but for example, the polymer (I) may be produced by copolymerization of a monomer which derives the repeating unit (1) and a monomer which derives the repeating unit (2).

An example of a monomer from which the repeating unit (1) is derived is represented by the following formula:
CH ₂ =C(-Q ¹ )C(=O)R ¹
[Wherein,
^Q1 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 , in each occurrence, is independently a monovalent organic group having a hydrocarbon group having from 4 to 40 carbon atoms.
The compound is represented by the following formula: The details of ^Q1 and ^R1 are as described above.

An example of a monomer from which the repeating unit (2) is derived is represented by the following formula:
_CH2 =C( ^-Q2 )C(=O) ^NHR2OH
[Wherein,
^Q2 is a hydrogen atom, a monovalent organic group or a halogen atom;
^R2 is an alkylene group having 1 to 10 carbon atoms.
The compound is represented by the following formula: The details of ^Q2 and ^R2 are as described above.

The copolymerization method is not limited, and any known polymerization method can be selected, and the polymerization reaction conditions can be selected as desired. Examples of such polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization.

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

The organic solvent is inert to the monomers and dissolves them, and may be, for example, aprotic polar solvents (e.g., DMSO, DMF), esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone), or alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, ethanol, butanol, isopropyl alcohol). Specific examples of organic solvents 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 3,000 parts by weight, for example 50 to 2,000 parts by weight, per 100 parts by weight of the total monomers.

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 replacement, the mixture is polymerized by stirring at a temperature in the range of 50 to 80°C for 1 to 20 hours. Polymerization initiators that can be used include water-soluble ones such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, sodium peroxide, potassium persulfate, and ammonium persulfate, and oil-soluble ones such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in the range of 0.01 to 10 parts by weight per 100 parts by weight of monomer.

In order to obtain a polymer aqueous dispersion with excellent shelf stability, it is desirable to use an emulsifier capable of applying strong crushing energy, such as a high-pressure homogenizer or ultrasonic homogenizer, to microparticulate the monomer in water and polymerize it. In addition, various anionic, cationic or nonionic emulsifiers can be used as emulsifiers, and are used in the range of 0.5 to 20 parts by weight per 100 parts by weight of the monomer. It is preferable to use anionic and/or nonionic and/or cationic emulsifiers. If the monomers are not completely compatible, it is preferable to add a compatibilizer that makes these monomers sufficiently compatible, such as a water-soluble organic solvent or a low molecular weight monomer. The addition of a compatibilizer can improve emulsifiability and copolymerizability.

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

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

[Method for producing polymer (II)]
The method for producing the polymer (II) comprises the steps of:
The following formula:
CH ₂ =C(-Q ¹ )C(=O)-X ^A -OR ² NHC(=O)C(-Q ² )=CH ₂
[Wherein,
^Q1 is a hydrogen atom, a monovalent organic group or a halogen atom;
^XA is a group removable by aminolysis;
^R2 is an alkylene group having 1 to 10 carbon atoms;
^Q2 is a hydrogen atom, a monovalent organic group, or a halogen atom.
to obtain a precursor (A) by cyclopolymerizing the precursor (A) and a divinyl monomer represented by the following formula:
_NH2 ( ^R11 ) or NH( ^R11 ) ₂
[In the formula, R ¹¹ is independently in each occurrence a monovalent organic group having a hydrocarbon group having 4 to 40 carbon atoms.]
With an amine compound represented by the formula:

(Step of Cyclopolymerizing Divinyl Monomer (A) to Obtain Precursor (A))
In this step, the divinyl monomer (A) is cyclopolymerized to obtain a precursor (A). By using the cyclopolymerization, it is possible to obtain a polymer (II) which is an alternating copolymer.

The divinyl monomer (A) has the following formula:
CH ₂ =C(-Q ¹ )C(=O)-X ^A -OR ² NHC(=O)C(-Q ² )=CH ₂
[Wherein,
^Q1 is a hydrogen atom, a monovalent organic group or a halogen atom;
^XA is a group removable by aminolysis;
^R2 is an alkylene group having 1 to 10 carbon atoms;
^Q2 is a hydrogen atom, a monovalent organic group, or a halogen atom.
It is expressed as:

The details of Q ¹ , R ² and Q ² are as described above.

X ^A is a group removable by aminolysis. Here, aminolysis refers to a reaction in which an ester reacts with an amine to cleave the ester. X ^A may be a group represented by -O-R ^A -(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., a 1,2-phenylene group)), for example, an aromatic group having a substituent, and in particular an aromatic group having an electron-withdrawing group (e.g., -CF ₃ , -CCl ₃ , -NO ₂ , -CN, etc.) to activate the aminolysis reaction. The molecular weight of R ^A may be 150 or less, or 100 or less. The number of carbon atoms in R ^A may be 10 or less, 8 or less, or 6 or less. Specific examples of R ^A include a 3-trifluoromethyl-1,2-phenylene group, a 5-trifluoromethyl-1,2-phenylene group, a 3,5-bis(trifluoromethyl)-1,2-phenylene group, a 3-trichloromethyl-1,2-phenylene group, a 5-trichloromethyl-1,2-phenylene group, a 3,5-bis(trichloromethyl)-1,2-phenylene group, and a 4-nitro-1,2-phenylene group.

The method of cyclopolymerization is not limited, and any known polymerization method can be selected, and the polymerization reaction conditions can be selected as desired. Examples of such polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization. Details of the polymerization method are as described above.

［式中、
Ｑ^１は水素原子、一価の有機基又はハロゲン原子であり、
Ｘ^Ａはアミノリシスにより除去可能な基であり、
Ｒ^２は炭素数１以上１０以下のアルキレン基であり、
Ｑ^２は水素原子、一価の有機基又はハロゲン原子である。］
で表される繰り返し単位を有する重合体である。 The precursor (A) is

[Wherein,
^Q1 is a hydrogen atom, a monovalent organic group or a halogen atom;
^XA is a group removable by aminolysis;
^R2 is an alkylene group having 1 to 10 carbon atoms;
^Q2 is a hydrogen atom, a monovalent organic group, or a halogen atom.
It is a polymer having a repeating unit represented by the following formula:

(Step of reacting precursor (A) with an amine compound)
In this step, the precursor (A) is reacted with an amine compound, whereby the ester in the precursor (A) reacts with the amine and is cleaved to give the polymer (II).

The amine compound has the following formula:
_NH2 ( ^R11 ) or NH( ^R11 ) ₂
[In the formula, R ¹¹ is independently in each occurrence a monovalent organic group having a hydrocarbon group having 4 to 40 carbon atoms.]
It is expressed as:

The details of R ¹¹ are as described above.

The reaction conditions for the precursor (A) and the amine compound can be set appropriately, and for example, the reaction may be carried out at 20°C to 80°C for 3 hours to 48 hours.

Two or more kinds of amine compounds may be used so that the polymer (II) contains two or more kinds of R ¹¹ .

[Method for producing polymer (III)]
The method for producing the polymer (III) includes the steps of:
The following formula:
CH ₂ =C(-Q ³ )C(=O)O-X ^E -OR ⁴¹ -OC(=O)C(-Q ⁴ )=CH ₂
[Wherein,
^Q3 is a hydrogen atom, a monovalent organic group or a halogen atom;
^XE is a group removable by acidolysis,
^Q4 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 cyclopolymerizing a divinyl monomer (E) represented by the formula:
A step of removing ^XE from the precursor (E1) by acid decomposition to obtain a precursor (E2); and a step of reacting the precursor (E2) with a compound represented by the following formula:
^R42 -NCO
[In the formula, R ⁴² is a monovalent organic group having a hydrocarbon group having 4 to 40 carbon atoms.]
With an isocyanate compound represented by the formula:

(Step of Cyclopolymerizing Divinyl Monomer (E) to Obtain Precursor (E1))
In this step, the divinyl monomer (E) is cyclopolymerized to obtain the precursor (A). By using the cyclopolymerization, it is possible to obtain the polymer (III), which is an alternating copolymer.

The divinyl monomer (E) has the following formula:
CH ₂ =C(-Q ³ )C(=O)O-X ^E -OR ⁴¹ -OC(=O)C(-Q ⁴ )=CH ₂
[Wherein,
^Q3 is a hydrogen atom, a monovalent organic group or a halogen atom;
^XE is a group removable by acidolysis,
^Q4 is a hydrogen atom, a monovalent organic group or a halogen atom;
R ⁴¹ is an alkylene group having 1 to 10 carbon atoms.
It is expressed as:

Details of Q ³ , Q ⁴ and R ⁴¹ are as described above.

^XE is a group removable by acid decomposition. ^XE may be a group represented by -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 in particular an alkyl group. The molecular weight of ^{R E} may be 150 or less, or 100 or less. The number of carbon atoms in R ^E may be 8 or less, 6 or less, 4 or less, 3 or less, or 2 or less. Specific examples of R ^E include a methyl group, an ethyl group, a propyl group, and the like.

The method of cyclopolymerization is not limited, and any known polymerization method can be selected, and the polymerization reaction conditions can also be selected arbitrarily. Examples of such polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization. Details of the polymerization method are as described above.

［式中、
Ｑ^３は水素原子、一価の有機基又はハロゲン原子であり、
Ｘ^Ｅは酸分解により除去可能な基であり、
Ｑ^４は水素原子、一価の有機基又はハロゲン原子であり、
Ｒ^４１は炭素数１以上１０以下のアルキレン基である。］
で表される繰り返し単位を有する重合体である。 The precursor (E1) is
The following formula:

[Wherein,
^Q3 is a hydrogen atom, a monovalent organic group or a halogen atom;
^XE is a group removable by acidolysis,
^Q4 is a hydrogen atom, a monovalent organic group or a halogen atom;
R ⁴¹ is an alkylene group having 1 to 10 carbon atoms.
It is a polymer having a repeating unit represented by the following formula:

(Step of Removing X ^{and E} from Precursor (E1) to Obtain Precursor (E2))
In this step, precursor (E1) is decomposed with an acid to remove ^XE from precursor (E1) to obtain precursor (E2).

The conditions for acid decomposition are not limited and can be set appropriately. For example, the reaction may be carried out at 20°C to 80°C for 3 to 48 hours.

［式中、
Ｑ^３は水素原子、一価の有機基又はハロゲン原子であり、
Ｑ^４は水素原子、一価の有機基又はハロゲン原子であり、
Ｒ^４１は炭素数１以上１０以下のアルキレン基である。］
で表される繰り返し単位を有する重合体である。 The precursor (E2) is
The following formula:

[Wherein,
^Q3 is a hydrogen atom, a monovalent organic group or a halogen atom;
^Q4 is a hydrogen atom, a monovalent organic group or a halogen atom;
R ⁴¹ is an alkylene group having 1 to 10 carbon atoms.
It is a polymer having a repeating unit represented by the following formula:

(Step of reacting precursor (E2) with an isocyanate compound)
In this step, the precursor (E2) is reacted with an isocyanate compound, whereby a hydroxy group in the precursor (E2) reacts with an isocyanate group in the isocyanate compound to produce a polymer (III).

The isocyanate compound has the following formula:
^R42 -NCO
[In the formula, R ⁴² is a monovalent organic group having a hydrocarbon group having 4 to 40 carbon atoms.]
It is expressed as:

For details about R ⁴² , the explanation for the polymer mentioned above can be used.

The reaction conditions for the precursor (E2) and the isocyanate compound can be set appropriately, and for example, the reaction may be carried out at 20°C to 80°C for 3 hours to 48 hours.

As the isocyanate compound, two or more kinds of amine compounds may be used so that the polymer (III) contains two or more kinds of R ⁴² .

[Amount of polymer]
The amount of the polymer in the repellent may be 0.01% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, or 30% by weight or more. The amount of the polymer in the repellent 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.

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

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

[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, relative 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, relative to 1 part by weight of the polymer.

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, per 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, per part by weight of the polymer.

The amount of organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, per part by weight of the polymer. The amount of 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, per part by weight of the polymer.

[Surfactant]
The repellent may include a surfactant, which may include one or more surfactants selected from a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant.

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

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

An example of an ester is an ester of an alcohol and a fatty acid. An example of an alcohol is a monohydric to hexahydric (particularly dihydric to pentahydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

An example of an ester ether is a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. An example of an alcohol is a monohydric to hexahydric (particularly dihydric to pentahydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

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

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

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

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.
Moreover, the nonionic surfactant preferably has a structure that does not contain an aromatic group in view of environmental issues (biodegradability, environmental hormones, etc.).

The nonionic surfactant has the formula:
R ¹ O-(CH ₂ CH ₂ O) _p -(R ² O) _q - R ³
[In the formula, R ¹ represents an alkyl group having 1 to 22 carbon atoms or an alkenyl group or acyl group having 2 to 22 carbon atoms,
Each R ² is independently the same or different and is an alkylene group having 3 or more carbon atoms (e.g., 3 to 10);
^R3 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 equal to or greater than 2;
q is 0 or a number equal to or greater than 1.
The compound may be represented by the formula:

R ¹ preferably has a carbon number of 8 to 20, particularly 10 to 18. Specific preferred examples of R ¹ include a lauryl group, a tridecyl group, and an oleyl group.
Examples of ^R2 include a propylene group and a butylene group.
In the nonionic surfactant, p may be a number of 3 or more (for example, 5 to 200), and 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, and a styrene chain, and among these, an oxypropylene chain is preferred.

Specific examples of nonionic surfactants include condensation products of ethylene oxide with hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkane (C ₁₂ -C ₁₆ ) thiols, sorbitan mono fatty acids (C ₇ -C ₁₉ ) or alkyl (C ₁₂ -C ₁₈ ) amines, and the like.

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

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

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

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

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 C12 or higher (e.g., C ₁₂ to C ₅₀ ) linear and/or branched aliphatic (saturated and/or unsaturated) group;
^R2 is H or a C1-4 alkyl group, a benzyl group, or a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50).
( _CH3 , _{C2H5 are} particularly preferred);
X is a halogen atom (for example), a _C1 - _C4 fatty acid base,
p is 1 or 2, q is 2 or 3, and p+q=4.
The carbon number of R ¹ may be 12 to 50, for example 12 to 30.

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.

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

[Amphoteric surfactant]
Examples of amphoteric surfactants include alanines, imidazolinium betaines, amido betaines, and betaine acetate. Specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetate betaine, and fatty acid amidopropyl dimethylamino acetate betaine.

The surfactant may be one or a combination of two or more of a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant.

[Amount of surfactant]
The amount of the surfactant may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative 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, relative to 100 parts by weight of the polymer.
It may be.

〔silicone〕
The repellent in the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, it is possible to obtain good texture and durability in addition to good liquid repellency.

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

The weight average molecular weight of the silicone may be 1,000 or more, 10,000 or more, or 50,000 or more. The weight average molecular weight of the silicone may be 500,000 or less, 2,500,000 or less, 100,000 or less, or 50,000 or less.

[Amount of silicone]
The amount of silicone may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 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, based on 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, based on 100 parts by weight of the polymer.

〔wax〕
The repellent in the present disclosure may contain a wax. By containing a wax, it is possible to impart good liquid repellency to the substrate.

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

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, and more preferably 60°C or higher. The melting point of the wax is measured in accordance with JIS K 2235-1991.

[Amount of wax]
The amount of the wax may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 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, relative to 100 parts by weight of the polymer. The amount of the 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, or 5 parts by weight or less, relative to 100 parts by weight of the polymer.

[Organic acids]
The repellent may contain an organic acid. As the organic acid, a known one may be used. As the organic acid, carboxylic acid, sulfonic acid, sulfinic acid, etc. are preferably mentioned, and carboxylic acid is particularly preferable. As the carboxylic acid, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc. are mentioned, and formic acid or acetic acid is particularly preferable. In the present disclosure, the organic acid may be used alone or in combination of two or more kinds. For example, formic acid and acetic acid may be used in combination.

[Amount of organic acid]
The amount of the organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, based on 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, based on 100 parts by weight of the polymer. The amount of the organic acid may be adjusted so that the pH of the repellent is 3 to 10, for example 5 to 9, particularly 6 to 8. The repellent may be acidic (pH 7 or less, for example 6 or less).

[Hardening agent]
The repellent agent may include a curing agent (an active hydrogen reactive compound or an active hydrogen containing compound).

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

The curing agent may include 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, 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.

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

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.

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

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 mixtures thereof, 2,4- or 2,6-tolylene diisocyanate or mixtures thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used alone or in combination of two or more.

Examples of polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biurets, allophanates, carbodiimides, uretdione, uretoimine, isocyanurates, and iminooxadiazinedione. These may be used alone or in combination of two or more.

These polyisocyanates can be used alone or in combination of two or more.
As the polyisocyanate compound, it is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of the polyisocyanate compound is blocked with a blocking agent. It is preferable to use a blocked polyisocyanate compound because it is relatively stable even in a solution and can be used in the same solution as the repellent.

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

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

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

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

[Other ingredients]
The repellent may contain other components in addition to the above components. Examples of the other components include polysaccharides, paper strength agents, flocculants, retention improvers, coagulants, binder resins, slip prevention agents, sizing agents, paper strength agents, 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 include other water and/or oil repellents, dispersants, texture adjusters, softeners, flame retardants, paint fixing agents, anti-wrinkle agents, drying speed adjusters, crosslinking agents, film-forming assistants, compatibilizers, antifreeze agents, viscosity adjusters, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrink prevention agents, laundry wrinkle prevention agents, shape retention agents, drape retention agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, dye transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, dirt release agents, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Ciba Specialty Chemicals' Tinopal CBS-X), dye fixatives, and discoloration inhibitors such as 1,4-bis(3-aminopropyl)piperazine. , stain removers, enzymes such as cellulase, amylase, protease, lipase, keratinase, etc. as fiber surface modifiers, foam inhibitors, silk protein powders, surface modified products or emulsified dispersions thereof (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemicals), hydrolyzed silk liquid (Jomo), Silkgen G Soluble S (Ichimaru Falcos)), stain inhibitors (e.g., nonionic polymer compounds consisting of alkylene terephthalate and/or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by GOO Chemical Industry Co., Ltd.), SRC-1 manufactured by Clariant Japan, etc.) that can impart silk texture and functions such as moisture absorption and release properties, etc. can be blended. These may be used alone or in combination of two or more.

[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, pullulan, etc. The polysaccharide may be a modified polysaccharide having a substitution, in particular a modified polysaccharide having a hydroxyl group or a cationic group introduced therein.

[Paper strength agents, flocculants, retention aids or coagulants]
Examples of the paper strength agent, flocculant, retention aid or coagulant include styrene polymers (styrene/maleic acid polymers, styrene/acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichlorides and polyalkylenepolyamines, dicyandiamide-formaldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin/maleic anhydride polymers.

[Sizing agent]
Examples of sizing agents include cellulose-reactive sizing agents, e.g., rosin-based sizing agents such as rosin-based soaps, rosin-based emulsions/dispersions, cellulose-reactive sizing agents, e.g., anhydride emulsions/dispersions such as alkyl and alkenyl succinic anhydrides (ASA), alkenyl and alkyl ketene dimers (AKD) and polymers, and anionic, cationic and amphoteric polymers of ethylenically unsaturated monomers, e.g., copolymers of styrene and acrylates.

[Antistatic Agent]
Examples of the antistatic agent include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfates, phosphonates, and phosphates; amphoteric antistatic agents such as alkylbetaines and their derivatives, imidazolines and their derivatives, alanines and their derivatives, nonionic antistatic agents such as aminoalcohols and their derivatives, glycerin and its derivatives, and polyethylene glycols and its derivatives. The antistatic agent may be an ion-conductive polymer obtained by polymerizing or copolymerizing monomers having these cationic, anionic, or amphoteric ion-conductive groups. These may be used alone or in combination of two or more.

[Preservatives]
The preservatives are mainly used to enhance the preservative and bactericidal power and to maintain the preservative properties during long-term storage. Examples of the preservatives include isothiazolone organic sulfur compounds, benzisothiazolone organic sulfur compounds, benzoic acids, 2-bromo-2-nitro-1,3-propanediol, etc.

[Ultraviolet absorber]
An ultraviolet absorber is a drug that has an ultraviolet protection effect, and is a component that absorbs ultraviolet light and converts it into infrared light, visible light, etc. Examples of ultraviolet absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, 4-t-butyl-4'-methoxybenzoylmethane, etc.

[Antibacterial Agent]
The antibacterial agent is a component that has the effect of suppressing the growth of bacteria on fibers and further suppressing the generation of unpleasant odors resulting from the decomposition products of microorganisms. Examples of the antibacterial agent include cationic bactericides such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide) zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, polylysine, etc.

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

[Amount of other ingredients]
The amount or total amount of each of the other components may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 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, relative to 100 parts by weight of the polymer. The amount or total amount of each of the 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, relative to 100 parts by weight of the polymer.

<Method of manufacturing treated substrate>
The method of making a repellent treated product of the present disclosure includes treating a substrate with the repellent agent described above.

"Treatment" means that the repellent is applied to the substrate by dipping, spraying, painting, etc. Treatment causes the polymer, which is the active ingredient of the repellent, to penetrate into the substrate and/or adhere to the surface of the substrate.

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

Examples of substrates for textile products include natural fibers of animal or plant origin, such as cotton, hemp, wool, and silk; synthetic fibers, such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers, such as rayon and acetate; inorganic fibers, such as glass fibers, carbon fibers, and asbestos fibers, or mixtures of these fibers. Textile products include woven fabrics, knitted fabrics, and nonwoven fabrics, as well as clothing fabrics and carpets, but the treatment may also be applied to fibers, yarns, and intermediate textile products (e.g., slivers or rovings) before they are made into fabric.

Examples of base materials for paper products include paper made from bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp or thermomechanical pulp, waste paper pulp such as newspaper, magazine, corrugated cardboard or deinked waste paper, paper containers, paper molded articles, etc. Specific examples of paper products include food packaging paper, gypsum board base paper, coated base paper, medium-weight paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-proof liners and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc.

Substrates that can be treated with the repellent of the present disclosure are not limited to textiles or paper products, but also include stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster.

[Processing method]
The repellent of the present disclosure can be applied to a substrate as a treatment agent (particularly a surface treatment agent) by a conventionally known method. The treatment method may be a method in which the repellent of the present disclosure is dispersed and diluted in an organic solvent or water as necessary, and attached to the surface of the substrate by a known method such as dip coating, spray coating, foam coating, etc., and then dried. After drying, a textile product to which the solid components of the repellent are attached is obtained. If necessary, it may be applied together with a suitable crosslinking agent and cured. The repellent of the present disclosure may be used in combination with various additives such as water and/or oil repellents, slip prevention agents, antistatic agents, texture adjusters, softeners, antibacterial agents, flame retardants, paint fixing agents, anti-wrinkle agents, drying speed adjusters, crosslinking agents, film-forming assistants, compatibilizers, antifreeze agents, viscosity adjusters, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, and defoamers. Examples of various additives may be the same as those described in the "other components" of the water repellent composition above. The concentration of the repellent in the treatment agent to be brought into contact with the substrate may be appropriately changed depending on the application, but may be 0.01 to 10% by weight, for example 0.05 to 5% by weight.

The repellent can be applied to the substrate by any of the methods known for treating substrates with liquids. The substrate may be immersed in the repellent, or the solution may be applied or sprayed onto the substrate. The treated substrate is preferably dried and cured by heating to develop liquid 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 is obtained even with low-temperature heating (e.g., 100°C to 140°C). In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes. When the textile product is paper, the paper may be coated with the repellent, or the solution may be applied or sprayed onto the paper, or the paper may be mixed with the pulp slurry before papermaking and treated. The treatment may be an external or internal treatment. Alternatively, the repellent may be applied to the textile product by a cleaning method, for example, a washing application or a dry cleaning method.

[Paper processing]
Examples of the paper substrate include paper, paper containers, and paper molded articles (for example, pulp molds).

The paper can be produced by a conventional papermaking method. An internal treatment method can be used in which the repellent is added to the pulp slurry before papermaking, or an external treatment method can be used in which the repellent is applied to the paper after papermaking.

The internal addition treatment method may mean a treatment method in which a repellent is added to a pulp slurry before papermaking. The internal addition treatment method may include, but is not limited to, one or more of the steps of adding a repellent to a pulp slurry and stirring and mixing it, suction-dehydrating the pulp composition prepared in the above step through a mesh body of a predetermined shape to deposit the pulp composition and form a pulp mold intermediate, and molding and drying the pulp mold intermediate in a heated mold to obtain paper, a paper container, or a paper molded product. The treated paper may be heat-treated, depending on the properties of the paper, after simple drying at room temperature or at a 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 may be particularly 80°C to 180°C. By performing heat treatment in such a temperature range, excellent oil resistance and water resistance, etc. can be exhibited.

The size press for external additive treatment can be divided into the following types according to the coating method:
One application method is a so-called pond-type two-roll size press, in which a coating liquid (size liquid) is supplied to a nip formed by passing paper between two rubber rolls, a coating liquid pool called a pond is created, and the paper is passed through this coating liquid pool to apply the size liquid to both sides of the paper. Other application 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 a pond-type two-roll size press, the size liquid is likely to penetrate into the inside of the paper, and in a surface transfer type, the size liquid component is likely to remain on the surface of the paper. In the surface transfer type, the coating layer is more likely to remain on the surface of the paper than in a pond-type two-roll size press, and the coating layer formed on the surface is greater than in a pond-type two-roll size press. In the present disclosure, performance can be imparted to the paper even when the former pond-type two-roll size press is used. The paper thus treated can exhibit excellent oil resistance, water resistance, etc., by optionally accompanying a heat treatment that can 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.

The present disclosure can be used in gypsum board base paper, coated base paper, medium-quality paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-proof liners and metal interleaving 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.

Pulp raw materials that can be used include bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulps such as groundwood pulp, mechanical pulp or thermomechanical pulp, and waste paper pulps such as used newspapers, used magazines, used corrugated cardboard, deinked used paper, etc. Also usable are mixtures of the above pulp raw materials with synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, polyvinyl alcohol, etc.

Sizing agents can be added to improve the water resistance of the paper. Examples of sizing agents are cationic sizing agents, anionic sizing agents, and rosin-based sizing agents (e.g., acidic rosin-based sizing agents, neutral rosin-based sizing agents). The amount of sizing agent may be 0.01 to 5% by weight of the pulp.

If necessary, the paper may contain additives used in the manufacture of paper, such as paper strength enhancers such as starch, modified starch, carboxymethyl cellulose, and polyamide polyamine-epichlorohydrin resin, as well as flocculants, fixing agents, retention improvers, dyes, fluorescent dyes, slime control agents, and defoamers, to the extent that they are commonly used. For example, starch or modified starch may be used. If necessary, repellents may be applied to the paper using starch, polyvinyl alcohol, dyes, coating colors, anti-slip agents, etc., using a size press, gate roll coater, building blade coater, calendar, etc.

In the case of external addition, the amount of the liquid repellent compound contained in the coating layer is preferably 0.01 to 2.0 g/ ^m2 , particularly preferably 0.1 to 1.0 g/ ^m2 . The coating layer may be formed from the repellent and starch and/or modified starch. The solid content of the paper repellent in the coating layer is preferably 2 g/ ^m2 or less.
In the case of internal addition, it is preferable to mix the repellent with the pulp so that the amount of the 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, and particularly 0.2 to 5.0 parts by weight, per 100 parts by weight of the pulp forming the paper.

In the case of external addition, oil resistance can also be imparted to paper by using a so-called pond-type two-roll size press process, in which the treatment liquid is stored between rolls and the base paper is passed through the treatment liquid between the rolls at any roll speed and nip pressure.

In the external additive treatment, the paper substrate may contain additives such as sizing agents, strength agents, flocculants, retention agents or coagulants. The additives may be nonionic, cationic, anionic or amphoteric. The ionic charge density of the additives may be -10000 to 10000 μeq/g, preferably -4000 to 8000 μeq/g, more preferably -1000 to 7000 μeq/g. Additives such as sizing agents, strength agents, flocculants, retention agents or coagulants (solids or active ingredients) can generally be used in amounts of 0.1 to 10% by weight (e.g., 0.2 to 5.0% by weight) based on the pulp. In the case of paper substrates containing cationic additives (e.g., sizing agents, strength agents, flocculants, retention agents or coagulants), it is preferred that the repellent is anionic.

In the internal addition process, it is preferable to make a pulp slurry having a pulp concentration of 0.5 to 5.0% by weight (e.g., 2.5 to 4.0% by weight). Additives (e.g., sizing agents, paper strength agents, flocculants, retention agents, coagulants, etc.) and liquid repellent compounds can be added to the pulp slurry. Examples of additives (e.g., sizing agents, paper strength agents, flocculants, retention agents, or coagulants) include alkylketene dimers, alkenyl succinic anhydrides, styrene polymers (styrene/maleic acid polymers, styrene/acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichlorides and polyalkylenepolyamines, dicyandiamide-formaldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin/maleic anhydride polymers.

[Pretreatment of textile products]
The textile product may be pretreated before being treated with the repellent of the present disclosure. Pretreatment of the textile product may impart excellent fastness to the textile product after treatment with the repellent.

Examples of pretreatments for textile products include cationization treatments such as by reaction with reactive quaternary ammonium salts, anionization treatments such as sulfonation, carboxylation, and phosphation, acetylation treatments after anionization treatments, benzoylation treatments, carboxymethylation treatments, grafting treatments, tannic acid treatments, and polymer coating treatments.

The method for pretreating a textile product is not limited, but the textile product can be pretreated by a conventionally known method. The pretreatment liquid may be dispersed and diluted in an organic solvent or water as necessary, and applied to the surface of the textile product 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 depending on the desired degree of treatment. As an example of a method for pretreating a textile product, a method for pretreating a textile product with a hydrocarbon-based water repellent will be described in detail.

The method for pretreating a textile product may ^include a step of providing a fiber with at least one functional group (hereinafter sometimes referred to as a "specific functional group") selected from the group consisting of a monovalent group represented by -SO ₃ M ¹ (wherein M 1 represents a monovalent cation), a monovalent group represented by -COOM ² (wherein M ² represents a monovalent cation) ^{, and a monovalent group represented by -O-P(O)(OX 1 )} (OX 2 ) (wherein X ¹ and X ² each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms).

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.

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

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

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

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

A phenol-based polymer can be used as the compound having the above-mentioned —SO ₃ M ^1. Such a phenol-based polymer can be, for example, one containing at least one compound represented by the following general formula.

［式中、Ｘ^２は－ＳＯ_３Ｍ^３（式中、Ｍ^３は１価のカチオンを示す）又は下記一般式で表される基を表し、ｎは２０～３０００の整数である。］

[In the formula, ^{X2 represents} _-SO3M3 (wherein ^M3 represents a monovalent cation) or a group represented by the following general formula, and n is an integer of 20 to 3000.]

［式中、Ｍ^４は１価のカチオンを表す。］

[In the formula, ^M4 represents a monovalent cation.]

The above ^M3 includes H, K, Na, and an ammonium ion which may have a substituent.

The above ^M4 includes H, K, Na, or an ammonium ion which may have a substituent.

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.

The compound having the above-mentioned ^-COOM2 includes a polycarboxylic acid polymer.

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

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

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

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

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

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

［式中、Ｘ^１又はＸ^２は上記と同義であり、Ｘ^３は炭素数１～２２のアルキル基を示す。］ An example of the compound having the above-mentioned --O--P(O)(OX ¹ )(OX ² ) is a phosphate compound represented by the following general formula:

[In the formula, ^X1 and ^X2 are as defined above, and ^X3 represents an alkyl group having 1 to 22 carbon atoms.]

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

From the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use lauryl phosphate ester or decyl phosphate ester.

For example, commercially available phosphate ester compounds such as "Phosphanol ML-200" (product name, manufactured by Toho Chemical Industry Co., Ltd.) can be used.

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

Examples of methods for treating textile materials with the above pretreatment liquid include padding, immersion, spraying, and coating. Examples of padding include the padding device described on pages 396-397 of Textile Dyeing and Processing Dictionary (published by Nikkan Kogyo Shimbun, 1963) and pages 256-260 of Color Dyeing Chemistry III (published by Jikkyo Publishing Co., Ltd., 1975). Examples of coating include the coating machine described on pages 473-477 of Dyeing and Finishing Equipment Directory (published by Sen-i-sha, 1981). Examples of immersion include the batch dyeing machine described on pages 196-247 of Dyeing and Finishing Equipment Directory (published by Sen-i-sha, 1981), and include liquid flow dyeing machines, air flow dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, and cheese dyeing machines. Examples of spray treatment include air spraying, which uses compressed air to spray the treatment liquid in the form of a mist, and air spraying using a liquid pressure atomization method. The treatment conditions, such as the concentration of the treatment liquid and the heat treatment after application, can be appropriately adjusted taking into account various conditions such as the purpose and performance. In addition, if the pretreatment liquid contains water, it is preferable to dry the pretreatment liquid after it is applied to the fiber material in order to remove the water. There is no particular limit to the drying method, and either a dry heat method or a wet heat method may be used. There is also no particular limit to the drying temperature, and it may be, for example, dried at room temperature to 200°C for 10 seconds to several days. If necessary, heat treatment at a temperature of 100 to 180°C for about 10 seconds to 5 minutes after drying may be performed.

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

The processing temperature for the immersion process can be 60 to 130°C. The processing time can be 5 to 60 minutes.

In the functional group introduction process using a pretreatment liquid, it is preferable to carry out the treatment in an amount such that the amount of the compound having the specific functional group adhered is 1.0 to 7.0 parts by weight per 100 parts by weight of the textile material. Within this range, it is possible to achieve a high level of both durable water repellency and texture.

It is preferable to adjust the pH of the pretreatment liquid to 3 to 5. The pH can be adjusted using a pH adjuster such as acetic acid or malic acid.

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

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 in excess. An example of a removal method is washing with water. By removing the compound sufficiently, it is possible to prevent the development of water repellency in the subsequent water repellent treatment from being hindered, and in addition, the feel of the resulting textile product is improved. In addition, it is preferable to thoroughly dry the resulting functional group-containing fiber before contacting it with a hydrocarbon-based water repellent agent.

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

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

Although the embodiments have been described above, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims.

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

<Test Method>
The test procedure is as follows.

[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). GPC was performed using tetrahydrofuran or DMF as a developing solution, and a Shodex LF-404 and KF-805L were used as columns, and the molecular weight and other values were calculated in terms of PMMA.

[Copolymer Composition by NMR (Nuclear Magnetic Resonance)]
For 1H-NMR (nuclear magnetic resonance) measurements, deuterated chloroform was used as the solvent.

[Measurement of Thermal Properties by Differential Scanning Calorimetry (DSC)]
The melting point of the polymer was calculated by differential scanning calorimetry (DSC). In the DSC measurement, the sample was cooled to -20°C under a nitrogen atmosphere, heated to 180°C at 10°C/min, cooled again to -20°C, and the melting point observed during the subsequent heating to 180°C at 10°C/min was measured. In the case of a polymer in which multiple melting peaks appear, the peak with the largest heat of fusion resulting from the melting of the long-chain alkyl group was taken as the melting point. The glass transition point (glass transition temperature) was determined as the temperature indicated by the midpoint between the intersection of the extension line of each baseline before and after the secondary transition of the DSC curve and the tangent line at the inflection point of the DSC curve.

[Static contact angle measurement]
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 prepare a coating film. 2 μL of water or hexadecane (n-HD) was dropped onto the coating film, and the static contact angle 1 second after the drop was attached was measured using a fully automatic contact angle meter (DropMaster 701 manufactured by Kyowa Interface Science Co., Ltd.).

[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.) having a thickness of 250 μm, and heated at 80° C. for 20 minutes to prepare a coating film.
A checkerboard pattern of 1 mm intervals was cut into the coating film with a cutter knife, cellophane tape was applied and then peeled off. Peeling was evaluated as follows: 0-15% peeled area was rated as ◯, 15-50% peeled area was △, and 50% or more peeled area was rated as ×.

[Water repellency test]
A treatment solution having a solid concentration of 1.5% was prepared using chloroform as a solvent, and a polyester fabric (PET) was immersed in this test solution and passed through a mangle to evaluate the water repellency of the heat-treated test fabric.
The test was carried out according to the spray method of JIS-L-1092 (AATCC-22), and the water repellency of the treated fabric was evaluated with a grade of ◯ or ×.
◯: No wetting is observed. ×: Wetting is observed throughout.

[Making paper plates]
The wood pulp slurry was used to make paper plates (untreated) weighing 10 g in an automatic molding machine.

[Water and oil resistance test]
A treatment solution with a solids concentration of 10% was prepared using chloroform as a solvent. Paper plates were immersed in this test solution, and then 100 mL of water or corn oil was poured onto the heat-treated test plates. The water resistance and oil resistance were evaluated with a grade of O or X depending on whether or not the water or oil soaked in.
〇: No stains on the back ×: Stain on the entire back

<Production Example>
The synthesis and cyclopolymerization of divinyl monomers were carried out as follows.

反応器に、4-(Trifluoromethyl)salicylic acid（250g）、N-(2-Hydroxyrthyl)acrylamide（167g）、4-ジメチルアミノピリジン（37g）、ジクロロメタン（2.1Ｌ）を加え、室温で1.5時間攪拌した。０℃冷却後、1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide Hydrochloride（278g）を加え、３時間攪拌し、室温で終夜攪拌した。反応終了後、クエン酸メタノール溶液でクエンチし、分液、カラムクロマトグラフィーで精製し、2-Acrylamidoethyl 4-(trifluoromethyl)salicylate（272g）を収率74％で得た。

反応器に、2-Acrylamidoethyl 4-(trifluoromethyl)salicylate（101g）、テトラヒドロフラン（1.4Ｌ）を加え、０℃攪拌下、アクリル酸クロライド（28mＬ）、トリエチルアミン（51mＬ）を加え、４時間攪拌した。反応終了後、メタノールでクエンチし、ろ過、カラムクロマトグラフィーで精製し、ジビニルモノマー１（93g）を収率78％で得た。 [Production Example 1: Synthesis of Divinyl Monomer 1]

Into a 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 stirred at room temperature for 1.5 hours. After cooling to 0°C, 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide Hydrochloride (278 g) was added and stirred for 3 hours and then overnight at room temperature. After completion of the reaction, the mixture was quenched with a citric acid methanol solution, separated, and purified by column chromatography to obtain 2-Acrylamidoethyl 4-(trifluoromethyl)salicylate (272 g) in a yield of 74%.

2-Acrylamidoethyl 4-(trifluoromethyl)salicylate (101 g) and tetrahydrofuran (1.4 L) were added to a reactor, and acrylic acid chloride (28 mL) and triethylamine (51 mL) were added under stirring at 0° C., and the mixture was stirred for 4 hours. After the reaction was completed, the mixture was quenched with methanol, filtered, and purified by column chromatography to obtain divinyl monomer 1 (93 g) in a yield of 78%.

反応器に、エチレングリコールモノビニルエーテル（196g）、トリエチルアミン（101g）、ジクロロメタン（1.9Ｌ）を加え、０℃攪拌下、アクリル酸クロライド（168g）を滴下、さらに室温で攪拌した。反応終了後、水でクエンチし、分液、カラムクロマトグラフィーで精製し、2-(vinyloxy)ethyl acrylate（124g）を収率47％で得た。

反応器に、メタクリル酸（271g）、2-(vinyloxy)ethyl acrylate（124g）、ジクロロメタン（1.1Ｌ）を加え、60℃ で86時間、加熱攪拌した。反応終了後、5%炭酸水素ナトリウム水溶液を加え、分液、カラムクロマトグラフィーで精製し、ジビニルモノマー２（189g）を収率95％で得た。 [Production Example 2: Synthesis of Divinyl Monomer 2]

Ethylene glycol monovinyl ether (196 g), triethylamine (101 g), and dichloromethane (1.9 L) were added to a reactor, and acrylic acid chloride (168 g) was added dropwise under stirring at 0° C., followed by stirring at room temperature. After the reaction was completed, the mixture was quenched with water, separated, and purified by column chromatography to obtain 2-(vinyloxy)ethyl acrylate (124 g) in a yield of 47%.

Methacrylic acid (271 g), 2-(vinyloxy)ethyl acrylate (124 g), and dichloromethane (1.1 L) were added to a reactor and stirred under heating at 60° C. for 86 hours. After the reaction was completed, a 5% aqueous solution of sodium hydrogen carbonate was added, and the mixture was separated and purified by column chromatography to obtain divinyl monomer 2 (189 g) in a yield of 95%.

反応器に、ジビニルモノマー１（715.7 mg）、AIBN（7.2 mg）、DME（19.7 mＬ）をアルゴン雰囲気下で加え、60℃ で6時間、加熱攪拌した後、-78℃に冷却して反応停止した。2つのビニル基（アクリレート; A, アクリルアミド; Am）の消費率は、1H-NMR（CDCl3）より共に88%であった。SECより、数平均分子量（Mn）は10300、分子量分布（Mw/Mn）は2.49であった。 [Production Example 3: Cyclopolymerization of Divinyl Monomer 1]

Divinyl monomer 1 (715.7 mg), AIBN (7.2 mg), and DME (19.7 mL) were added to the reactor under an argon atmosphere, and the mixture was heated and stirred at 60°C for 6 hours, and then cooled to -78°C to stop the reaction. The consumption rates of the two vinyl groups (acrylate; A, acrylamide; Am) were both 88% by 1H-NMR (CDCl3). The number average molecular weight (Mn) was 10,300 and the molecular weight distribution (Mw/Mn) was 2.49 by SEC.

反応器に、ジビニルモノマー２（6.85 g）、AIBN（0.02 eq.）、トルエン（300 mＬ）をアルゴン雰囲気下で加え、60℃ で4時間、加熱攪拌した後、-78℃に冷却して反応停止した。2つのビニル基（メタクリレート; M, アクリレート; A）の消費率は、1H-NMR（CDCl3）より共に82%であった。SECより、数平均分子量（Mn）は25300、分子量分布（Mw/Mn）は3.04であった。 [Production Example 4: Cyclopolymerization of Divinyl Monomer 2]

Divinyl monomer 2 (6.85 g), AIBN (0.02 eq.), and toluene (300 mL) were added to the reactor under an argon atmosphere, and the mixture was heated and stirred at 60°C for 4 hours, and then cooled to -78°C to terminate the reaction. The consumption rates of the two vinyl groups (methacrylate; M, acrylate; A) were both 82% by 1H-NMR (CDCl3). The number average molecular weight (Mn) was 25,300 and the molecular weight distribution (Mw/Mn) was 3.04 by SEC.

反応器に、ジビニルモノマー１（2.5g）、AIBN（23 mg）、DME（70 mＬ）をアルゴン雰囲気下で加え、60℃ で6時間、加熱攪拌した後、-78℃に冷却して反応停止した。SECより、数平均分子量（Mn）は7400、分子量分布（Mw/Mn）は2.31であった。 Production Example 5: Scale-up of cyclopolymerization of divinyl monomer 1

Divinyl monomer 1 (2.5 g), AIBN (23 mg), and DME (70 mL) were added to a reactor under an argon atmosphere, and the mixture was heated and stirred at 60°C for 6 hours, and then cooled to -78°C to stop the reaction. SEC revealed that the number average molecular weight (Mn) was 7,400 and the molecular weight distribution (Mw/Mn) was 2.31.

<Examples and Comparative Examples>
A polymer was synthesized as follows: The obtained polymer was used to carry out the above-mentioned tests.

反応器に、製造例３の重合溶液（5 mＬ; モノマーユニット0.5 mmol）、ドデシルアミン（10eq.）を加え、室温で終夜攪拌した後、メタノール透析で精製した。SECより、数平均分子量（Mn）は10400、分子量分布（Mw/Mn）は1.85であった。 Example 1: Alternating Copolymer 1 (Conversion with C12 Amine)

The polymerization solution (5 mL; monomer unit 0.5 mmol) of Production Example 3 and dodecylamine (10 eq.) were added to a reactor, stirred overnight at room temperature, and purified by methanol dialysis. SEC showed that the number average molecular weight (Mn) was 10,400 and the molecular weight distribution (Mw/Mn) was 1.85.

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.

Example 3
The reaction was carried out in the same manner as in Example 1, except that the amine was changed to n-octylamine.

Example 4
The reaction was carried out in the same manner as in Example 1, except that the amine was changed to 2-ethylhexylamine.

Example 5
The reaction was carried out in the same manner as in Example 1, except that the amine was changed to cyclooctylamine.

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.

Example 7
The polymerization solution (5 mL; monomer unit 0.5 mmol) of Production Example 3 and 4-tBu-benzylamine (10 eq.) were added to the reactor and stirred at room temperature overnight to convert one side chain. Furthermore, to complete the conversion to a hydroxyethyl group, n-butylamine (5 eq.) was added and stirred at room temperature overnight, and then purified by methanol dialysis. SEC showed that the number average molecular weight (Mn) was 10,300 and the molecular weight distribution (Mw/Mn) was 2.09.

反応器に、N-ドデシルアクリルアミド（166 mg）、N-ヒドロキシエチルアクリルアミド（80 mg）、AIBN（2.3 mg）、DMF（7 mＬ）をアルゴン雰囲気下で加え、60℃ で48時間、加熱攪拌した後、-78℃に冷却して反応停止した。SECより、数平均分子量（Mn）は5500、分子量分布（Mw/Mn）は1.71であった。1H-NMR（CDCl3）より、組成比1:1のランダム共重合体であることを確認した。 [Example 8: Random Copolymer 1]

N-dodecylacrylamide (166 mg), N-hydroxyethylacrylamide (80 mg), AIBN (2.3 mg), and DMF (7 mL) were added to a reactor 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. SEC revealed that the number average molecular weight (Mn) was 5,500 and the molecular weight distribution (Mw/Mn) was 1.71. 1H-NMR (CDCl3) confirmed that the product was a random copolymer with a composition ratio of 1:1.

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

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.

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

反応器に、環化ポリマー２（0.18 g）、THF（20 mＬ）、トリフルオロ酢酸（1 mＬ）、水（0.5 mＬ）を加え、30℃で24時間、攪拌した。反応終了後、溶媒留去し、ジエチルエーテル再沈殿で精製し、中間体ポリマーを得た。
中間体ポリマー（0.18 g）、オクタデシルイソシアネート（1.05 eq.）、DMSO（5 mＬ）、THF（5 mＬ）を加え、室温で終夜攪拌した後、メタノール透析で精製した。SECより、数平均分子量（Mn）は15100、分子量分布（Mw/Mn）は3.11であった。 Example 12: Alternating Copolymer 2 (Cleavage with TFA, Conversion with C18 Isocyanate)

Cyclized polymer 2 (0.18 g), THF (20 mL), trifluoroacetic acid (1 mL), and water (0.5 mL) were added to a reactor and stirred for 24 hours at 30° C. After completion of the reaction, the solvent was distilled off, and the mixture was purified by reprecipitation with diethyl ether to obtain an intermediate polymer.
The intermediate polymer (0.18 g), octadecyl isocyanate (1.05 eq.), DMSO (5 mL), and THF (5 mL) were added and stirred overnight at room temperature, and then purified by methanol dialysis. SEC showed that the number average molecular weight (Mn) was 15,100 and the molecular weight distribution (Mw/Mn) was 3.11.

Example 13
The reaction was carried out in the same manner as in Example 12, except that octadecyl isocyanate was changed to dodecyl isocyanate and the solvent was changed to THF alone.

反応器に、製造例３の重合溶液（14 mＬ; モノマーユニット1.4 mmol）にシクロオクチルアミン0.89g（7mmol、5eq.）／ドデシルアミン1.30g（7mmol、5eq.）を加え、室温で２４時間攪拌した。
次いで、Spectra/Por 7 透析膜に反応溶液を入れて、メタノール(2.0 Ｌ)中で透析を行った。約5時間毎にメタノールを入れ替えて、4回実施した。得られた白色懸濁液を減圧濃縮して、アモルファス状の固体の交互ポリマー0.25 gを得た。NMR分析からシクロオクチルアミンとドデシルアミンの導入比率(モル比)は1：3.25であった。
SECより、数平均分子量（Mn）は8613、分子量分布（Mw/Mn）は1.38であった。 [Example 14: Synthesis of alternating copolymers using two types of amines (conversion using C12 amine and cyclooctylamine)]

In a reactor, 0.89 g (7 mmol, 5 eq.) of cyclooctylamine/1.30 g (7 mmol, 5 eq.) of dodecylamine were added to the polymerization solution of Production Example 3 (14 mL; monomer unit 1.4 mmol) and stirred at room temperature for 24 hours.
The reaction solution was then placed in a Spectra/Por 7 dialysis membrane and dialyzed in methanol (2.0 L). The methanol was replaced about every 5 hours, and dialyzed four times. The resulting white suspension was concentrated under reduced pressure to obtain 0.25 g of an amorphous solid alternating polymer. NMR analysis showed that the molar ratio of cyclooctylamine to dodecylamine was 1:3.25.
SEC revealed that the number average molecular weight (Mn) was 8613 and the molecular weight distribution (Mw/Mn) was 1.38.

Example 15: Scale-up of the synthesis of alternating copolymers with two types of amines (conversion with C12 amine and cyclooctylamine)
The procedure of Example 14 was scaled up.
In a reactor, 4.45g (35mmol, 5eq.) of cyclooctylamine/6.48g (35mmol, 5eq.) of dodecylamine were added to the polymerization solution (70mL; monomer unit 7mmol) of Production Example 3, and the mixture was stirred at room temperature for 24 hours. The post-treatment was carried out in the same manner as in Example 14, and 1.7g of an amorphous solid alternating polymer was obtained. NMR analysis showed that the amine introduction ratio was cyclooctylamine/dodecylamine = 1:21.03. SEC showed that the number average molecular weight (Mn) was 10514 and the molecular weight distribution (Mw/Mn) was 1.48. As a result of scaling up, the introduction rate of cyclooctylamine was significantly reduced.

反応器に、tBuMA（0.41 mＬ）、C18URA（1.03 g）、AIBN（8.6 mg）、1,4-ジオキサン（5.2 mＬ）をアルゴン雰囲気下で加え、60℃ で22時間、加熱攪拌した後、-78℃に冷却して反応停止した。2つのビニル基（メタクリレート; M, アクリレート; A）の消費率は、1H-NMR（CDCl3）よりM: 99%, A: 95%であった。SECより、数平均分子量（Mn）は27400、分子量分布（Mw/Mn）は3.95であった。メタノール再沈殿で精製し、1H-NMR（CDCl3）より、組成比1:1のランダム共重合体であることを確認した。
反応器に、共重合体のtBuMAユニット濃度2 mmolに対し、HCl（100 eq.）、1,4-ジオキサン（200 mＬ）を加え、90℃で12時間、加熱攪拌した。反応終了後、溶媒留去し、1H-NMR（CDCl3）より、tBu基が脱保護されたランダム共重合体２であることを確認した。 [Comparative Example 1: Random Copolymer 2]

tBuMA (0.41 mL), C18URA (1.03 g), AIBN (8.6 mg), and 1,4-dioxane (5.2 mL) were added to the reactor under an argon atmosphere, and the mixture was heated and stirred at 60°C for 22 hours, after which it was cooled to -78°C to stop the reaction. The consumption rates of the two vinyl groups (methacrylate; M, acrylate; A) were M: 99%, A: 95% by 1H-NMR (CDCl3). The number average molecular weight (Mn) was 27,400 and the molecular weight distribution (Mw/Mn) was 3.95 by SEC. The product was purified by methanol reprecipitation, and it was confirmed to be a random copolymer with a composition ratio of 1:1 by 1H-NMR (CDCl3).
To a reactor, HCl (100 eq.) and 1,4-dioxane (200 mL) were added to the copolymer (tBuMA unit concentration: 2 mmol), and the mixture was heated and stirred at 90° C. for 12 hours. After the reaction was completed, the solvent was distilled off, and it was confirmed by 1H-NMR (CDCl3) that the copolymer was a random copolymer 2 in which the tBu groups had been deprotected.

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

反応器に、N-ドデシルアクリルアミド（4.79 g）、AIBN（32.8 mg）、THF（5.2 mＬ）をアルゴン雰囲気下で加え、60℃ で3時間、加熱攪拌した後、-78℃に冷却して反応停止した。SECより、数平均分子量（Mn）は27200、分子量分布（Mw/Mn）は1.97であった。 [Comparative Example 3] Homopolymer 1

N-dodecylacrylamide (4.79 g), AIBN (32.8 mg), and THF (5.2 mL) were added to a reactor under an argon atmosphere, and the mixture was heated and stirred at 60°C for 3 hours, and then cooled to -78°C to stop the reaction. SEC revealed that the number average molecular weight (Mn) was 27,200 and the molecular weight distribution (Mw/Mn) was 1.97.

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.

〔result〕
The results are summarized in the table below.

[Table 1]
(Static contact angle test (water))

[Table 2]
(Static Contact Angle Test (n-HD))

[Table 3]
(Adhesion test)

[Table 4]
(Water repellency test (textile))

[Table 5]
(Static Contact Angle Test (Water and n-HD))

[Table 6]
(Water and oil resistance test (paper))

[Abbreviation]
The abbreviations have the following meanings:
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 (10)

A repellent comprising a polymer selected from polymers (I) to (II) defined below.
(I) A compound of the following formula:
-[CH ₂ C(-Q ¹ )C(=O)R ¹ ]-
[Wherein,
^Q1 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 , in each occurrence, is independently a monovalent organic group having a hydrocarbon group having from 4 to 40 carbon atoms.
and a repeating unit (1) represented by the following formula:
-[CH ₂ C(-Q ² )C(=O)NHR ² OH]-
[Wherein,
^Q2 is a hydrogen atom, a monovalent organic group or a halogen atom;
^R2 is an alkylene group having 1 to 10 carbon atoms.
A polymer having a repeating unit (2) represented by
A polymer in which the molar ratio of the repeating unit (1) to the repeating unit (2) (repeating unit (1)/repeating unit (2)) is 0.5 or more and 2 or less .
(II) A polymer having an alternating sequence (A) consisting of the repeating unit (1) and the repeating unit (2) . The repellent according to claim 1, comprising polymer (II). The repellent according to claim 1, wherein 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 ) is 30% by weight or more in the polymer. The repellent of claim 1, comprising a liquid medium that is water, an organic solvent, or a mixture of water and an organic solvent. The repellent according to claim 1, which is for textiles or paper. A substrate having the polymer in the repellent agent according to any one of claims 1 to 5 adhered thereto. A method for producing a treated substrate comprising applying a repellent agent according to any one of claims 1 to 5 to a substrate. A repellent comprising a polymer, which is polymer (II) as defined below.
(II) a compound of the following formula:
-[CH ₂ C(-Q ¹ )C(=O)R ¹ ]-
[Wherein,
^Q1 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 , in each occurrence, is independently a monovalent organic group having a hydrocarbon group having from 4 to 40 carbon atoms.
and a repeating unit (1) represented by the following formula:
-[CH ₂ C(-Q ² )C(=O)NHR ² OH]-
[Wherein,
^Q2 is a hydrogen atom, a monovalent organic group or a halogen atom;
^R2 is an alkylene group having 1 to 10 carbon atoms.
and (2) an alternating sequence (A) represented by the following repeating unit:
The repeating unit (1) comprises two or more types of R ¹¹ . The repellent according to claim 8 , wherein the amount of the alternating sequence (A 2 ) is 30% by weight or more in the polymer. A method for producing a repellent containing a polymer (II), comprising the steps of:
The following formula:
CH ₂ =C(-Q ¹ )C(=O)-X ^A -OR ² NHC(=O)C(-Q ² )=CH ₂
[Wherein,
^Q1 is a hydrogen atom, a monovalent organic group or a halogen atom;
^XA is a group removable by aminolysis;
^R2 is an alkylene group having 1 to 10 carbon atoms;
^Q2 is a hydrogen atom, a monovalent organic group, or a halogen atom.
to obtain a precursor (A) by cyclopolymerizing the precursor (A) and a divinyl monomer represented by the following formula:
_NH2 ( ^R11 ) or NH( ^R11 ) ₂
[In the formula, R ¹¹ is independently in each occurrence a monovalent organic group having a hydrocarbon group having 4 to 40 carbon atoms.]
With an amine compound represented by the formula
The polymer (II) has the following formula:
-[CH ₂ C(-Q ¹ )C(=O)R ¹ ]-
[Wherein,
^Q1 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 , in each occurrence, is independently a monovalent organic group having a hydrocarbon group having from 4 to 40 carbon atoms.
and a repeating unit (1) represented by the following formula:
-[CH ₂ C(-Q ² )C(=O)NHR ² OH]-
[Wherein,
^Q2 is a hydrogen atom, a monovalent organic group or a halogen atom;
^R2 is an alkylene group having 1 to 10 carbon atoms.
and an alternating sequence (A) consisting of a repeating unit (2) represented by
A method for producing a repellent comprising a polymer (II), wherein the repeating unit (1) contains two or more types of R ¹¹ .