JP2024063767A - Oilproofing agent - Google Patents

Abstract

To provide a novel oilproofing agent capable of imparting oil resistance to a base material (e.g., fiber and paper).SOLUTION: A novel oilproofing agent capable of imparting oil resistance to a base material is provided which contains a compound expressed by the formula in the figure. In the formula, Y- is a counter anion, X is a direct bond or a group having a valence of n+m, R is a C6-40 linear or branched monovalent hydrocarbon group, Z is a C1-6 alkyl group, a C1-4 alkoxy group, -N(R')2 (where R' is a hydrogen atom or a C1-4 hydrocarbon group), a hydroxyl group, a carboxyl group, or a halogen atom, m is an integer of 1-10, n is an integer of 1-3, and p is an integer of 0-5, and -X-Rn does not include -O-R or -NHC(=O)-R.SELECTED DRAWING: None

Description

This disclosure relates to oil-resistant agents.

In recent years, research has been conducted into materials and methods that can impart water repellency, oil repellency, etc. to various substrates. Patent Document 1 discloses a method for imparting water repellency and oil repellency to a fiber substrate by using a combination of a pyridinium compound and a fluorine compound. In the invention described in Patent Document 1, a fluorine-containing compound is an essential component.

U.S. Pat. No. 3,034,925

The objective of this disclosure is to provide a novel oil-resistant agent that can impart oil resistance to substrates (e.g., textiles, paper).

［式中、
Ｙ^－はカウンターアニオンであり、
Ｘは直接結合又はｎ＋ｍ価の基であり、
Ｒは炭素数６以上４０以下の直鎖状または分岐鎖状の一価の炭化水素基であり、
Ｚは炭素数１～６のアルキル基、炭素数１～４のアルコキシ基、－Ｎ（Ｒ’）_２（式中、Ｒ’は、水素原子又は炭素数１～４の炭化水素基である）、ヒドロキシル基、カルボキシル基、又はハロゲン原子であり、
ｍは１以上１０以下の整数であり、
ｎは１以上３以下の整数であり、
ｐは０以上５以下の整数である。］
で表される化合物を含み、
－Ｘ－Ｒ_ｎは－Ｏ－Ｒ及び－ＮＨＣ（＝Ｏ）－Ｒを含まない、耐油剤。
［項２］
Ｙ^－は、ハロゲン化物イオン、スルホン酸イオン、リン酸イオン、及びカルボン酸イオンからなる群から選択される少なくとも一種である、項１に記載の耐油剤。
［項３］
Ｘは、直接結合、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｃ（＝ＮＲ’）－、－Ｓ－、－Ｓ（＝Ｏ）_２－、－ＮＲ’－、－Ｃ（ＯＲ’）Ｒ’－、－Ｃ（ＯＲ’）（－）_２、－Ｎ（－）_２、２～４価の炭素数１～２０の脂肪族炭化水素基、２～４価の炭化水素芳香環、及び２～４価のヘテロ環
［式中、Ｒ’は、水素原子又は炭素数１～４の炭化水素基である。］
からなる群から選択される少なくとも一種以上で構成されるｎ＋ｍ価の基である、項１又は２に記載の耐油剤。
［項４］
Ｒの炭素数が１２以上である、項１～３のいずれか一項に記載の耐油剤。
［項５］
前記化合物の融点が４０℃以上である、又は融点が存在しない、項１～４のいずれか一項に記載の耐油剤。
［項６］
前記化合物のｎ－ヘキサデカン接触角が１０°以上である、項１～５のいずれか一項に記載の耐油剤。
［項７］
液状媒体を含み、
前記耐油剤の粘度が、前記化合物濃度１４．８ｍｇ／ｍＬ、２０℃において、５ｃＰ以上１００ｃＰ以下である、項１～６のいずれか一項に記載の耐油剤。
［項８］
水分散液である、項１～７のいずれか一項に記載の耐油剤。
［項９］
紙用である、項１～８のいずれか一項に記載の耐油剤。
［項１０］
フッ素化合物を含まない、項１～９のいずれか一項に記載の耐油剤。
［項１１］
項１～１０のいずれか一項に記載の耐油剤における前記化合物が付着した、又は項１～１０のいずれか一項に記載の耐油剤における前記化合物が繊維の水酸基に修飾された、繊維製品。
［項１２］
項１～１０のいずれか一項に記載の耐油剤における前記化合物が付着した、又は項１～１０のいずれか一項に記載の耐油剤における前記化合物が繊維の水酸基に修飾された、耐油紙。
［項１３］
項１～１０のいずれか一項に記載の耐油剤における前記化合物が付着した、又は項１～１０のいずれか一項に記載の耐油剤における前記化合物が繊維の水酸基に修飾された、ガラス製品。
［項１４］
食品包装材又は食品容器である、項１２に記載の耐油紙。
［項１５］
項１～１０のいずれか一項に記載の耐油剤で紙を外添処理又は内添処理する工程を含む、耐油紙の製造方法。
［項１６］
下記式：

［式中、
Ｙ^－はカウンターアニオンであり、
Ｒは炭素数６以上４０以下の直鎖状または分岐鎖状の一価の炭化水素基であり、
Ｚは炭素数１～６のアルキル基、炭素数１～４のアルコキシ基、－Ｎ（Ｒ’）_２（式中、Ｒ’は、水素原子又は炭素数１～４の炭化水素基である）、ヒドロキシル基、カルボキシル基、又はハロゲン原子であり、
ｐは０以上５以下の整数である。］
で表される化合物。
［項１７］
下記式：

［式中、
Ｙ^－はカウンターアニオンであり、
Ｒは炭素数６以上４０以下の直鎖状または分岐鎖状の一価の炭化水素基であり、
Ｚは炭素数１～６のアルキル基、炭素数１～４のアルコキシ基、－Ｎ（Ｒ’）_２（式中、Ｒ’は、水素原子又は炭素数１～４の炭化水素基である）、ヒドロキシル基、カルボキシル基、又はハロゲン原子であり、
ｐは０以上５以下の整数である。］
で表される化合物。
［項１８］
下記式：

［式中、
Ｙ^－はカウンターアニオンであり、
Ｘは直接結合又はｎ＋ｍ価の基であり、
Ｒは炭素数６以上４０以下の直鎖状または分岐鎖状の一価の炭化水素基であり、
Ｚは、炭素数１～６のアルキル基、炭素数１～４のアルコキシ基、－Ｎ（Ｒ’）_２（式中、Ｒ’は、水素原子又は炭素数１～４の炭化水素基である）、ヒドロキシル基、カルボキシル基、又はハロゲン原子であり、
ｍは１以上１０以下の整数であり、
ｎは１以上３以下の整数であり、
ｐは１以上５以下の整数である。］
で表される化合物を含む水分散体であって、
さらに、非フッ素界面活性剤、シリコーン、ワックス、有機酸、及び硬化剤からなる群から選択される少なくとも一種を含む、水分散体。 The present disclosure includes the following aspects:
[Item 1]
The following formula:

[Wherein,
Y ⁻ is a counter anion,
X is a direct bond or a group having a valence of n+m;
R is a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms,
Z is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -N(R') ₂ (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), a hydroxyl group, a carboxyl group, or a halogen atom;
m is an integer of 1 to 10,
n is an integer of 1 to 3,
p is an integer of 0 to 5.
The compound includes a compound represented by
An oil resistant agent, where --X--R _n does not include --O--R or --NHC(.dbd.O)--R.
[Item 2]
2. The oil-resistant agent according to item 1, wherein Y ^{1 −} is at least one selected from the group consisting of a halide ion, a sulfonate ion, a phosphate ion, and a carboxylate ion.
[Item 3]
X represents a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O) ₂ -, -NR'-, -C(OR')R'-, -C(OR')(-) ₂ , -N(-) ₂ , a di- to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a di- to tetravalent hydrocarbon aromatic ring, or a di- to tetravalent heterocycle [wherein R' represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.]
Item 3. The oil-resistant agent according to item 1 or 2, wherein the n+m valent group is at least one selected from the group consisting of:
[Item 4]
Item 4. The oil-resistant agent according to any one of Items 1 to 3, wherein R has 12 or more carbon atoms.
[Item 5]
Item 5. The oil-resistant agent according to any one of items 1 to 4, wherein the compound has a melting point of 40° C. or higher or has no melting point.
[Item 6]
Item 6. The oil-resistant agent according to any one of Items 1 to 5, wherein the compound has an n-hexadecane contact angle of 10° or more.
[Item 7]
A liquid medium is included.
Item 7. The oil-resistant agent according to any one of items 1 to 6, wherein the viscosity of the oil-resistant agent is 5 cP or more and 100 cP or less at a compound concentration of 14.8 mg/mL and at 20° C.
[Item 8]
Item 8. The oil-resistant agent according to any one of items 1 to 7, which is an aqueous dispersion.
[Item 9]
Item 9. The oil-proofing agent according to any one of items 1 to 8, which is for paper.
[Item 10]
Item 10. The oil-resistant agent according to any one of items 1 to 9, which does not contain a fluorine compound.
[Item 11]
Item 11. A textile product to which the compound in the oil-resistant agent according to any one of items 1 to 10 is attached, or in which the compound in the oil-resistant agent according to any one of items 1 to 10 is modified on a hydroxyl group of a fiber.
[Item 12]
Item 11. Grease-resistant paper to which the compound in the oil-resistant agent according to any one of items 1 to 10 is attached, or the compound in the oil-resistant agent according to any one of items 1 to 10 is modified on a hydroxyl group of a fiber.
[Item 13]
Item 11. A glass product to which the compound in the oil-resistant agent according to any one of items 1 to 10 is attached, or in which the compound in the oil-resistant agent according to any one of items 1 to 10 is modified on a hydroxyl group of a fiber.
[Item 14]
Item 13. The grease-resistant paper according to item 12, which is a food packaging material or a food container.
[Item 15]
Item 11. A method for producing grease-resistant paper, comprising a step of externally or internally treating paper with the grease-resistant agent according to any one of items 1 to 10.
[Item 16]
The following formula:

[Wherein,
Y ⁻ is a counter anion,
R is a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms,
Z is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -N(R') ₂ (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), a hydroxyl group, a carboxyl group, or a halogen atom;
p is an integer of 0 to 5.
A compound represented by the formula:
[Item 17]
The following formula:

[Wherein,
Y ⁻ is a counter anion,
R is a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms,
Z is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -N(R') ₂ (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), a hydroxyl group, a carboxyl group, or a halogen atom;
p is an integer of 0 to 5.
A compound represented by the formula:
[Item 18]
The following formula:

[Wherein,
Y ⁻ is a counter anion,
X is a direct bond or a group having a valence of n+m;
R is a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms,
Z is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -N(R') ₂ (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), a hydroxyl group, a carboxyl group, or a halogen atom;
m is an integer of 1 to 10,
n is an integer of 1 to 3,
p is an integer of 1 to 5.
An aqueous dispersion comprising a compound represented by the formula:
The aqueous dispersion further comprises at least one selected from the group consisting of a non-fluorinated surfactant, a silicone, a wax, an organic acid, and a curing agent.

The oil-resistant agent of the present disclosure can impart oil resistance to substrates (e.g., textiles, paper).

<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. A cyclic group may contain a chain structure. 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 to 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.

The chemical structures described herein should be understood not to include chemical structures that would be recognized by those skilled in the art as being chemically impossible or highly unstable.

<Oil resistant agent>
The oil-proofing agent in the present disclosure provides oil resistance to a substrate (e.g., a fiber substrate, a paper substrate). The oil-proofing agent in the present disclosure may function as at least one selected from the group consisting of a repellent, a water-repellent, an oil-repellent, and a water-resistant agent, instead of or in addition to an oil-proofing agent.

Due to its structure, compound α, which is the active ingredient in the oil-resistant agent of the present disclosure, has excellent dispersibility in liquid media, and the oil-resistant agent of the present disclosure can have stable performance.

Conventional oil-resistant agents that use polymeric compounds as their active ingredients tend to have a broad molecular weight distribution and contain relatively large amounts of impurities. On the other hand, the active ingredient of the oil-resistant agent of the present invention is a low molecular weight agent, which can narrow (unify) the molecular weight distribution and improve performance.

The oil-resistant agent in the present disclosure includes compound α. The oil-resistant agent in the present disclosure may be compound α alone. The oil-resistant agent in the present disclosure may contain other components such as a liquid medium in addition to compound α.

The oil-resistant 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 oil-resistant agent in the present disclosure can impart oil resistance to the substrate even if it does not contain these fluorine compounds.

The oil-resistant agent of the present disclosure may be preferably used as a dispersion (particularly an aqueous dispersion) together with a liquid medium. The viscosity of the oil-resistant agent may be 1 cP or more, 5 cP or more, 10 cP or more, 30 cP or more, 50 cP or more, 75 cP or more, or 90 cP or more, preferably 5 cP or more, at a compound concentration of 14.8 mg/mL and 20°C. The viscosity of the oil-resistant agent may be 500 cP or less, 300 cP or less, 200 cP or less, 100 cP or less, 75 cP or less, 50 cP or less, 30 cP or less, or 20 cP or less, preferably 100 cP or less, at a compound concentration of 14.8 mg/mL and 20°C.

[Compound α]
The compound α in the present disclosure is capable of adhering to a substrate and imparting liquid repellency to the substrate.

The HD (n-hexadecane) contact angle of compound α may be 10° or more, 15° or more, 25° or more, 35° or more, 55° or more, 55° or more, or 65° or more. The HD contact angle of compound α may be 100° or less, 90° or less, or 75° or less. When compound α has an HD contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (especially oil repellency) to the substrate. The HD contact angle is the static contact angle of compound α with respect to the spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle 1 second after the drop lands.

The water contact angle of compound α may be 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more. The water contact angle of compound α may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When compound α has a water contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (particularly water repellency) to the substrate. The water contact angle is the static contact angle of compound α with respect to the spin-coated film, and is obtained by dropping 2 μL of water onto the spin-coated film and measuring the contact angle 1 second after the drop lands.

The melting point of compound α may be 30°C or higher, 40°C or higher, 60°C or higher, 80°C or higher, 100°C or higher, or 120°C or higher, and is preferably 40°C or higher. The melting point of compound α may be 200°C or lower, 150°C or lower, 100°C or lower, or 50°C or lower. Compound α may not have a melting point.

The molecular weight of compound α may be 200 or more, 300 or more, 500 or more, or 750 or more. The molecular weight of compound α may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

Compound α in the present disclosure may not have any of the following groups: 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 having 4 or more carbon atoms, perfluoroalkyl groups, fluoroalkyl groups, and fluorine atoms. Even if compound α does not contain these fluorine-containing groups, it can impart oil resistance to the substrate.

Compound α in the present disclosure may not have an active hydrogen-containing group. Examples of active hydrogen-containing groups include amino groups (amino groups that are not adjacent to a carbonyl group, for example, a primary amino group or a secondary amino group), hydroxy groups, and carboxyl groups. In particular, compound α in the present disclosure may not have a hydroxy group from the viewpoint of oil resistance.

［式中、
Ｙ^－はカウンターアニオンであり、
Ｘは直接結合又はｎ＋ｍ価の基であり、
Ｒは炭素数６以上４０以下の直鎖状または分岐鎖状の一価の炭化水素基であり、
Ｚは炭素数１～６のアルキル基、炭素数１～４のアルコキシ基、－Ｎ（Ｒ’）_２（式中、Ｒ’は、水素原子又は炭素数１～４の炭化水素基である）、ヒドロキシル基、カルボキシル基、又はハロゲン原子であり、
ｍは１以上１０以下の整数であり、
ｎは１以上３以下の整数であり、
ｐは０以上５以下の整数である。］
で表されてよい。ここで、Ｘ－Ｒ_ｎは－Ｏ－Ｒ及び－ＮＨＣ（＝Ｏ）－Ｒを含まなくてよい。 Compound α has the following formula:

[Wherein,
Y ⁻ is a counter anion,
X is a direct bond or a group having a valence of n+m;
R is a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms,
Z is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -N(R') ₂ (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), a hydroxyl group, a carboxyl group, or a halogen atom;
m is an integer of 1 to 10,
n is an integer of 1 to 3,
p is an integer of 0 to 5.
where X—R _n does not have to include —O—R and —NHC(═O)—R.

[ ^Y- ]
Y ^{1 −} is a counter anion of pyridinium, and examples of Y ^{1 −} may be at least one selected from the group consisting of a halide ion (e.g., a fluoride ion, a chloride ion, a bromide ion, an iodide ion, etc., e.g., a chloride ion), a sulfonate ion, a phosphate ion, and a carboxylate ion.

[X]
X is a direct bond or a group having a valency of n+m. X functions as a linker connecting m pyridinium methylene groups and n R's.

n is the number of Rs bonded to X and may be an integer between 1 and 3. n may be 1 or more, 2 or more, or 3 or more. n may be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

m is the number of pyridinium methylene groups bonded to X and may be an integer of 1 to 10. m may be 1 or more, 2 or more, 4 or more, or 6 or more. m may be 9 or less, 6 or less, or 3 or less, for example, 2 or less.

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

X may be an aliphatic group (unsaturated aliphatic group or saturated aliphatic group) or an aromatic group.

X may have one or more groups selected from the group consisting of an amide group, a urea group, a urethane group, and an imide group. Examples of such X include:
—O—C(═O)—NR′—,
—NR′-C(═O)-,
—NR′-C(═O)-O-,
--NR'-C(=O)-NR'-
—C(═O)—NR′—
—C(═O)—NR′—C(═O)—
[In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.]
The NR′ group in the amide group, urea group, urethane group, and imide group does not have to be adjacent to an aromatic ring.

X is a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O) ₂ -, -NR'-, -C(OR')R'-, -C(OR')(-) ₂ , -N(-) ₂ , a di- to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a di- to tetravalent hydrocarbon aromatic ring, or a di- to tetravalent heterocycle [wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.]
The group may be an n+m valent group composed of at least one selected from the group consisting of:

X is,
X 1 consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O) ₂ -, -NR'-, -C(OR')R'-, -C(OR')(-) ₂ , -N(-) ₂ (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having ¹ to 4 carbon atoms);
X ² is one or more selected from the group consisting of a di- to tetra-valent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a di- to tetra-valent hydrocarbon aromatic ring, and a di- to tetra-valent heterocycle;
In this specification, the left side of the group described as X is bonded to a pyridinium methylene group, and the right side is bonded to R.

[X ¹ ]
^X1 is a non-hydrocarbon linker.

X ¹ is a direct bond or a divalent or higher group. The valence of X ¹ may be 2 to 4, 2 to 3, or 2. It is preferable that X ¹ is not only a direct bond.

The molecular weight of ^X1 may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more. The molecular weight of ^X1 may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

X ¹ is one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O) ₂ -, -NR'-, -C(OR')R'-, -C(OR')(-) ₂ , and -N(-) ₂ (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms). Examples of X ¹ include:
Direct bond,
-O-,
-O-C(=O)-,
—O—C(═O)—O—,
—O—C(═O)—NR′—,
-NR'-,
—NR′-C(═O)-,
—NR′-C(═O)-O-,
—NR′-C(═O)-NR′-,
-C(=O)-,
-C(=O)-O-,
—C(═O)—NR′—,
—C(═O)—NR′—C(═O)—,
-C(=NR')-,
-S-,
_-SO2- ,
_-SO2NR'- ,
-C(OR')R'-,
-C(OR')(-) ₂ ,
-N(-) ₂ , etc., wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
Examples include:

[ ^X2 ]
^X2 is a hydrocarbon or aromatic linker.

^X2 may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). ^X2 may be aliphatic or aromatic. ^X2 may be linear, branched, or cyclic.

^X2 is a divalent or higher group. The valence of ^X2 may be, for example, 2 to 4, 2 to 3, or 2.

The number of carbon atoms in ^X2 may be 1 or more, 2 or more, 3 or more, 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. The number of carbon atoms in ^X2 may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

^X2 is composed of one or more selected from the group consisting of di- to tetravalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, di- to tetravalent aromatic hydrocarbon rings, and di- to tetravalent heterocycles.

The di- to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be a cyclic, branched, or straight chain hydrocarbon group. The di- to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 20 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 20 carbon atoms may be 15 or less, 10 or less, or 5 or less.

Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from a hydrocarbon aromatic ring such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The hydrocarbon aromatic ring may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -N(R') ₂ (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), a hydroxyl group, a carboxyl group, or a halogen atom. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

The divalent to tetravalent heterocycle may be an aliphatic group or an aromatic group. Examples of divalent to tetravalent heterocycles include groups obtained by removing 2 to 4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring-constituting atoms of the heterocycle is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The heterocycle may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -N(R') ₂ (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), a hydroxyl group, a carboxyl group, or a halogen atom. The valence of the heterocycle may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2. X may have one or more (e.g., 1 to 3, especially 1) heterocycle, particularly a triazole ring. X may not have a hydrocarbon ring (e.g., a hydrocarbon aromatic ring, especially a benzene ring).

Examples of ^X2 include:
-Ali-
-Cy-
-Ali(-) ₂
-Cy(-) ₂
(-) ₂ Ali-
(-) ₂ Cy-
(-) ₂ Ali (-) ₂
(-) ₂ Cy(-) ₂
-Ali-Cy-
-Cy-Ali-
-Cy-Ali-Cy-
-Ali-Cy-Ali-
[In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or heterocycle.]
etc.

Specific examples of ^X2 include:
-( _CH2 ) _p- (p is 1 to 20, for example 1 to 10),
A linear hydrocarbon group having 1 to 40 carbon atoms, for example 1 to 10 unsaturated bonds,
a hydrocarbon group having a branched structure and having 1 to 40 carbon atoms, for example 1 to 10 carbon atoms;
-( _CH2 ) _q -Cy-( _CH2 ) _r- (q and r each independently represent an integer of 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle).
etc.

[Examples of X]
Examples of X are as follows: In the following, R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

Examples of X, when X is divalent, include -X ¹ -, -X ¹ -X ² -, -X ¹ -X ² -X ¹ -, -X ¹ -X ² -X ¹ -X ^{2 -} , -X 2 -, -X ² -X ¹ -, -X ² -X ¹ -X ² -, -X ² -X ¹ -X ² -X ¹ -, and the like.

Examples of X, when X is trivalent, include -X ¹ (-) ₂ , -X ¹ -X ² (-) ₂ , -X ¹ -(X ² -) ₂ , -X ¹ -X ² -X ¹ (-) ₂ , -X ¹ -X ² (-X ¹ -) ₂ , -X ¹ -(X ² -X ¹ -) ₂ , -X ¹ -X ² -X ¹ -X ² (-) ₂ , -X ¹ -X ² -X ¹ -(X ² -) _{2 ,} -X ¹ -X ² -(X ¹ -X ² -) _{2 ,} -X ¹ -(X ² -X ¹ -X ² -) ₂ ;
(-) ₂ X ¹ -, (-) ₂ X ¹ -X ² -, (-X ¹ ) ₂ X ² -, (-) ₂ X ¹ -X ² -X ¹ -, (-X ¹ ) ₂ -X ² -X ¹ -, (-X ¹ -X ² ) ₂ -X ¹ -, (-) ₂ X ¹ -X ² -X ¹ -X ² -, (-X ¹ ) ₂ -X ² -X ¹ -X ² -, (-X ¹ -X ² ) ₂ -X ¹ -X ² -, (-X ¹ -X ² -X ¹ ) ₂ -X ² -;
-X ² (-) ₂ , -X ² -X ¹ (-) ₂ , -X ² -(X ¹ -) ₂ , -X ² -X ¹ -X ² (-) ₂ , -X ² -X ¹ (-X ² -) ₂ , -X ² -(X ¹ -X ² -) ₂ , -X ² -X ¹ -X ² -X ¹ (-) ₂ , -X ² -X ¹ -X ² -(X ¹ -) _{2 ,} -X ² -X ¹ -(X ² -X ¹ -) _{2 ,} -X ² -(X ¹ -X ² -X ¹ -) ₂ ;
Examples of such a group include (-) _2X ² -, (-) _2X ² -X ¹ -, (-X ² ) _2X ¹ -, (-) _2X ² -X ¹ -X ² -, (-X ² ) ₂ -X ¹ -X ² -, (-X ² -X ¹ ) ₂ -X ² -, (-) _2X ² -X ¹ -X ² -X ¹ -, (-X ² ) ₂ -X ¹ -X ² -X ¹ -, (-X ² -X ¹ ) ₂ -X ² -X ¹ -, (-X ² -X ¹ -X ² ) ₂ -X ¹ -, and the like.

Examples of X, when X is tetravalent, include -X ¹ (-) ₃ , -X ¹ -X ² (-) ₃ , -X ¹ -(X ² -) ₃ , -X ¹ -X ² -X ¹ (-) ₃ , -X ¹ -X ² (-X ¹ -) ₃ , -X ¹ -(X ² -X ¹ -) 3 , -X ¹ -X ² -X ¹ -X ² (-) ₃ , -X ¹ -X ² -X ¹ -(X ² -) ₃ , -X 1 -X 2 -(X 1 -X 2 -) _{3 ,} -X ¹ -X ² -(X ¹ -X ² -) _{3 ,} -X ¹ -(X ² -X ¹ -X ² -) ₃ ;
(-) ₂ X ¹ (-) ₂ , (-) ₂ X ¹ -X ² (-) ₂ , (-X ¹ ) ₂ X ² (-) ₂ , (-) ₂ X ¹ -X ² -X ¹ (-) ₂ , (-X ¹ ) ₂ -X ² -X ¹ (-) ₂ , (-X ¹ -X ² ) ₂ -X ¹ (-) ₂ , (-) ₂ X ¹ -X ² -X ¹ -X ² (-) ₂ , (-X ¹ ) ₂ -X ² -X ¹ -X ² (-) ₂ , (-X ¹ -X ² ) ₂ -X ¹ -X ² (-) ₂ , (-X ¹ -X ² -X ¹ ) ₂ ^-X2 (-) ₂ ;
(-) ₃ X ¹ -, (-) ₃ X ¹ -X ² -, (-X ¹ ) ₃ X ² -, (-) ₃ X ¹ -X ² -X ¹ -, (-X ¹ ) ₃ -X ² -X ¹ -, (-X ¹ -X ² ) ₃ -X ¹ -, (-) ₃ X ¹ -X ² -X ¹ -X ² -, (-X ¹ ) ₃ -X ² -X ¹ -X ² -, (-X ¹ -X ² ) ₃ -X ¹ -X ² -, (-X ¹ -X ² -X ¹ ) ₃ -X ² -;
-X ² (-) ₃ , -X ² -X ¹ (-) ₃ , -X ² -(X ¹ -) ₃ , -X ² -X ¹ -X ² (-) ₃ , -X ² -X ¹ (-X ² -) ₃ , -X ² -(X ¹ -X ² -) ₃ , -X ² -X ¹ -X ² -X ¹ (-) ₃ , -X ² -X ¹ -X ² -(X ¹ -) _{3 ,} -X ² -X ¹ -(X ² -X ¹ -) _{3 ,} -X ² -(X ¹ -X ² -X ¹ -) ₃ ;
(-) ₂ X ² (-) ₂ , (-) ₂ X ² -X ¹ (-) ₂ , (-X ² ) ₂ X ¹ (-) ₂ , (-) ₂ X ² -X ¹ -X ² (-) ₂ , (-X ² ) ₂ -X ¹ -X ² (-) ₂ , (-X ² -X ¹ ) ₂ -X ² (-) ₂ , (-) ₂ X ² -X ¹ -X ² -X ¹ (-) ₂ , (-X ² ) ₂ -X ¹ -X ² -X ¹ (-) ₂ , (-X ² -X ¹ ) ₂ -X ² -X ¹ (-) ₂ , (-X ² -X ¹ -X ² ) ₂ ^-X1 (-) ₂ ;
Examples of such a group include (-) _3X ² -, (-) _3X ² -X ¹ -, (-X ² ) _3X ¹ -, (-) _3X ² -X ¹ -X ² -, (-X ² ) ₃ -X ¹ -X ² -, (-X ² -X ¹ ) ₃ -X ² -, (-) _3X ² -X ¹ -X ² -X ¹ -, (-X ² ) ₃ -X ¹ -X ² -X ¹ -, (-X ² -X ¹ ) ₃ -X ² -X ¹ -, (-X ² -X ¹ -X ² ) ₃ -X ¹ - and the like.

Preferred examples of X include ^-X1- , -X1- ^{X2- , -X1} -X2- ^X1- , ^{-X1 - X2} (-) ₂ , -( ^X1 ) ₂ - ^X2- (wherein ^X2 is trivalent), -( ^X1 ) _2X2 ⁽ -) ₂ (wherein ^X2 is tetravalent),
-X ² -, -X ² -X ¹ -, -X ² -X ¹ -X ² -, -X ² -X ¹ (-) ₂ , -(X ² ) ₂ -X ¹ - (wherein X ¹ is trivalent), -(X ² ) ₂ X ¹ (-) ₂ (wherein X ¹ is tetravalent)
etc.

X is preferably
-X ¹ -, -X ¹ -X ² -, -X ¹ -X ² -X ¹ -, -X ¹ -X ² (-) ₂ , -(X ¹ ) ₂ -X ² - (wherein X ² is trivalent), -(X ¹ ) ₂ X ² (-) ₂ (wherein X ² is tetravalent),
-X ² -, -X ² -X ¹ -, -X ² -X ¹ -X ² -, -X ² -X ¹ (-) ₂ , -(X ² ) ₂ -X ¹ - (wherein X ¹ is trivalent), or -(X ² ) ₂ X ¹ (-) ₂ (wherein X ¹ is tetravalent).
[Wherein,
^X1 , independently in each occurrence,
Direct bond,
-O-,
-O-C(=O)-,
—O—C(═O)—O—,
—O—C(═O)—NR′—,
-NR'-,
—NR′-C(═O)-,
—NR′-C(═O)-O-,
—NR′-C(═O)-NR′-,
-C(=O)-,
-C(=O)-O-, or -C(=O)-NR'-
—C(═O)—NR′—C(═O)—
[wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.]
and
^X2 is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a divalent aromatic group (e.g., a divalent phenyl group, a divalent triazole group).
This makes it possible to impart good oil resistance to the substrate.

（－）_２Ｃ（ＣＨ_２Ｏ（Ｃ＝Ｏ）ＮＲ’－）_２
［式中、Ｒ’は、各出現において独立して、水素原子又は炭素数１～４の炭化水素基である。］
等が挙げられる。 Further specific examples of X include:
-O-
-NR'-(C=O)-
—NR′—(C═O)—CH ₂ —O—(C═O)—
-NR'-(C=O) _-CH2 -N(-)(C=O)-
—NR′—(C═O)—Ph-O—
--(C.dbd.O)--NR'--
-(C=O)O-

(-) _2C ( _CH2O (C=O)NR'-) ₂
[wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.]
etc.

[R]
R is a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms. R is branched or linear, and more preferably linear. R may be saturated or unsaturated. 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.

[Z]
Z is a group that replaces a ring hydrogen of the pyridinium group and may be an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -N(R') ₂ (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), a hydroxyl group, a carboxyl group, or a halogen atom.

p represents the number of Z's modifying the pyridinium group (how many of the five ring hydrogens of the pyridinium group are substituted) and is an integer of 0 to 5. p may be 0 or more, 1 or more, 2 or more, or 3 or more. p may be 5 or less, 4 or less, 3 or less, 2 or less, or 1 or less, for example, 2 or less (for example, 1 or 0).

[Examples of compound α]
Examples of compound α include compounds represented by the following formula: In the following formula, the above explanations are incorporated for details of Y ⁻ , R, Z and p.

[Production method of compound α]
The method for producing compound α is not limited, but includes a method of reacting pyridine with an R-group-containing alkyl halide, a method of reacting pyridine with an R-group-containing alcohol together with a halogenating agent such as thionyl chloride, etc. The method of reacting pyridine with an R-group-containing alcohol together with a halogenating agent such as thionyl chloride allows for one-pot synthesis, and is therefore highly productive and industrially advantageous. Those skilled in the art can appropriately set the reaction conditions in order to obtain the target compound.

[Amount of compound α]
The amount of compound α in the oil-resistant agent 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 compound α in the oil-resistant agent 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 oil-proofing agent of the present disclosure may include a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The oil-proofing 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 compound α. 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 compound α.

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, relative to 1 part by weight of compound α. 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, relative to 1 part by weight of compound α.

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, relative to 1 part by weight of compound α. 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, relative to 1 part by weight of compound α.

[Surfactant]
The oil-resistant agent may include a surfactant. The surfactant may include one or more surfactants selected from a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant. The surfactant may be non-fluorinated.

[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.
In addition, 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 is 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, sorbitan fatty acid esters, glycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, lecithin derivatives, 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 single type or a mixture of two or more types. 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.

[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, benzalkonium chloride, 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 compound α. 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 compound α.

〔silicone〕
The oil-resistant agent 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, relative to 100 parts by weight of compound α. 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, relative to 100 parts by weight of compound α.

〔wax〕
The oil-resistant agent 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 compound constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be 200 to 2000, for example, 250 to 1500, or 300 to 1000. These may be used alone or in combination of two or more.

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 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 compound α. The amount of wax may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of compound α.

[Organic acids]
The oil-resistant agent 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, relative to 100 parts by weight of the compound α. 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, relative to 100 parts by weight of the compound α. The amount of the organic acid may be adjusted so that the pH of the oil-resistant agent is 3 to 10, for example, 5 to 9, particularly 6 to 8. The oil-resistant agent may be acidic (pH 7 or less, for example 6 or less).

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

The curing agent (crosslinking agent) in the oil-resistant agent can effectively cure compound α. 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 compound α. 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 oil-resistant agent.

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, relative to 100 parts by weight of the compound α. 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, relative to 100 parts by weight of the compound α.

[Other ingredients]
The oil-resistant agent may contain other components in addition to the above-mentioned components. Examples of the other components include polysaccharides, paper strength agents, flocculants, retention aids, 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 enhancer, flocculant, retention improver 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 polyalkylene polyamines, 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., emulsions/dispersions of anhydrides 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.

[Preservative]
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.

[Deodorants]
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 WO 2012/090580).

[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 compound α. 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 compound α.

<Method of manufacturing treated textile or paper products>
The method of producing an oil-resistant product according to the present disclosure includes treating a substrate with the oil-resistant agent described above.

"Treatment" means that the oil-resistant agent is applied to the substrate by immersion, spraying, coating, etc. The treatment causes compound α, which is the active ingredient of the oil-resistant agent, to adhere to the inside and/or surface of the substrate. Here, adhesion may be physical or chemical, and for example, compound α may be physically or chemically (by reacting with) modified with hydroxyl groups of the substrate (fiber, paper, glass, etc.).

[Base material]
The substrate to be treated with the oil-resistant agent 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 fiber, carbon fiber, and asbestos fiber, or mixtures of these fibers. Textile products include woven fabrics, knitted fabrics, and nonwoven fabrics, as well as clothing (e.g., water-repellent clothing, e.g., raincoats) 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 of 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, containers made of paper, molded articles made of paper, etc. Specific examples of paper products include food packaging materials, food containers, 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, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral heat-sensitive paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc., and suitable examples include food packaging materials and food containers.

Substrates that can be treated with the oil-resistant agent 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.

When the substrate is glass, the glass product produced may be an optical member. The surface (outermost layer) of the glass substrate may have some layer (or film), such as a hard coat layer or an anti-reflection layer. The anti-reflection layer may be either a single-layer anti-reflection layer or a multi-layer anti-reflection layer. Examples of inorganic substances that can be used for the anti-reflection layer include SiO ₂ , SiO, ZrO ₂ , TiO ₂ , TiO, Ti ₂ O ₃ , Ti ₂ O ₅ , Al ₂ O ₃ , Ta ₂ O ₅ , CeO ₂ , MgO, Y ₂ O ₃ , SnO ₂ , MgF ₂ , and WO _3. These inorganic substances may be used alone or in combination of two or more of them (for example, as a mixture). When a multi-layer anti-reflection layer is used, it is preferable to use SiO ₂ and/or SiO for the outermost layer. When the product to be manufactured is an optical glass part for a touch panel, a transparent electrode, for example, a thin film using indium tin oxide (ITO) or indium zinc oxide, may be provided on a part of the surface of the substrate (glass). In addition, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomizing film layer, a hard coating film layer, a polarizing film, a phase difference film, a liquid crystal display module, etc., depending on the specific specifications.

[Processing method]
The oil-resistant agent 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 oil-resistant agent of the present disclosure is dispersed and diluted in an organic solvent or water as necessary, and attached to the inside and/or 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 is obtained to which the solid components of the oil-resistant agent are attached. If necessary, it may be applied together with a suitable crosslinking agent and cured. The oil-resistant agent of the present disclosure may be used in combination with various additives such as water- and/or oil-repellent agents, 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 oil-resistant agent 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 oil-resistant agent can be applied to the substrate by any of the methods known for treating substrates with liquids. The substrate may be immersed in the oil-resistant agent, 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 oil-resistant agent, 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 addition treatment. Alternatively, the oil-resistant agent may be applied to the textile product by a cleaning method, for example, in 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).

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

The internal addition treatment method may mean a treatment method in which an oil-resistant agent 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 following steps: adding an oil-resistant agent 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 to form a pulp mold intermediate; and molding and drying the pulp mold intermediate using 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 within such a temperature range, excellent oil resistance and water resistance 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 agents such as starch, modified starch, carboxymethyl cellulose, and polyamide polyamine-epichlorohydrin resin, coagulants, fixing agents, retention aids, dyes, fluorescent dyes, slime control agents, and defoamers, to the extent that they are commonly used. It is preferable to use starch or modified starch. If necessary, oil-resistant agents can 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 an oil-proofing agent and starch and/or modified starch. The solid content of the paper oil-proofing agent in the coating layer is preferably 2 g/ ^m2 or less.
In the case of internal addition, it is preferred to mix the oil-proofing agent with the pulp so that the amount of the oil-proofing agent 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 grease-resistant agent 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/treatment of textile products]
The textile product may be pretreated before being treated with the oil-proofing agent of the present disclosure. Pretreatment of the textile product can impart excellent fastness to the textile product after treatment with the oil-proofing agent.

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 interior and/or 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 imparting to a fiber one or ^more functional groups (hereinafter sometimes referred to as "specific functional groups") 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 oil-resistant agent can be applied to a fibrous substrate (e.g., a textile product that may have been pretreated as described above) by any of the methods known for treating textile products with liquids. When the textile product is a fabric, the fabric may be immersed in the solution or the solution may be applied or sprayed onto the fabric. The treated textile product is dried and preferably heated, for example, at 80°C to 200°C, to develop liquid repellency (water and/or oil repellency). Alternatively, the oil-resistant agent may be applied to the textile product by a cleaning method, such as, for example, in a wash application or a dry cleaning method.

The textile products to be treated are typically fabrics, including woven, knitted and nonwoven fabrics, clothing forms and carpets, but may also be fibers or yarns or intermediate textile products (e.g., slivers or rovings). The textile material may be natural fibers (e.g., cotton or wool), chemical fibers (e.g., viscose rayon or leocell), or synthetic fibers (e.g., polyester, polyamide or acrylic fibers), or may be a mixture of fibers (e.g., a mixture of natural and synthetic fibers). The disclosed method also generally renders textiles hydrophobic and water repellent. Alternatively, the fibrous substrate may be leather. The manufactured polymer may be applied to the leather from an aqueous solution or emulsion at various stages of leather processing, for example, during wet processing of the leather or during finishing of the leather, to render the leather hydrophobic and oleophobic.

"Treatment" means that the oil-resistant agent is applied to the object to be treated by immersion, spray application, etc. Treatment causes the active ingredients of the oil-resistant agent to penetrate into the interior of the object to be treated and/or to adhere to the surface of the object to be treated.

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 on 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-sha, 1981). Examples of immersion include the batch dyeing machine described on pages 196-247 of Dyeing and Finishing Equipment Directory (published by Sen-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 spraying include air spraying, which sprays the treatment liquid in a mist using compressed air, and air spraying using a hydraulic atomization method. The treatment conditions, such as the concentration of the treatment liquid and the heat treatment after application, can be adjusted appropriately 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 application to the fiber material to remove the water. There are no particular limitations on the drying method, and either a dry heat method or a wet heat method may be used. There are also no particular limitations on the drying temperature, but for example, drying at room temperature to 200°C for 10 seconds to several days may be sufficient. If necessary, after drying, heat treatment may be performed at a temperature of 100 to 180°C for about 10 seconds to 5 minutes.

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 treatment 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 described 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.

[Preparation of treated paper]
A 14.9 mg/ ^cm3 solution of the compound was applied three times to a thin paper with water resistance (Cobb value) of 52 g/ ^m2 , basis weight of 45 g/ ^m2 , and density of 0.60 g/ ^m3 using a Baker-type applicator with a gap set to 0 mil, and then annealed at 140°C for 1 minute to produce treated paper. Chloroform was used to adjust the solution for the coating liquid. When the compound was insoluble in chloroform, an organic solvent such as toluene or acetone was used.

[KIT test (oil resistance)]
Measurements were made using the 3M Kit Test (TAPPI T-559cm-02). In the 3M Kit Test, a test oil containing castor oil, toluene, and heptane is placed on the surface of treated paper, and after 15 seconds, the test oil is wiped off and the treated paper is evaluated based on whether or not there is oil staining. Tests were performed using test oils with kit numbers 1 to 6, and the highest kit number that did not produce any stains was used as the evaluation result for oil resistance.

[Corn oil resistance test (oil resistance)]
Corn oil is placed on the surface of the treated paper, and when the test oil is wiped off after 15 seconds, the treated paper is evaluated based on the presence or absence of oil stains.
If there is no stain, mark it as a circle; if there is a stain, mark it as an X.

[HD Contact Angle]
A solution (or dispersion) of compound α with a solid content concentration of 1.0% was spin-coated on a silicon wafer at 2500 rpm for 25 seconds to obtain a smooth spin-coated film. This was heated at 140° C. for 1 minute to produce a compound-treated silicon wafer. Chloroform was used as the solvent or dispersion medium. 2 μL of HD (hexadecane) was dropped onto the compound-treated silicon wafer, and the static contact angle 1 second after the drop was deposited was taken as the HD contact angle of compound α.

[Water repellency test]
A treatment solution containing compound α at a solid content of 16.8 mg/mL was prepared using chloroform as a solvent, and a cloth was immersed in the treatment solution and then passed through a mangle to heat-treat the test cloth, and the water repellency was evaluated. The water repellency of the treated cloth was evaluated according to the spray method of JIS-L-1092 (AATCC-22). It is expressed by a water repellency number as shown in the table below. The higher the score, the better the water repellency.

[Mold Creation]
A mold was formed using an automatic molding machine. A mesh-like body was placed on a metallic pulp mold mold having a large number of suction holes at the bottom, and a metallic tank was placed on the top, with the pulp slurry being placed in the upper metallic tank. The pulp-containing aqueous composition was sucked and dehydrated through the pulp mold mold and mesh-like body at 0.1 to 1 MPa by a vacuum pump from the side opposite to the side where the mesh-like body was placed in the pulp mold mold, and the solid content (pulp, etc.) contained in the pulp-containing aqueous composition was deposited on the mesh-like body to obtain a pulp mold intermediate. Next, the obtained pulp mold intermediate was dried under a pressure of 0.1 to 1 MPa from above and below with a metallic male-female mold heated to 60 to 200°C. In this way, a pulp molded product molded into a container shape was produced.

[Mold test, practical oil resistance test]
100 ml of corn oil at 65° C. was poured into the mold, and after leaving it at room temperature for 45 minutes, the corn oil was removed from the mold and the degree of oil staining of the mold was evaluated. Depending on the degree of staining, the following evaluation values were set.
5: No stains on the inside 4: Stains on the inside. No stains on the back.
3: Stain on the inside. Slight seepage on the back.
2: Stain on the inside. Less than 50% of the area has seeped through to the back.
1: Stain on the inside. Stain on the back is 50% or more but less than 100% of the area.
0: Seeping through to the entire back side.

[Mold test, practical water resistance test]
100 ml of water at 100° C. was poured into the mold, and after leaving it at room temperature for 30 minutes, the water was removed from the mold and the degree of staining of the mold was evaluated. Depending on the degree of staining, the following evaluation values were set.
5: No stains on the inside 4: Stains on the inside. No stains on the back.
3: Stain on the inside. Slight seepage on the back.
2: Stain on the inside. Less than 50% of the area has seeped through to the back.
1: Stain on the inside. Stain on the back is 50% or more but less than 100% of the area.
0: Seeping through to the entire back side.

<Synthesis of Compounds>
The compounds used in the test were synthesized by the following method.

[Compound 2]

¹H NMR (CDCl₃, 400 MHz) δ: 0.87 (t, 3 H), 1.24-1.68 (m, 32 H), 4.04 (s, 2 H), 4.17 (t, 2 H). 8.00 g of octadecanol (Tokyo Chemical Industry Co., Ltd.) was dissolved in 65.0 mL of dehydrated tetrahydrofuran (Fujifilm Wako Pure Chemical Industries, Ltd.) and cooled in an ice bath. After 10 minutes, 4.53 mL of triethylamine and 2.82 mL of 2-chloroacetic acid chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) were added in that order and stirred overnight. The next day, the reaction solution was filtered, the filtrate was concentrated, and the residue was stirred in methanol for 10 minutes and then stored in a refrigerator. After 3 hours, the solid was filtered and dried to obtain 9.36 g of compound 1 shown below.

^1H NMR ( _CDCl3 , 400 MHz) δ: 0.87 (t, 3H), 1.24-1.68 (m, 32H), 4.04 (s, 2H), 4.17 (t, 2H).

¹H NMR (CDCl₃, 400 MHz) δ: 0.87 (t, 3 H), 1.24-1.68 (m, 32 H), 4.04 (s, 2 H), 4.21 (t, 2 H), 6.33 (s, 1 H), 8.04 (t, 2 H), 8.47 (t, 1 H), 9.43 (d, 2 H). Compound 1 (4.23 g) was dissolved in 20.0 mL of dehydrated tetrahydrofuran (Fujifilm Wako Pure Chemicals), and then 2.95 mL of dehydrated pyridine (Fujifilm Wako Pure Chemicals) was added and stirred overnight at an oil bath temperature of 50° C. The next day, the reaction solution was stored in a refrigerator. After 3 hours, the solid was filtered and dried to obtain 1.51 g of compound 2 shown below.

^1H NMR ( _CDCl3 , 400 MHz) δ: 0.87 (t, 3H), 1.24-1.68 (m, 32H), 4.04 (s, 2H), 4.21 (t, 2H), 6.33 (s, 1H), 8.04 (t, 2H), 8.47 (t, 1H), 9.43 (d, 2H).

[Compound 3]
Compound 3 shown below was synthesized with reference to Journal of Chemical Research (2013), 37(4), 205-207.

[Compound 6]
First, compound 4 shown below was synthesized with reference to ChemMedChem (2016), 11(21), 2367-2371.

¹H NMR (CDCl₃, 400 MHz) δ: 0.87 (t, 3 H), 1.24-1.68 (m, 32 H), 4.33 (t, 2 H), 4.78 (t, 2 H), 7.50 (s, 1 H). 5 g of compound 4, 1.3 mL of propargyl alcohol (Fujifilm Wako Pure Chemicals), 0.85 g of copper sulfate pentahydrate (Fujifilm Wako Pure Chemicals), 1.34 g of sodium L-ascorbate (Fujifilm Wako Pure Chemicals), and 0.625 g of tetrabutylammonium iodide (Fujifilm Wako Pure Chemicals) were dissolved in a mixed solvent of 20.0 mL of tetrahydrofuran (Fujifilm Wako Pure Chemicals) and 20.0 mL of water, and then stirred overnight. The next day, the reaction solution was filtered, and the solid was washed with water and methanol. After washing, the solid was dried to obtain 5.95 g of compound 5 shown below.

^1H NMR ( _CDCl3 , 400 MHz) δ: 0.87 (t, 3H), 1.24-1.68 (m, 32H), 4.33 (t, 2H), 4.78 (t, 2H), 7.50 (s, 1H).

¹H NMR (CDCl₃, 400 MHz) δ: 0.86 (t, 3 H), 1.24-1.68 (m, 32 H), 4.32 (t, 2 H), 6.39 (s, 1 H), 8.04 (t, 2 H), 8.38 (t, 1 H), 8.72 (s, 1 H), 9.73 (d, 2 H). Next, 2.5 g of compound 5 was dissolved in 10.0 mL of dehydrated pyridine (Fuji Film Wako Pure Chemicals), 1.03 mL of thionyl chloride (Fuji Film Wako Pure Chemicals) was added, and the mixture was stirred overnight at an oil bath temperature of 80° C. The next day, the mixture was cooled to room temperature, and 20.0 mL of methanol was added to the reaction solution and stirred for 5 minutes. After 5 minutes, the solid was filtered and dried to obtain 2.29 g of compound 6 shown below.

^1H NMR ( _CDCl3 , 400 MHz) δ: 0.86 (t, 3H), 1.24-1.68 (m, 32H), 4.32 (t, 2H), 6.39 (s, 1H), 8.04 (t, 2H), 8.38 (t, 1H), 8.72 (s, 1H), 9.73 (d, 2H).

¹H NMR (CDCl₃, 400 MHz) δ: 0.87 (t, 3 H), 1.24-1.30 (m, 30 H), 2.23 (t, 2 H), 3.94 (d, 2 H). [Compound 8]
10.0 g of stearic acid (Tokyo Kasei Co., Ltd.), 0.429 g of 4,4-dimethylaminopyridine (Fuji Film Wako Pure Chemical Industries, Ltd.), and 5.05 g of glycine amide hydrochloride (Fuji Film Wako Pure Chemical Industries, Ltd.) were dissolved in 100.0 mL of dehydrated dimethylformamide (Fuji Film Wako Pure Chemical Industries, Ltd.), and then 6.37 mL of triethylamine and 8.76 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (Tokyo Kasei Co., Ltd.) were added in that order, and the mixture was stirred overnight at an oil bath temperature of 100° C. The next day, the reaction solution was cooled to 40° C., and then 50 mL of methanol was added and the mixture was filtered. The solid was washed with methanol and diethyl ether. After washing, the solid was dried to obtain 7.35 g of compound 7 shown below.

^1H NMR ( _CDCl3 , 400 MHz) δ: 0.87 (t, 3H), 1.24-1.30 (m, 30H), 2.23 (t, 2H), 3.94 (d, 2H).

¹H NMR (CDCl₃, 400 MHz) δ: 0.87 (t, 3 H), 1.24-1.30 (m, 30 H), 2.39 (t, 2 H), 3.99 (d, 2 H), 6.00 (d, 2 H), 8.02 (t, 2 H), 8.45 (t, 1 H), 9.45 (d, 2 H), 10.72 (m, 1 H). 8.5 g of compound 7, 4.61 g of pyridine hydrochloride (Fuji Film Wako Pure Chemicals), and 1.05 g of paraformaldehyde (Fuji Film Wako Pure Chemicals) were dissolved in 90.0 mL of dehydrated pyridine (Fuji Film Wako Pure Chemicals), and then stirred overnight at an oil bath temperature of 85° C. The next day, the reaction solution was cooled to room temperature, and the solid was filtered and washed with pyridine and acetone. After washing, the solid was dried to obtain 6.76 g of compound 8 shown below.

^1H NMR ( _CDCl3 , 400 MHz) δ: 0.87 (t, 3H), 1.24-1.30 (m, 30H), 2.39 (t, 2H), 3.99 (d, 2H), 6.00 (d, 2H), 8.02 (t, 2H), 8.45 (t, 1H), 9.45 (d, 2H), 10.72 (m, 1H).

[Compound 10]
10.0 g of stearic acid (Tokyo Kasei Co., Ltd.), 6.7 g of 4-aminobenzamide (Fuji Film Wako Pure Chemical Industries, Ltd.), and 0.429 g of 4,4-dimethylaminopyridine (Fuji Film Wako Pure Chemical Industries, Ltd.) were dissolved in 100.0 mL of dehydrated dimethylformamide (Fuji Film Wako Pure Chemical Industries, Ltd.), and 8.76 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (Tokyo Kasei Co., Ltd.) were added in this order, and the mixture was stirred overnight at an oil bath temperature of 100° C. The next day, the reaction solution was cooled to 40° C., and then 50 mL of methanol was added and the mixture was filtered. The solid was washed with water, methanol, and diethyl ether. After washing, the solid was dried to obtain 10.59 g of compound 9 shown in the following formula.

¹H NMR (CDCl₃, 400 MHz) δ: 0.87 (t, 3 H), 1.24-1.70 (m, 30 H), 2.36 (t, 2 H), 6.22 (s, 2 H), 7.63 (m, 2 H), 8.00-8.11 (m, 4 H), 8.40 (t, 1 H), 9.73 (d, 2 H), 11.05 (br s, 1 H). 7.5 g of compound 9, 3.01 g of pyridine hydrochloride (Fuji Film Wako Pure Chemicals), and 0.81 g of paraformaldehyde (Fuji Film Wako Pure Chemicals) were dissolved in 90.0 mL of dehydrated pyridine (Fuji Film Wako Pure Chemicals), and the mixture was stirred overnight at an oil bath temperature of 83° C. The next day, the reaction solution was cooled to 50° C., and the solid was filtered and washed with pyridine and methanol. After washing, the solid was dried to obtain 5.60 g of compound 10 shown below.

^1H NMR ( _CDCl3 , 400 MHz) δ: 0.87 (t, 3H), 1.24-1.70 (m, 30H), 2.36 (t, 2H), 6.22 (s, 2H), 7.63 (m, 2H), 8.00-8.11 (m, 4H), 8.40 (t, 1H), 9.73 (d, 2H), 11.05 (br s, 1H).

¹H NMR (CDCl₃, 400 MHz) δ: 0.87 (t, 3 H), 1.24-1.70 (m, 30 H), 2.40 (t, 2 H), 3.94 (d, 2 H), 4.59 (s, 2 H), 5.75 (br s, 1 H), 6.06 (br s, 1 H). [Compound 12]
First, 10.0 g of stearic acid (Tokyo Kasei Co., Ltd.), 7.4 g of 2-chloroacetamide (Fuji Film Wako Pure Chemical Industries, Ltd.), and 7.0 g of potassium carbonate (Fuji Film Wako Pure Chemical Industries, Ltd.) were dissolved in 60.0 mL of dehydrated dimethylformamide (Fuji Film Wako Pure Chemical Industries, Ltd.), and then stirred overnight at an oil bath temperature of 100° C. The next day, the reaction solution was cooled to 40° C., and then 50 mL of water was added and filtered. The solid was washed with 1N hydrochloric acid, water, acetone, and diethyl ether. After washing, the solid was dried to obtain 6.93 g of compound 11 shown below.

^1H NMR ( _CDCl3 , 400 MHz) δ: 0.87 (t, 3H), 1.24-1.70 (m, 30H), 2.40 (t, 2H), 3.94 (d, 2H), 4.59 (s, 2H), 5.75 (br s, 1H), 6.06 (br s, 1H).

¹H NMR (CDCl₃, 400 MHz) δ: 0.87 (t, 3 H), 1.24-1.70 (m, 30 H), 2.57 (t, 2 H), 4.63 (s, 2 H), 6.14 (s, 2 H), 8.02 (t, 2 H), 8.44 (t, 1 H), 9.56 (d, 2 H), 10.64 (br s, 1 H). Next, 11.05 g of compound 11, 5.38 g of pyridine hydrochloride (Fujifilm Wako Pure Chemicals), and 1.28 g of paraformaldehyde (Fujifilm Wako Pure Chemicals) were dissolved in 70.0 mL of dehydrated pyridine (Fujifilm Wako Pure Chemicals), and the mixture was stirred overnight at an oil bath temperature of 83° C. The next day, the reaction solution was cooled to room temperature, and the solid was filtered and washed with methanol and acetone. After washing, the solid was dried to obtain 5.11 g of compound 12 shown below.

^1H NMR ( _CDCl3 , 400 MHz) δ: 0.87 (t, 3H), 1.24-1.70 (m, 30H), 2.57 (t, 2H), 4.63 (s, 2H), 6.14 (s, 2H), 8.02 (t, 2H), 8.44 (t, 1H), 9.56 (d, 2H), 10.64 (br s, 1H).

[Compound 13]
Compound 13 shown below was synthesized with reference to Journal of Organic Chemistry (1951), 16, 1111-16.

<Test Results>
The evaluation results of the KIT test, the corn oil resistance test, and the HD contact angle are shown in Table 1.

[Table 1]

The results of the mold test are shown in Table 2. The mold was prepared by the following method.
Compound 8 was pulverized in a mortar and powdered. 0.1 g of polyoxyethylene (10) oleyl ether and 8.9 g of water were added to 1 g of this powder and mixed with a mix rotor for 6 hours. The mixture was stirred for 20 minutes at 10,000 rpm with a homogenizer to obtain an aqueous dispersion composition of Compound 8. Subsequently, the aqueous dispersion composition of Compound 8 was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the pulp to the solid content was 5 wt%, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was put into an automatic molding machine to prepare a mold.

Compound 13 was pulverized in a mortar to obtain a powder. 0.1 g of polyoxyethylene (10) oleyl ether and 8.9 g of water were added to 1 g of this powder and mixed with a mix rotor for 6 hours. The mixture was stirred with a homogenizer at 10,000 rpm for 20 minutes to obtain an aqueous dispersion composition of compound 13. Next, the aqueous dispersion composition of compound 13 was added to a pulp slurry with a concentration of 0.5 wt % so that the ratio of the solid content to the pulp was 10 wt %, thereby preparing a pulp-containing aqueous composition. The pulp-containing aqueous composition was placed in an automatic molding machine to prepare a mold.

[Table 2]

The results of the water repellency test are shown in Table 3. A water repellency test was conducted on compound 3 against PET fiber (PET cloth). The adhesion rate of compound 3 to the PET fiber after treatment was 2.1 wt%.

[Table 3]

Claims (18)

The following formula:

[Wherein,
Y ⁻ is a counter anion,
X is a direct bond or a group having a valence of n+m;
R is a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms,
Z is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -N(R') ₂ (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), a hydroxyl group, a carboxyl group, or a halogen atom;
m is an integer of 1 to 10,
n is an integer of 1 to 3,
p is an integer of 0 to 5.
The compound represented by the formula:
An oil resistant agent, where --X--R _n does not include --O--R or --NHC(.dbd.O)--R. 2. The oil-resistant agent according to claim 1, wherein Y ^{1 −} is at least one selected from the group consisting of a halide ion, a sulfonate ion, a phosphate ion, and a carboxylate ion. X is a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O) ₂ -, -NR'-, -C(OR')R'-, -C(OR')(-) ₂ , -N(-) ₂ , a di- to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a di- to tetravalent hydrocarbon aromatic ring, or a di- to tetravalent heterocycle [wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.]
The oil-resistant agent according to claim 1 or 2, wherein the n+m valent group is at least one selected from the group consisting of: The oil-resistant agent according to claim 1 or 2, wherein R has 12 or more carbon atoms. The oil-resistant agent according to claim 1 or 2, wherein the compound has a melting point of 40°C or higher, or does not have a melting point. The oil-resistant agent according to claim 1 or 2, wherein the compound has an n-hexadecane contact angle of 10° or more. A liquid medium is included.
The oil-resistant agent according to claim 1 or 2, wherein the viscosity of the oil-resistant agent is 5 cP or more and 100 cP or less at a compound concentration of 14.8 mg/mL and at 20° C. The oil-resistant agent according to claim 1 or 2, which is an aqueous dispersion. The oil-resistant agent according to claim 1 or 2, which is for paper. The oil-resistant agent according to claim 1 or 2, which does not contain a fluorine compound. A textile product to which the compound in the oil-resistant agent according to claim 1 or 2 is attached, or to which the compound in the oil-resistant agent according to claim 1 or 2 is modified on the hydroxyl groups of the textile. A grease-resistant paper to which the compound in the grease-resistant agent according to claim 1 or 2 has been attached, or to which the compound in the grease-resistant agent according to claim 1 or 2 has been modified to a hydroxyl group of the paper. A glass product to which the compound in the oil-resistant agent according to claim 1 or 2 is attached, or to which the compound in the oil-resistant agent according to claim 1 or 2 is modified on the hydroxyl groups of the glass. The greaseproof paper according to claim 12, which is a food packaging material or food container. A method for producing grease-resistant paper, comprising a step of externally or internally treating paper with the grease-resistant agent according to claim 1 or 2. The following formula:

[Wherein,
Y ⁻ is a counter anion,
R is a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms,
Z is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -N(R') ₂ (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), a hydroxyl group, a carboxyl group, or a halogen atom;
p is an integer of 0 to 5.
A compound represented by the formula: The following formula:

[Wherein,
Y ⁻ is a counter anion,
R is a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms,
Z is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -N(R') ₂ (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), a hydroxyl group, a carboxyl group, or a halogen atom;
p is an integer of 0 to 5.
A compound represented by the formula: The following formula:

[Wherein,
Y ⁻ is a counter anion,
X is a direct bond or a group having a valence of n+m;
R is a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms,
Z is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -N(R') ₂ (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), a hydroxyl group, a carboxyl group, or a halogen atom;
m is an integer of 1 to 10,
n is an integer of 1 to 3,
p is an integer of 1 to 5.
An aqueous dispersion comprising a compound represented by the formula:
The aqueous dispersion further comprises at least one selected from the group consisting of a non-fluorine-containing surfactant, a silicone, a wax, an organic acid, and a curing agent.