Oil-resistant agent

Abstract

To provide a novel oilproofing agent that is capable of imparting oil resistance to a base material, such as a fiber or paper.SOLUTION: The present invention provides an oilproofing agent containing a compound expressed by a formula below [where, 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].SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to an oil-resistant agent. [Background technology]

[0002] In recent years, research has been progressing on materials and methods that can impart water-repellent and oil-repellent properties to various substrates. Patent Document 1 discloses a method for imparting water-repellent and oil-repellent properties to a fibrous substrate by using a combination of a pyridinium compound and a fluorine compound. In the invention described in Patent Document 1, the fluorine-containing compound is an essential component. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] U.S. Patent No. 3034925 [Overview of the project] [Problems that the invention aims to solve]

[0004] The object of this disclosure is to provide a novel oil-resistant agent that can impart oil resistance to a substrate (e.g., fibers, paper). [Means for solving the problem]

[0005] This disclosure includes the following aspects: [Section 1] The following formula: TIFF0007832525000001.tif3853[in the formula, Y - It is a counter anion, X is a directly bonded or n+m valence group, R is a monovalent hydrocarbon group having 6 to 40 carbon atoms, either linear or branched. 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 between 1 and 10, n is an integer between 1 and 3, p is an integer between 0 and 5 (inclusive). It contains a compound represented by, -XR n It is an oil-resistant agent that does not contain -OR and -NHC(=O)-R. [Section 2] Y - The oil-resistant agent according to item 1, wherein is at least one selected from the group consisting of halide ions, sulfonate ions, phosphate ions, and carboxylate ions. [Section 3] X can be 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 with 1 to 20 carbon atoms, a di- to tetravalent hydrocarbon aromatic ring, or a di- to tetravalent heterocycle. [In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.] An oil-resistant agent according to item 1 or 2, comprising at least one n+m valent group selected from the group consisting of the following. [Section 4] An oil-resistant agent according to any one of items 1 to 3, wherein R has 12 or more carbon atoms. [Section 5] An oil-resistant agent according to any one of claims 1 to 4, wherein the melting point of the compound is 40°C or higher, or the compound has no melting point. [Section 6] The oil-resistant agent according to any one of claims 1 to 5, wherein the n-hexadecane contact angle of the compound is 10° or more. [Section 7] Containing a liquid medium, The oil-resistant agent according to any one of claims 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 20°C. [Section 8] An oil-resistant agent described in any one of items 1 to 7, which is an aqueous dispersion. [Section 9] An oil-resistant agent for paper, as described in any one of items 1 to 8. [Section 10] An oil-resistant agent according to any one of items 1 to 9, which does not contain fluorine compounds. [Section 11] A textile product to which the compound in any one of the oil-resistant agents described in item 1 to 10 is attached, or to which the compound in any one of the oil-resistant agents described in item 1 to 10 is modified on the hydroxyl groups of the fibers. [Section 12] Oil-resistant paper to which the compound in any one of the oil-resistant agents described in item 1 to 10 is attached, or to which the compound in any one of the oil-resistant agents described in item 1 to 10 is modified on the hydroxyl groups of the fibers. [Section 13] Glass products to which the compound in any one of the oil-resistant agents described in items 1 to 10 is attached, or to which the compound in any one of the oil-resistant agents described in items 1 to 10 is modified on the hydroxyl groups of the fibers. [Section 14] Oil-resistant paper as described in item 12, which is a food packaging material or food container. [Section 15] A method for producing oil-resistant paper, comprising the step of externally or internally applying an oil-resistant agent described in any one of items 1 to 10. [Section 16] The following formula: TIFF0007832525000002.tif4045[in the formula, Y - It is a counter anion, R is a monovalent hydrocarbon group having 6 to 40 carbon atoms, either linear or branched. 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 between 0 and 5 (inclusive). A compound represented by the formula. [Section 17] The following formula: TIFF0007832525000003.tif4057[In the formula, Y - It is a counter anion, R is a monovalent hydrocarbon group having 6 to 40 carbon atoms, either linear or branched. 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 between 0 and 5 (inclusive). A compound represented by the formula. [Section 18] The following formula: TIFF0007832525000004.tif3853[In the formula, Y - It is a counter anion, X is a directly bonded or n+m valence group, R is a monovalent hydrocarbon group having 6 to 40 carbon atoms, either linear or branched. 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 between 1 and 10, n is an integer between 1 and 3, p is an integer between 1 and 5 (inclusive). An aqueous dispersion containing a compound represented by, Furthermore, an aqueous dispersion comprising at least one selected from the group consisting of non-fluorinated surfactants, silicones, waxes, organic acids, and curing agents. [Effects of the Invention]

[0006] The oil-resistant agent of this disclosure can impart oil resistance to a substrate (e.g., textiles, paper). [Modes for carrying out the invention]

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

[0008] As used herein, "hydrocarbon group" means a group containing carbon and hydrogen, obtained by removing a hydrogen atom from a hydrocarbon. Such hydrocarbon groups are not particularly limited, but include C 1-20 Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The above-mentioned "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. Cyclic groups may include a chain-like structure. Hydrocarbon groups may be substituted with one or more substituents.

[0009] In this specification, unless otherwise stated, whether or not the phrases "independently in each occurrence," "independently of each other," "independently of each other," or similar expressions are explicitly stated, when a term (symbol) that may occur multiple times in a chemical structure is defined, the definition shall apply independently to each occurrence.

[0010] The chemical structures described herein should be understood to exclude any chemical structures that would be considered chemically impossible or extremely unstable by those skilled in the art.

[0011] <Oil-resistant agent> The oil-resistant agents in this disclosure impart oil resistance to a substrate (e.g., a fibrous substrate, a paper substrate). The oil-resistant agents in this disclosure may also function as, in place of, or in addition to, an oil-resistant agent, at least one selected from the group consisting of repellents, water-repellents, oil-repellents, and water-resistant agents.

[0012] Compound α, the active ingredient in the oil-resistant agent of this disclosure, has excellent dispersibility in liquid media due to its structure, and the oil-resistant agent of this disclosure can have stable performance.

[0013] Conventional oil repellents using polymer-type compounds as active ingredients tend to have a broad molecular weight distribution and contain a relatively large amount of impurities. On the other hand, the active ingredient of the oil repellent of this invention is low molecular weight, which allows for a narrower (single-molecule) molecular weight distribution and potentially better performance.

[0014] The oil-resistant agent in this disclosure comprises compound α. The oil-resistant agent in this disclosure may be compound α alone. In addition to compound α, the oil-resistant agent in this disclosure may also contain other components such as a liquid medium.

[0015] The oil-resistant agent in this disclosure does not necessarily have to contain any of the compounds selected from the group consisting of compounds having 8 or more carbon atoms in a fluoroalkyl group, compounds having 8 or more carbon atoms in a perfluoroalkyl group, compounds having 4 or more carbon atoms in a fluoroalkyl group, compounds having 4 or more carbon atoms in a perfluoroalkyl group, compounds having a perfluoroalkyl group, compounds having a fluoroalkyl group, and compounds having a fluorine atom. The oil-resistant agent in this disclosure can impart oil resistance to a substrate even without containing these fluorine compounds.

[0016] The oil-resistant agents in this disclosure can preferably be used as a dispersion (particularly an aqueous dispersion) along 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 at a compound concentration of 14.8 mg / mL and 20°C, and is preferably 5 cP or more. 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 at a compound concentration of 14.8 mg / mL and 20°C, and is preferably 100 cP or less.

[0017] [Compound α] Compound α in this disclosure can adhere to a substrate and impart liquid-repellent properties to the substrate.

[0018] 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. By having an HD contact angle of compound α above the lower limit mentioned above, good liquid repellency (especially oil repellency) can be imparted 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.

[0019] The water contact angle of compound α may be 35° or higher, 40° or higher, 45° or higher, 50° or higher, 55° or higher, 65° or higher, 75° or higher, 85° or higher, 90° or higher, or 100° or higher. The water contact angle of compound α may be 160° or lower, 140° or lower, 130° or lower, 120° or lower, 110° or lower, 100° or lower, or 90° or lower. By having a water contact angle of compound α above the lower limit of the above limits, good liquid repellency (especially water repellency) can be imparted 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.

[0020] 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, 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.

[0021] 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.

[0022] Compound α in the present disclosure may not have any selected from the group consisting of a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, and a fluorine atom. Even if compound α does not contain these fluorine-containing groups, it can impart oil resistance to the base material.

[0023] Compound α in the present disclosure may not have an active hydrogen-containing group. Examples of the active hydrogen group-containing group include an amino group (an amino group not adjacent to a carbonyl group, for example, a primary amino group or a secondary amino group), a hydroxy group, and a carboxyl group. In particular, compound α in the present disclosure may not have a hydroxy group from the viewpoint of oil resistance.

[0024] Compound α has the following formula: TIFF00078,325,250,000,005.tif3853[where, Y - is a counter anion, X is a direct bond or an n + m-valent group, 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 (where 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 or more and 10 or less, n is an integer of 1 or more and 3 or less, p is an integer of 0 or more and 5 or less.] It may be represented by. Here, X-R n may not include -O-R and -NHC(=O)-R.

[0025] [Y - Y - is a counter anion of pyridinium, Y - ​Examples of such ions include at least one selected from the group consisting of halide ions (e.g., fluoride ions, chloride ions, bromide ions, iodide ions, etc., e.g., chloride ions), sulfonate ions, phosphate ions, and carboxylate ions.

[0026] [X] X is either a direct bond or an n+m valence group. X functions as a linker connecting m pyridinium methylene groups to n R groups.

[0027] n is the number of R elements that combine with X, and can be an integer between 1 and 3. n can be 1 or greater, 2 or greater, or 3 or greater. n can be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0028] m is the number of pyridinium methylene groups bonded to X, and may be an integer between 1 and 10. m may be 1 or greater, 2 or greater, 4 or greater, or 6 or greater. m may be 9 or less, 6 or less, or 3 or less, for example, 2 or less.

[0029] 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.

[0030] X may be an aliphatic group (unsaturated aliphatic group or saturated aliphatic group) or an aromatic group.

[0031] X may have one or more selected from the group consisting of amide groups, urea groups, urethane groups, and imides. Examples of such X include: -OC(=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.] Examples of groups include those such as the following. The amide group, urea group, urethane group, and NR' group in imide do not necessarily have to be adjacent to the aromatic ring.

[0032] X can be 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 with 1 to 20 carbon atoms, a di- to tetravalent hydrocarbon aromatic ring, or a di- to tetravalent heterocycle. [In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.] It may be an n+m valence base consisting of at least one selected from the group comprising the above.

[0033] X is X is composed of one or more selected from the group consisting of direct bonds, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2, -N(-)2 (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms in each occurrence). 1 and, X is composed of one or more selected from the group consisting of a di- to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a di- to tetravalent hydrocarbon aromatic ring, and a di- to tetravalent heterocycle. 2 and, It may be an n+m valency group consisting of one or more selected from the group comprising the above. In this specification, the group referred to as X has a pyridinium methylene group on the left and is bonded to R on the right.

[0034] [X 1 ] X 1 It is a non-hydrocarbon linker.

[0035] X 1 X is a directly bonded or divalent or more group. 1 The valence of X may be 2-4, 2-3, or 2. 1It is preferable that the bonding is not solely direct.

[0036] X 1 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more. 1 The molecular weight may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0037] X 1 It consists of one or more selected from the group consisting of direct bonds, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms in each occurrence). 1 Examples include, direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -C(=O)-NR'-C(=O)-, -C(=NR')-, -S-, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2 etc. [In the formula, R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms in each instance.] These are some examples.

[0038] [X 2 ] X2 It is a hydrocarbon or aromatic linker.

[0039] X 2 X may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). 2 X may be aliphatic or aromatic. 2 The chain may be linear, branched, or annular.

[0040] X 2 X is a group with two or more valent values. 2 The valence may be, for example, 2-4, 2-3, or 2.

[0041] X 2 The number of carbon atoms 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. 2 The number of carbon atoms 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.

[0042] X 2 It is composed of one or more selected from the group consisting of aliphatic hydrocarbon groups having 1 to 20 carbon atoms with a 2 to 4 valent charge, aromatic hydrocarbon rings with a 2 to 4 valent charge, and heterocycles with a 2 to 4 valent charge.

[0043] A divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be a cyclic, branched, or linear hydrocarbon group. A divalent 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 a divalent 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 a divalent to 20 carbon atoms may be 15 or less, 10 or less, or 5 or less.

[0044] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring constituent atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The hydrocarbon aromatic ring may have substituents, and examples of substituents include alkyl groups having 1 to 6 carbon atoms, alkoxy groups 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), hydroxyl groups, carboxyl groups, or halogen atoms. The valency of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0045] The 2-4 valent heterocycle may be an aliphatic group or an aromatic group. Examples of 2-4 valent heterocycles include groups obtained by removing 2-4 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 constituent atoms of the heterocycle is 3-20, 4-16, or 5-12, preferably 5-12. The heterocycle may have substituents, examples of which include C1-C6 alkyl groups, C1-C4 alkoxy groups, -N(R')2 (wherein R' is a hydrogen atom or a C1-C4 hydrocarbon group), hydroxyl groups, carboxyl groups, or halogen atoms. The valency 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 heterocycles, particularly triazole rings (e.g., 1-3, particularly 1). X may not have hydrocarbon rings (e.g., hydrocarbon aromatic rings, particularly benzene rings).

[0046] X2 Examples include, -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali(-)2 (-)2Cy(-)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.] These are some examples.

[0047] X 2 Specific examples include: -(CH2) p -(p is between 1 and 20, for example, between 1 and 10) A linear hydrocarbon group having 1 to 40 carbon atoms, for example, 1 to 10 unsaturated bonds, A hydrocarbon group having 1 to 40 carbon atoms, for example, a branched structure with 1 to 10 carbon atoms. -(CH2) q -Cy-(CH2) r -(q and r are each independently between 0 and 20, for example between 1 and 10, and Cy is a hydrocarbon aromatic ring or heterocycle) These are some examples.

[0048] [Example of X] Let's explain the example of X. In the following, R' is independently either a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms in each instance.

[0049] An example of X is when X is divalent, -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 -、 etc. can be mentioned.

[0050] Examples of X include, when X is trivalent, -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; (-)2X 1 -、(-)2X 1 -X 2 -、(-X 1 )2X 2 -、(-)2X 1 -X 2 -X 1 -、(-X 1 )2-X 2 -X 1 -、(-X 1 -X 2 )2-X1 -、(-)2X 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; (-)2X 2 -、(-)2X 2 -X 1 -、(-X 2 )2X 1 -、(-)2X 2 -X 1 -X 2 -、(-X 2 )2-X 1 -X2 -, (-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 - are some examples.

[0051] An example of X is when X is tetravalent, -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; (-)2X 1 (-)2, (-)2X 1 -X 2 (-)2, (-X 1 )2X2 (-)2、(-)2X 1 -X 2 -X 1 (-)2、(-X 1 )2-X 2 -X 1 (-)2、(-X 1 -X 2 )2-X 1 (-)2、(-)2X 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-X 2 (-)2; (-)3X 1 -、(-)3X 1 -X 2 -、(-X 1 )3X 2 -、(-)3X 1 -X 2 -X 1 -、(-X 1 )3-X 2 -X 1 -、(-X 1 -X 2 )3-X 1 -、(-)3X 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、-X2 -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; (-)2X 2 (-)2、(-)2X 2 -X 1 (-)2、(-X 2 )2X 1 (-)2、(-)2X 2 -X 1 -X 2 (-)2、(-X 2 )2-X 1 -X 2 (-)2、(-X 2 -X 1 )2-X 2 (-)2、(-)2X 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-X 1 (-)2; (-)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 - are some examples.

[0052] A preferred example of X is -X 1 -, -X 1 -X 2 -, -X 1 -X 2 -X 1 -, -X 1 -X 2 (-)2, -(X 1 )2-X 2 -(Here, X 2 (is trivalent), -(X 1 )2X 2 (-)2(Here, X 2 (It is tetravalent), -X 2 -, -X 2 -X 1 -, -X 2 -X 1 -X 2 -, -X 2 -X1 (-)2, -(X 2 )2-X 1 -(Here, X 1 (is trivalent), -(X 2 )2X 1 (-)2(Here, X 1 (It is tetravalent.) These are some examples.

[0053] 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 -(Here, X 2 (is trivalent), -(X 1 )2X 2 (-)2(Here, X 2 (It is tetravalent), -X 2 -, -X 2 -X 1 -, -X 2 -X 1 -X 2 -, -X 2 -X 1 (-)2, -(X 2 )2-X 1 -(Here, X 1 (is trivalent), or -(X 2 )2X 1 (-)2(Here, X 1 (It is tetravalent.) [In the formula, X 1 However, in each appearance independently, direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, or -C(=O)-NR'- -C(=O)-NR'-C(=O)- [In the formula, R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms in each instance.] And, X 2 This 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 is a group represented by [formula]. This allows for good oil resistance to be imparted to the substrate.

[0054] Further examples of X include: -O- -NR'-(C=O)- -NR'-(C=O)-CH2-O-(C=O)- -NR'-(C=O)-CH2-N(-)(C=O)- -NR'-(C=O)-Ph-O- -(C=O)-NR'- -(C=O)O- TIFF0007832525000006.tif1627(-)2C(CH2O(C=O)NR'-)2 [In the formula, R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms in each instance.] These are some examples.

[0055] [R] R is a monovalent hydrocarbon group having 6 to 40 carbon atoms, either linear or branched. R is branched or linear, more preferably linear. R may be saturated or unsaturated. R is preferably a saturated aliphatic hydrocarbon group (alkyl group).

[0056] The carbon number of R may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, preferably 10 or more, more preferably 12 or more. The carbon number of R may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, more preferably 25 or less.

[0057] [Z] Z is a group that replaces the 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 (where 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.

[0058] p represents the number of Z that modifies the pyridinium group (how many of the 5 ring hydrogens of the pyridinium group are substituted) and is an integer from 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, and may be, for example, 2 or less (for example, 1 or 0).

[0059] [Examples of Compound α] Examples of Compound α include compounds represented by the following formula. In the following formula, Y - For the details of Y, R, Z, and p, the above descriptions are incorporated by reference.

[0060] TIFF0007832525000007.tif3236

[0061] TIFF0007832525000008.tif3447

[0062] TIFF0007832525000009.tif3053

[0063] TIFF0007832525000010.tif3554

[0064] TIFF0007832525000011.tif3260

[0065] TIFF0007832525000012.tif4050

[0066] [Method for producing compound α] Methods for producing compound α are not limited to those described above, but include reacting pyridine with an R-group-containing alkyl halide, and reacting pyridine with an R-group-containing alcohol together with a halogenating agent such as thionyl chloride. 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, which offers excellent productivity and can be industrially advantageous. The reaction conditions can be appropriately set by those skilled in the art to obtain the desired compound.

[0067] [Amount of compound α] The amount of compound α may be 0.01% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, or 30% by weight or more in the oil resistant agent. The amount of compound α may be 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight or less in the oil resistant agent.

[0068] [Liquid media] The oil-resistant agent in this 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-resistant agent may be a dispersion or a solution.

[0069] Examples of organic solvents include esters (e.g., esters with 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2 to 40 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols with 1 to 40 carbon atoms, specifically isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes with 5 to 10 carbon atoms, specifically naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain compounds having at least one hydroxyl group (e.g., polyhydric alcohols such as alcohols and glycol-based solvents, or ether forms of polyhydric alcohols (e.g., monoether forms)). These may be used individually or in combination of two or more.

[0070] [Amount of liquid medium] The amount of 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, or 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, per 1 part by weight of compound α. The amount of 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, per 1 part by weight of compound α.

[0071] The amount of water may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, per 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, per 1 part by weight of compound α.

[0072] The amount of organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, per 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, per 1 part by weight of compound α.

[0073] [Surfactants] The oil-resistant agent may contain a surfactant. The surfactant may include one or more surfactants selected from nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. The surfactant may also be fluorine-free.

[0074] [Nonionic surfactants] Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides.

[0075] Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0076] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are 1-6 valent (especially 2-5 valent) alcohols with 1-50 carbon atoms (especially 10-30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2-50 carbon atoms, especially 5-30 carbon atoms.

[0077] Examples of ester ethers are compounds formed by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are 1-6 valent (especially 2-5 valent) alcohols with 1-50 carbon atoms (especially 3-30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2-50 carbon atoms, especially 5-30 carbon atoms.

[0078] Examples of alkanolamides are formed from fatty acids and alkanolamines. Alkanolamides may be monoalkanolamides or dialkanolaminos. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. Alkanolamines may be alkanols having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0079] Polyhydric alcohols may be divalent to pentavalent alcohols with 10 to 30 carbon atoms. The amine oxide may be an oxide of an amine (a secondary amine or preferably a tertiary amine) (for example, having 5 to 50 carbon atoms).

[0080] 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 of the oxyalkylene group is preferably 2 to 10. In general, the number of oxyalkylene groups in the molecule of the nonionic surfactant is 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.

[0081] The nonionic surfactant may be an alkylene oxide adduct of a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, etc. Among these, those in which the structure of the alkylene oxide adduct portion and the polyalkylene glycol portion is polyoxyethylene (POE) or polyoxypropylene (POP) or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Also, the nonionic surfactant preferably has a structure that does not contain an aromatic group due to environmental problems (biodegradability, environmental hormones, etc.).

[0082] The nonionic surfactant has the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [In the formula, R 1 is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an acyl group, Each of R 2 is independently the same or different and is an alkylene group having 3 or more carbon atoms (for example, 3 to 10), R 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, q is 0 or a number of 1 or more.] It may be a compound represented by.

[0083] ​1 The carbon atoms have 8 to 20 carbon atoms, and are more preferably 10 to 18 carbon atoms. 1 Preferred specific examples include the lauryl group, tridecyl group, and oleyl group. R 2 Examples include the propylene group and the butylene group. In nonionic surfactants, p may be a number greater than or equal to 3 (for example, 5 to 200). q may be a number greater than or equal to 2 (for example, 5 to 200). That is, -(R 2 O) q - may form a polyoxyalkylene chain. The nonionic surfactant may be a polyoxyethylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) in the center. Examples of hydrophobic oxyalkylene chains include oxypropylene chains, oxybutylene chains, and styrene chains, but among these, oxypropylene chains are preferred.

[0084] Specific examples of nonionic surfactants include ethylene oxide, hexylphenol, isooctatylphenol, hexadecanol, oleic acid, and alkanes (C 12 -C 16 ) Thiol, sorbitan monofatty acid (C7-C 19 ) or alkyl (C 12 -C 18 This includes condensation products with amines, sorbitan fatty acid esters, glycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, lecithin derivatives, and the like.

[0085] The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example, 30 to 75% by weight, and especially 40 to 70% by weight, relative to the molecular weight of the nonionic surfactant (copolymer). The average molecular weight of nonionic surfactants is generally between 300 and 5,000, for example, between 500 and 3,000. Nonionic surfactants may be a single type or a mixture of two or more types. Nonionic surfactants may be a mixture of compounds with an HLB (hydrophilic-hydrophobic balance) of less than 15 (especially 5 or less) and compounds with an HLB of 15 or more.

[0086] [Cationic surfactants] The cationic surfactant is preferably a compound that does not have an amide group.

[0087] Cationic surfactants may be amine salts, quaternary ammonium salts, or oxyethylene-added ammonium salts. Specific examples of cationic surfactants are not limited to alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt-type surfactants such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, benzethonium chloride, and other quaternary ammonium salt-type surfactants.

[0088] Preferred examples of cationic surfactants are: R 21 -N + (-R 22 )(-R 23 )(-R 24 )X - [In the formula, R 21 , R 22 , R 23 and R 24 These are hydrocarbon groups with 1 to 40 carbon atoms. X is an anionic group. It is a compound of [the compound]. R 21 , R 22 , R 23 and -R 24 Specific examples of X are alkyl groups (e.g., methyl group, butyl group, stearyl group, palmityl group). 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 group with 4 to 40 carbon atoms).

[0089] The cationic surfactant is preferably an ammonium salt. The cationic surfactant has the formula: R 1 p -N + R 2 q X - [In the formula, R 1 is C12 or higher (for example, C 12 ~C 50 ) linear and / or branched aliphatic (saturated and / or unsaturated) groups, R 2 These are H or C1-C4 alkyl groups, benzyl groups, and polyoxyethylene groups (number of oxyethylene groups e.g., 1 (especially 2, particularly 3) to 50). (CH3 and C2H5 are particularly preferred.) X is a halogen atom (for example), a C1-C4 fatty acid base, p is either 1 or 2, q is either 2 or 3, and p + q = 4. It may be an ammonium salt represented by R. 1 The number of carbon atoms can be 12 to 50, for example, 12 to 30.

[0090] 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.

[0091] [Anionic surfactants] Examples of anionic surfactants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfone fatty acid salts, N-acyl amino acid type surfactants, phosphate mono or diester type surfactants, and sulfosuccinate esters.

[0092] [Amphoteric surfactants] Examples of amphoteric surfactants include alanines, imidazolinium betaines, amide betaines, and betaine acetate. Specifically, these include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetic acid betaine, and fatty acid amidopropyl dimethylaminoacetic acid betaine.

[0093] The surfactant may consist of one or more nonionic surfactants, cationic surfactants, and amphoteric surfactants.

[0094] [Amount of surfactant] The amount of 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, per 100 parts by weight of compound α. The amount of 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, per 100 parts by weight of compound α.

[0095] 〔silicone〕 The oil-repellent agent in this disclosure may contain silicone (polyorganosiloxane). By including silicone, it is possible to achieve good liquid repellency in addition to good texture and durability.

[0096] As the silicone, known silicones can be used. Examples of silicones include polydimethylsiloxane and modified silicones (amino-modified, epoxy-modified, carboxy-modified, methylhydrogen silicones, etc.). The silicone may also be a silicone wax having waxy properties. These may be used alone or in combination of two or more.

[0097] The weight-average molecular weight of the silicone may be 1000 or more, 10000 or more, or 50000 or more. The weight-average molecular weight of the silicone may be 500000 or less, 2500000 or less, 100000 or less, or 50000 or less.

[0098] [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, per 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, per 100 parts by weight of compound α.

[0099] 〔wax〕 The oil-resistant agent in this disclosure may include wax. Including wax can effectively impart liquid repellency to the substrate.

[0100] 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 plant waxes, and mineral waxes. Paraffin wax is preferred. Specific examples of compounds that constitute the wax include n-alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentacontane, hexatriacontane) and n-alkenes (e.g., 1-eicosene, 1-docosene, 1-tricocene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentacontane, hexatriacontane). The number of carbon atoms in the compounds that constitute 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.

[0101] 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.

[0102] [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, per 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, per 100 parts by weight of compound α.

[0103] [Organic acid] The oil-resistant agent may contain an organic acid. Known organic acids can be used. Preferred organic acids include carboxylic acids, sulfonic acids, and sulfinic acids, with carboxylic acids being particularly preferred. Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, and citric acid, with formic acid or acetic acid being particularly preferred. In this disclosure, one organic acid may be used, or two or more may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0104] [Amount of organic acids] The amount of organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 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, per 100 parts by weight of compound α. The amount of 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, per 100 parts by weight of compound α. The amount of organic acid may be adjusted so that the pH of the oil resistant agent is 3 to 10, for example 5 to 9, and especially 6 to 8. The oil resistant agent may be acidic (pH 7 or less, for example 6 or less).

[0105] [Hardening agent] The oil-resistant agent may contain a curing agent (an active hydrogen-reactive compound or an active hydrogen-containing compound).

[0106] The curing agent (crosslinking agent) in oil-resistant agents 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 present in compound α. Examples of active hydrogen-reactive compounds include isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of active hydrogen-containing compounds include hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0107] The curing agent may contain an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. A polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound acts as a crosslinking agent. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (for example, a blocked polyisocyanate compound). A blocked isocyanate compound is a compound in which the isocyanate groups of an isocyanate compound are masked with a blocking agent to suppress the reaction.

[0108] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diiso These include 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.

[0109] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used individually or in combination of two or more.

[0110] Examples of aromatic aliphatic polyisocyanates include aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of aromatic aliphatic polyisocyanates include 1,3- or 1,4-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 individually or in combination of two or more.

[0111] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylenediisocyanate, p-phenylenediisocyanate, 4,4'-diphenyldiisocyanate, 1,5-naphthalenediisocyanate, 2,4'- or 4,4'-diphenylmethanediisocyanate or mixtures thereof, 2,4- or 2,6-tolylenediisocyanate or mixtures thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used individually or in combination of two or more.

[0112] Examples of polyisocyanate derivatives include various derivatives of the polyisocyanate compounds described above, such as dimers, trimers, biuretes, allophanates, carbodiimides, uretodiones, uretoimines, isocyanurates, and iminooxadiazinediones. These may be used individually or in combination of two or more.

[0113] These polyisocyanates can be used individually or in combination of two or more types. It is preferable to use blocked polyisocyanate compounds (blocked isocyanates), which are compounds in which the isocyanate groups of a polyisocyanate compound are blocked with a blocking agent, as the polyisocyanate compound. Blocked polyisocyanate compounds are preferred because they are relatively stable in solution and can be used in the same solution as oil-resistant agents.

[0114] Blocking agents sequester free isocyanate groups. Blocked polyisocyanate compounds can be easily reacted with hydroxyl groups by heating them to, for example, 100°C or higher, such as 130°C or higher, which regenerates the isocyanate groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. Polyisocyanate compounds can be used alone or in combination of two or more.

[0115] Epoxy compounds are compounds that have an epoxy group. Examples of epoxy compounds include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. A chloromethyl group-containing compound is a compound that has a chloromethyl group. Examples of chloromethyl group-containing compounds include chloromethyl polystyrene. Carboxyl group-containing compounds are compounds that have a carboxyl group. Examples of carboxyl group-containing compounds include (poly)acrylic acid and (poly)methacrylic acid.

[0116] Specific examples of ketone group-containing compounds include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of hydrazide compounds include hydrazine, carbohydrazide, and adipic acid hydrazide. Specific examples of melamine compounds include melamine resin and methyl etherified melamine resin.

[0117] [Amount of hardener] The amount of curing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of compound α. The amount of 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, per 100 parts by weight of compound α.

[0118] [Other ingredients] Oil-resistant agents may contain other components besides those listed above. Examples of other components include polysaccharides, paper strength enhancers, flocculants, yield enhancers, coagulants, binder resins, anti-slip agents, sizing agents, paper strength enhancers, fillers, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorizers, and fragrances. These may be used individually or in combination of two or more. In addition to the above-mentioned components, other components include other water-repellent and / or oil-repellent agents, dispersants, texture modifiers, softeners, flame retardants, paint fixatives, wrinkle inhibitors, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage inhibitors, wrinkle inhibitors, shape-retaining agents, drape-retaining agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, color transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain removers, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyldisodium (Chinopearl CBS-X, manufactured by Ciba Specialty Chemicals), dye fixatives, and color-fading inhibitors such as 1,4-bis(3-aminopropyl)piperazine. In addition, enzymes such as cellulase, amylase, protease, lipase, and keratinase can be used as stain removers and fiber surface modifiers; silk protein powder can be used as a foam inhibitor and to impart the texture and functionality of silk, such as moisture absorption and release properties; surface modifiers or emulsified dispersions thereof (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk liquid (Jomo), Silkgen G Solubble S (Ichimaru Falcos)); and anti-fouling agents (e.g., nonionic polymer compounds consisting of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by Go-o Chemical Industry), SRC-1 manufactured by Clariant Japan, etc.). These may be used individually or in combination of two or more.

[0119] [Polysaccharides] Examples of polysaccharides include starch, xanthan gum, karaya gum, gellan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, and pullulan. The polysaccharides may be substituted or modified polysaccharides, and in particular, modified polysaccharides to which hydroxyl groups or cationic groups have been introduced.

[0120] [Paper strength enhancers, flocculants, yield improvers, or coagulants] Examples of paper strength enhancers, flocculants, yield improvers, or coagulants include styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, alkylenedichloride-polyalkylene polyamine condensates, dicyandiamide-formaldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0121] [Cyssing agent] Examples of sizing agents include cellulose-reactive sizing agents, such as rosin-based sizing agents like rosin soap, rosin-based emulsions / dispersions, cellulose-reactive sizing agents, such as emulsions / dispersions of acid anhydrides like alkyl and alkenyl succinic anhydrides (ASA), alkenyl and alkyl ketene dimers (AKD) and polymers, and anionic, cationic and amphoteric polymers of ethylenically unsaturated monomers, such as copolymers of styrene and acrylate.

[0122] [Antistatic agent] Examples of antistatic agents include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate esters, phosphonates, and phosphate esters; amphoteric antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, alanine and its derivatives; and nonionic antistatic agents such as amino alcohols and their derivatives, glycerin and its derivatives, polyethylene glycol and its derivatives. These may also be ion-conductive polymers obtained by polymerizing or copolymerizing monomers having cationic, anionic, or amphoteric ion-conductive groups. These may be used individually or in combination of two or more.

[0123] [Preservatives] Preservatives are primarily used to enhance preservative and bactericidal properties and maintain preservation during long-term storage. Examples of preservatives include isothiazolone-type organosulfur compounds, benzisothiazolone-type organosulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol.

[0124] [UV absorber] UV absorbers are chemicals that have the effect of protecting against ultraviolet rays. They absorb ultraviolet rays and convert them into infrared rays, visible light, etc., and release them. Examples of UV absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, and 4-t-butyl-4'-methoxybenzoylmethane.

[0125] [Antibacterial agent] Antibacterial agents are components that suppress the growth of bacteria on fibers and also suppress the generation of unpleasant odors derived from microbial decomposition products. Examples of antibacterial agents include cationic disinfectants such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide)zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, and polylysine.

[0126] [Deodorizer] Examples of deodorizers include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, and aminocarboxylic acid metal complexes (such as the zinc complex of trisodium methylglycinediacetate described in International Publication No. 2012 / 090580).

[0127] [Amount of other ingredients] The individual or total amounts 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 individual or total amounts 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.

[0128] <Method for manufacturing processed textile or paper products> The method for manufacturing a product treated with an oil-resistant agent in this disclosure includes a processing step of treating a substrate with the oil-resistant agent described above.

[0129] "Treatment" means applying the oil-resistant agent to the substrate by immersion, spraying, coating, etc. Through treatment, compound α, which is the active ingredient of the oil-resistant agent, adheres to the interior and / or surface of the substrate. Here, adhesion may be physical or chemical, and for example, compound α may be physically or chemically modified (by reaction) to the hydroxyl groups present in the substrate (fiber, paper, glass, etc.).

[0130] [Base material] The substrates treated with the oil-resistant agents in this disclosure are not limited, but are preferably textile products or paper products.

[0131] Examples of base materials for textile products include natural animal and plant fibers such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers; or blends thereof. Textile products include woven fabrics, knitted fabrics, and nonwoven fabrics; fabrics in the form of clothing (e.g., water-repellent clothing, e.g., raincoats) and carpets; however, fibers, yarns, and intermediate textile products (e.g., slivers or rovings) in their pre-fabric state may also be treated.

[0132] Examples of base materials for paper products include paper made from bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulps such as crushed wood pulp, mechanical pulp or thermomechanical pulp, recycled paper pulp such as recycled newspaper, recycled magazine, recycled corrugated cardboard or deinked paper, as well as containers and molded bodies made of paper. Specific examples of paper products include food packaging materials, food containers, gypsum board base paper, coated base paper, medium-grade paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-preventive liners and metal interleaving paper, kraft paper, neutral printing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc. Preferred examples include food packaging materials and food containers.

[0133] Substrates treated with the oil-resistant agent of this disclosure are not limited to textile 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, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster.

[0134] When the substrate is glass, the manufactured glass product may be an optical component. A layer (or film), such as a hard coat layer or an anti-reflective layer, may be formed on the surface (outermost layer) of the glass substrate. Either a single-layer anti-reflective layer or a multi-layer anti-reflective layer may be used for the anti-reflective layer. Examples of inorganic materials that can be used for the anti-reflective layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, and WO3. These inorganic materials may be used individually or in combination of two or more (for example, as a mixture). When a multi-layer anti-reflective layer is used, it is preferable to use SiO2 and / or SiO for the outermost layer. When the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode, such as indium tin oxide (ITO) or indium zinc oxide, may be present on part of the surface of the substrate (glass). Furthermore, 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, and a liquid crystal display module, depending on its specific specifications.

[0135] [Processing method] The oil-resistant agent of this disclosure can be applied to a substrate by conventionally known methods as a treatment agent (particularly a surface treatment agent). The treatment method may involve diluting the oil-resistant agent of this disclosure by dispersing it in an organic solvent or water as needed, and then applying it to the interior and / or surface of the substrate by known methods such as immersion coating, spray coating, or foam coating, followed by drying. After drying, a textile product with the solid components of the oil-resistant agent attached is obtained. Furthermore, if necessary, it may be applied together with a suitable crosslinking agent and cured. The oil-resistant agent of this disclosure may also be used in combination with various additives as needed, such as water-repellent and / or oil-repellent agents, anti-slip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, anti-wrinkle agents, drying rate modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insecticides, and defoaming agents. Examples of various additives may be the same as those described in "other components" in the water-repellent composition described above. The concentration of the oil-resistant agent in the treatment agent that comes into contact with the substrate may be changed as appropriate depending on the application, but it may be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0136] The oil repellent can be applied to the substrate by any known method for treating the substrate with a liquid. The substrate may be immersed in the oil repellent, or the solution may be applied to or sprayed onto the substrate. The treated substrate is preferably dried and cured by heating to exhibit 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 this disclosure, good performance can be obtained even with low-temperature heating (e.g., 100°C to 140°C). In this 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 oil repellent may be coated onto the paper, or the solution may be applied to or sprayed onto the paper, or it may be mixed with the pulp slurry before papermaking. The treatment may be an external or internal addition. Alternatively, the oil repellent may be applied to the textile product by a cleaning method, for example, by washing or dry cleaning.

[0137] [Paper processing] Examples of paper-based materials include paper, paper containers, and molded products made from paper (e.g., pulp molds).

[0138] Paper can be manufactured using conventionally known papermaking methods. Either an internal additive treatment method, in which an oil-resistant agent is added to the pulp slurry before papermaking, or an external additive treatment method, in which an oil-resistant agent is applied to the paper after papermaking, can be used.

[0139] The internal additive treatment method may refer to a treatment method in which an oil-resistant agent is added to the pulp slurry before papermaking. The internal additive treatment method may include, but is not limited to, one or more of the following steps: adding an oil-resistant agent to the pulp slurry and stirring and mixing it; dewatering the pulp composition prepared in the first step by suction through a mesh-like body of a predetermined shape to deposit the pulp composition and 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 body. After simple drying at room temperature or high temperature, the treated paper may optionally be heat-treated depending on the properties of the paper. The heat treatment temperature 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 particularly be between 80°C and 180°C. By performing heat treatment in such a temperature range, excellent oil resistance and water resistance can be obtained.

[0140] The size press for external additive processing can also be classified as follows, depending on the application method. One coating method is the so-called pound-type two-roll sizing press, in which a coating liquid (sizing liquid) is supplied to a nip formed by passing paper between two rubber rolls, creating a coating liquid reservoir called a pound, and the sizing liquid is applied to both sides of the paper by passing it through this reservoir. Other coating methods include the gate-roll type and the rod-metering sizing press, which apply the sizing liquid by surface transfer. In the pound-type two-roll sizing press, the sizing liquid easily penetrates into the interior of the paper, while in the surface transfer type, the sizing liquid components tend to remain on the surface of the paper. Compared to the pound-type two-roll sizing press, the surface transfer type allows the coating layer to remain on the surface of the paper more easily, and the coating layer formed on the surface is greater than that of the pound-type two-roll sizing press. In this disclosure, performance can be imparted to the paper even when the former pound-type two-roll sizing press is used. Paper treated in this way can exhibit excellent oil resistance and water resistance, etc., after simple drying at room temperature or high temperature, and optionally with heat treatment that can be performed at temperatures up to 300°C, for example up to 200°C, particularly in the temperature range of 80°C to 180°C, depending on the properties of the paper.

[0141] This 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-preventive liners and metal laminates, kraft paper, and the like. 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.

[0142] Pulp raw materials include bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, wood pulp, mechanical pulp or thermomechanical pulp, etc. Any type of recycled paper pulp can be used, including bleached or unbleached high-yield pulp, recycled newspaper, recycled magazine, recycled corrugated cardboard, or deinked recycled paper. Mixtures of the above pulp raw materials with synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, and polyvinyl alcohol can also be used.

[0143] The water resistance of paper can be improved by adding a sizing agent. Examples of sizing agents include 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 relative to the pulp.

[0144] If necessary, the paper may contain additives used in papermaking, such as paper strength enhancers, flocculants, fixatives, yield improvers, dyes, fluorescent dyes, slime control agents, and defoamers, as commonly used papermaking agents, including starch, modified starch, carboxymethylcellulose, and polyamide polyamine-epichlorohydrin resin. Starch or modified starch is preferred. If necessary, an oil resistant agent can be applied to the paper using a size press, gate roll coater, bill blade coater, calender, etc., with starch, polyvinyl alcohol, dyes, coating colors, anti-slip agents, etc.

[0145] In external additions, the amount of liquid-repellent compound contained in the coating layer is 0.01 to 2.0 g / m². 2 Especially 0.1~1.0g / m 2 Preferably, the coating layer is formed of an oil resistant agent and starch and / or modified starch. The solid content of the paper oil resistant agent in the coating layer is 2 g / m². 2 The following is preferable: In the case of internal additives, it is preferable to mix the oil resistant agent with the pulp such that the amount of oil resistant 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 pulp used to form the paper.

[0146] In external application, oil resistance can also be imparted to paper by using a so-called pound-type two-roll size press process, in which the processing liquid is stored between the rolls and the base paper is passed through the processing liquid between the rolls at an arbitrary roll speed and nip pressure.

[0147] In external additive processing, the paper substrate may contain additives such as sizing agents, paper strength enhancers, flocculants, yield enhancers, or coagulants. The additives may be nonionic, cationic, anionic, or amphoteric. The ionic charge density of the additives is -10,000 to 10,000 μeq / g, preferably -4,000 to 8,000 μeq / g, and more preferably -1,000 to 7,000 μeq / g. Additives such as sizing agents, paper strength enhancers, flocculants, yield enhancers, or coagulants (solid content or active ingredients) can generally be used in an amount of 0.1 to 10% by weight (e.g., 0.2 to 5.0% by weight) relative to the pulp. In the case of a paper substrate containing cationic additives (e.g., sizing agents, paper strength enhancers, flocculants, yield enhancers, or coagulants), the oil repellent is preferably anionic.

[0148] In the internal additive treatment, it is preferable to papermake a pulp slurry having a pulp concentration of 0.5 to 5.0% by weight (for example, 2.5 to 4.0% by weight). Additives (for example, sizing agents, paper strength enhancers, flocculants, yield enhancers or coagulants, etc.) and liquid-repellent compounds can be added to the pulp slurry. Examples of additives (e.g., sizing agents, paper strength enhancers, flocculants, yield enhancers, or coagulants) include alkyl ketene dimers, alkenyl succinic anhydride, styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimines, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, alkylenedichloride and polyalkylene polyamine condensates, dicyandiamide-formaldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0149] [Pre-treatment / processing of textile products] Textile products may be pre-treated before being treated with the oil-resistant agent of this disclosure. Pre-treating textile products can impart excellent durability to them after treatment with the oil-resistant agent.

[0150] Examples of pretreatments for textile products include cationization by reaction with reactive quaternary ammonium salts, anionization by sulfonation, carboxylation, phosphorylation, etc., acetylation, benzoylation, carboxymethylation, grafting, tannic acid treatment, and polymer coating after anionization.

[0151] The method for pre-treating textile products is not limited, but conventionally known methods can be used. The pre-treatment solution may be diluted by dispersing it in an organic solvent or water as needed, and then applied to the interior and / or surface of the textile product by known methods such as immersion coating, spray coating, or foam coating, followed by drying. The pH and temperature of the pre-treatment solution may be adjusted according to the desired degree of treatment. As an example of a method for pre-treating textile products, a method of pre-treating textile products with a hydrocarbon-based water repellent will be described in detail.

[0152] The pretreatment method for textile products involves applying -SO3M to the fibers. 1 (In the formula, M 1 (represents a monovalent cation) a monovalent group represented by -COOM 2 (In the formula, M 2 A monovalent group represented by (where is a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(wherein, X 1 and X 2 The process may include a step of adding one or more functional groups (hereinafter sometimes referred to as "specific functional groups") selected from the group consisting of monovalent groups (each representing a hydrogen atom or an alkyl group having 1 to 22 carbon atoms).

[0153] M 1 Examples include H, K, Na, or ammonium ions which may have substituents. 2 Examples include H, K, Na, or ammonium ions which may have substituents. 1 or X 2 If it 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.

[0154] Fibers containing the above-mentioned 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 above-mentioned specific functional group is attached to the fiber material. The attachment of the compound may be such that a portion of the compound and a portion of the fiber are chemically bonded, to the extent that a sufficient amount of the above-mentioned specific functional group remains. (ii) Prepare a fiber in which the above-mentioned specific functional group is directly introduced into the material constituting the fiber.

[0155] (i) For example, a functional group-containing fiber can be obtained by a functional group introduction step in which the fiber material is treated with a pretreatment solution containing one or more compounds having the above-mentioned specific functional group.

[0156] The oil-resistant agent can be applied to a fibrous substrate (e.g., a textile product that may have undergone the pretreatment described above) by any known method for treating textile products with liquids. When the textile product is a cloth, the cloth may be immersed in the solution, or the solution may be applied to or sprayed onto the cloth. The treated textile product is dried, preferably heated, for example, at 80°C to 200°C, to develop liquid-repellent (water-repellent and / or oil-repellent) properties. Alternatively, the oil-resistant agent may be applied to the textile product by a cleaning method, for example, by washing or dry cleaning.

[0157] The textile products to be processed are typically cloths, including woven, knitted and nonwoven fabrics, cloths in garment form 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 reocell), or synthetic fibers (e.g., polyester, polyamide or acrylic fibers), or a mixture of fibers (e.g., a mixture of natural and synthetic fibers). The methods of this disclosure generally make the textile products hydrophobic and water-repellent. Alternatively, the fibrous substrate may be leather. The manufacturing polymer may be applied to the leather in the form of an aqueous solution or aqueous emulsion at various stages of leather processing, for example, during the wetting process of the leather or during the finishing process of the leather, in order to make the leather hydrophobic and oleophobic.

[0158] "Treatment" refers to applying an oil-resistant agent to the object to be treated by means of immersion, spray coating, etc. Through treatment, the active ingredients of the oil-resistant agent penetrate into the interior of the object and / or adhere to the surface of the object to be treated.

[0159] There are no particular restrictions on the material of the fiber material, and examples include natural fibers such as cotton, linen, silk, and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene; and composite fibers and blended fibers thereof. The fiber material may take any form, such as fibers (tow, sliver, etc.), yarn, knitted fabrics (including interwoven fabrics), woven fabrics (including interwoven fabrics), and nonwoven fabrics.

[0160] In this embodiment, from the viewpoint of obtaining good water repellency in the resulting textile product, it is preferable to use a fiber material containing polyamide and polyester as a base material. In particular, it is preferable to use nylon such as nylon 6 and nylon 6,6, polyester such as polyethylene terephthalate (PET), polytrimethyl terephthalate, and polylactic acid, and mixed fibers containing these.

[0161] The above -SO3M 1As a compound having this property, phenolic polymers can be used. Examples of such phenolic polymers include those containing at least one compound represented by the following general formula.

[0162] TIFF0007832525000013.tif4678 [In the formula, X 2 ha-SO3M 3 (In the formula, M 3 (where n represents a monovalent cation) or a group represented by the following general formula, where n is an integer between 20 and 3000.

[0163] TIFF0007832525000014.tif2661 [In the formula, M 4 This represents a monovalent cation.

[0164] The above M 3 Examples include H, K, Na, or ammonium ions which may have substituents.

[0165] The above M 4 Examples include H, K, Na, or ammonium ions which may have substituents.

[0166] The compound represented by the above general formula may, for example, be a formalin condensate of phenolsulfonic acid or a formalin condensate of sulfonated bisphenol S.

[0167] The above-COOM 2 Examples of compounds having this property include polycarboxylic acid polymers.

[0168] As polycarboxylic acid polymers, for example, polymers synthesized by conventionally known radical polymerization methods using acrylic acid, methacrylic acid, maleic acid, etc. as monomers, or commercially available polymers can be used.

[0169] One method for producing polycarboxylic acid polymers is to add a radical polymerization initiator to an aqueous solution of the monomer and / or its salt, and heat the reaction at 30 to 150°C for 2 to 5 hours. At this time, alcohols such as methanol, ethanol, isopropyl alcohol, or aqueous solvents such as acetone may be added to the aqueous solution of the monomer and / or its salt. Examples of radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, redox polymerization initiators using combinations of persulfates and sodium bisulfite, hydrogen peroxide, and water-soluble azo 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.

[0170] In radical polymerization, copolymerizable monomers can be used in addition to the monomers mentioned above. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, as well as acrylamide, acrylates, and methacrylates. Acrylates and methacrylates are preferably those having a hydrocarbon group with 1 to 3 carbon atoms, which may have substituents such as hydroxyl groups. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, and propyl methacrylate. These copolymerizable monomers may be used individually or in combination of two or more.

[0171] The carboxyl groups in the polycarboxylic acid polymer may be free or neutralized by alkali metals or amine compounds. Examples of alkali metals include sodium, potassium, and lithium, while examples of amine compounds include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0172] 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 obtaining good water repellency in the resulting textile product.

[0173] For polycarboxylic acid polymers, commercially available products such as "NeoCrystal 770" (manufactured by Nikka Chemical Co., Ltd., product name) and "Cellopol PC-300" (manufactured by Sanyo Chemical Industries, Ltd., product name) can be used.

[0174] The above - OP(O)(OX 1 )(OX 2 Examples of compounds having the following general formula include phosphate ester compounds. TIFF0007832525000015.tif3243[where, X 1 or X 2 This is synonymous with the above, X 3 This represents an alkyl group with 1 to 22 carbon atoms.

[0175] As the phosphate ester compound mentioned above, phosphate monoesters, diesters, and triesters in which the alkyl ester portion has an alkyl group having 1 to 22 carbon atoms, as well as mixtures thereof, can be used.

[0176] From the viewpoint of obtaining good water repellency in the resulting textile product, it is preferable to use lauryl phosphate esters and decyl phosphate esters.

[0177] For the phosphate ester compound, commercially available products such as "Phosphanol ML-200" (manufactured by Toho Chemical Industry Co., Ltd., trade name) can be used.

[0178] The pretreatment solution containing one or more compounds having the above-mentioned specific functional groups can, for example, be an aqueous solution of the compounds described above. The pretreatment solution may also contain acids, alkalis, surfactants, chelating agents, etc.

[0179] Methods for treating fibrous materials with the above-mentioned pretreatment solution include, for example, padding, immersion, spraying, and coating. For padding, for example, methods using padding equipment described on pages 396-397 of the Dictionary of Textile Dyeing and Processing (published in 1963 by Nikkan Kogyo Shimbun) and pages 256-260 of Color Dyeing Chemistry III (published in 1975 by Jikkyo Shuppan Co., Ltd.) can be used. For coating, for example, methods using coating machines described on pages 473-477 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senryo-sha) can be used. For immersion, for example, methods using batch-type dyeing machines described on pages 196-247 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senryo-sha) can be used, and liquid flow dyeing machines, air flow dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, cheese dyeing machines, etc. can be used. Examples of spray treatments include air sprays that atomize the treatment solution using compressed air, and air sprays that use a hydraulic atomization system. The concentration of the treatment solution and the treatment conditions such as heat treatment after application can be adjusted as appropriate, taking into account the purpose, performance, and other conditions. If the pretreatment solution contains water, it is preferable to dry it to remove the water after it has been applied to the fiber material. There are no particular restrictions on the drying method, and either a dry heat method or a wet heat method may be used. There are no particular restrictions on the drying temperature, but for example, drying at room temperature to 200°C for 10 seconds to several days is 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.

[0180] Furthermore, if the fiber material is to be dyed, the pretreatment with the pretreatment solution may be performed before dyeing or in the same bath as the dyeing. However, if reducing soaping is performed, there is a risk that the compounds having the specific functional groups (e.g., phenolic polymer compounds, etc.) that have been adsorbed during the process may be removed. Therefore, it is preferable to perform the pretreatment after reducing soaping following dyeing.

[0181] The treatment temperature during the immersion process can be 60 to 130°C. The treatment time can be 5 to 60 minutes.

[0182] In the functional group introduction step using the pretreatment solution, it is preferable to treat the material in such an amount that the amount of compound having the specified functional group attached is 1.0 to 7.0 parts by weight per 100 parts by weight of the fiber material. Within this range, a high level of both durable water repellency and texture can be achieved.

[0183] The pretreatment solution is preferably adjusted to a pH of 3-5. pH adjustment can be done using pH adjusting agents such as acetic acid or malic acid.

[0184] The pretreatment solution may also contain salt to effectively adsorb the compound having the above-mentioned specific functional group onto the fiber material through a salting-out effect. Examples of salts that can be used include sodium chloride. Examples include sodium carbonate, ammonium sulfate, and sodium sulfate.

[0185] In the functional group introduction step using a pretreatment solution, it is preferable to remove any compounds having the specified functional groups that have been excessively treated. One method of removal is washing with water. By ensuring sufficient removal, it is possible to suppress the inhibition of water repellency development in the subsequent water-repellent treatment, and in addition, the texture of the resulting textile product will be improved. Furthermore, it is preferable to thoroughly dry the resulting functional group-containing fibers before contacting them with a hydrocarbon-based water repellent.

[0186] (ii) Examples of fibers in which the above-mentioned specific functional groups are directly introduced into the material constituting the fiber include cationic dyeable polyester (CD-PET).

[0187] From the viewpoint of obtaining good water repellency in the resulting textile product, the functional group-containing fibers preferably have a surface zeta potential of -100 to -0.1 mV, and more preferably -50 to -1 mV. The surface zeta potential of the fibers can be measured, for example, using the zeta potential / particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0188] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims. [Examples]

[0189] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0190] <Testing Method> The examination procedure is as follows:

[0191] [Preparation of processed paper] Water resistance (Cobb value): 52g / m 2 , basis weight 45g / m 2 , density 0.60g / m 3 For thin paper, 14.9 mg / cm³ 3 The treated paper was prepared by coating a solution of the compound three times using a Baker-type applicator with a gap set to 0 mil, and then annealing it at 140°C for 1 minute. Chloroform was used to prepare the coating solution. If the compound was insoluble in chloroform, organic solvents such as toluene or acetone were used.

[0192] [KIT Test (Oil Resistance)] The results were measured using the 3M Kit Test (TAPPI T-559cm-02). The 3M Kit Test method involves placing a test oil containing castor oil, toluene, and heptane onto the surface of treated paper, and then wiping off the test oil after 15 seconds. The presence or absence of oil stains on the treated paper is used for evaluation. Tests were conducted with test oils numbered 1 to 6, and the kit number with the highest number of unstained test results was used as the evaluation result for oil resistance.

[0193] [Corn oil resistance test (oil resistance)] Corn oil is placed on the surface of the treatment paper, and after 15 seconds, the test oil is wiped off. The evaluation is based on whether or not there is an oil stain on the treatment paper. Mark with ○ if there are no stains, and with × if stains are visible.

[0194] [HD contact angle] A 1.0% solid content solution (or dispersion) of compound α was spin-coated onto a silicon wafer at 2500 rpm for 25 seconds to obtain a smooth spin-coated film. This film was then 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 drop was taken as the HD contact angle of compound α.

[0195] [Water repellency test] A treatment solution containing compound α at a solid content of 16.8 mg / mL was prepared using chloroform as the solvent. A cloth was immersed in this treatment solution, passed through a mangle, and heat-treated. The water repellency of the test cloth was then evaluated. The water repellency of the treated cloth was evaluated according to the spray method of JIS-L-1092 (AATCC-22). The water repellency is expressed by a water repellency number as shown in the table below. A higher score indicates better water repellency. TIFF0007832525000016.tif45152

[0196] [Mold creation] An automatic mold forming machine was used to form the mold. At the bottom, a mesh structure was placed on top of a metal pulp mold with numerous suction holes, and at the top, a metal tank was placed, into which the pulp slurry was placed. From the side of the pulp mold opposite the mesh structure, the pulp-containing aqueous composition was sucked and dewatered at 0.1 to 1 MPa using a vacuum pump, and the solid components (pulp, etc.) contained in the pulp-containing aqueous composition were deposited on the mesh structure to obtain a pulp mold intermediate. Next, the obtained pulp mold intermediate was dried from above and below at a pressure of 0.1 to 1 MPa using a metal male-female mold heated to 60 to 200°C. This produced a pulp mold product molded into the shape of a container.

[0197] [Mold Test: Practical Oil Resistance Test] 100 ml of corn oil at 65°C was poured into the mold, left at room temperature for 45 minutes, and then the corn oil was removed from the mold. The degree of oil staining on the mold was then evaluated. The following evaluation values ​​were set based on the degree of staining. 5: No stains on the inside. 4: Stain on the inside. No stain on the reverse side. 3: There is a stain on the inside. There is a slight seepage on the reverse side. 2: There is a stain on the inside. The stain has seeped through to the back over less than 50% of the area. 1: There is a stain on the inside. The stain has seeped through to the back, covering more than 50% but less than 100% of the area. 0: Staining across the entire back side.

[0198] [Mold Test, Practical Water Resistance Test] 100 ml of 100°C water was poured into the mold, left at room temperature for 30 minutes, and then the water was removed from the mold. The degree of staining of the mold was then evaluated. The following evaluation values ​​were set based on the degree of staining. 5: No stains on the inside. 4: Stain on the inside. No stain on the reverse side. 3: There is a stain on the inside. There is a slight seepage on the reverse side. 2: There is a stain on the inside. The stain has seeped through to the back over less than 50% of the area. 1: There is a stain on the inside. The stain has seeped through to the back, covering more than 50% but less than 100% of the area. 0: Staining across the entire back side.

[0199] <Synthesis of Compounds> The compounds used in the test were synthesized by the following method.

[0200] [Compound 2]

[0201] 8.00 g of octadecanol (Tokyo Chemical Products) was dissolved in 65.0 mL of anhydrous tetrahydrofuran (Fujifilm Wako Pure Chemical Industries), and the mixture was cooled in an ice bath. After 10 minutes, 4.53 mL of triethylamine and 2.82 mL of 2-chloroacetate chloride (Fujifilm Wako Pure Chemical Industries) were added in that order, and the mixture was stirred overnight. The next day, the reaction solution was filtered, the filtrate was concentrated, and the residue was stirred in methanol for 10 minutes before being stored in the refrigerator. After 3 hours, the solid was filtered and dried to obtain 9.36 g of compound 1 shown below. TIFF0007832525000017.tif2065 1 H 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).

[0202] 4.23 g of compound 1 was dissolved in 20.0 mL of anhydrous tetrahydrofuran (Fujifilm Wako Pure Chemical Industries), then 2.95 mL of anhydrous pyridine (Fujifilm Wako Pure Chemical Industries) was added, and the mixture was stirred overnight at an oil bath temperature of 50°C. The next day, the reaction solution was stored in the refrigerator. After 3 hours, the solid was filtered and dried to obtain 1.51 g of compound 2 shown below. TIFF0007832525000018.tif2867 1 H 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).

[0203] [Compound 3] Compound 3, shown below, was synthesized with reference to Journal of Chemical Research (2013), 37(4), 205-207. TIFF0007832525000019.tif2867

[0204] [Compound 6] First, referring to ChemMedChem (2016), 11(21), 2367-2371, we synthesized compound 4 shown below. TIFF0007832525000020.tif1647

[0205] 5g of compound 4, 1.3mL of propargyl alcohol (Fujifilm Wako Pure Chemical Industries), 0.85g of copper sulfate pentahydrate (Fujifilm Wako Pure Chemical Industries), 1.34g of sodium L-ascorbate (Fujifilm Wako Pure Chemical Industries), and 0.625g of tetrabutylammonium iodide (Fujifilm Wako Pure Chemical Industries) were dissolved in a mixed solvent of 20.0mL of tetrahydrofuran (Fujifilm Wako Pure Chemical Industries) and 20.0mL of water, and the mixture was 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 5.95g of compound 5 shown below. TIFF0007832525000021.tif2367 1 H 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).

[0206] Next, 2.5 g of compound 5 was dissolved in 10.0 mL of anhydrous pyridine (Fujifilm Wako Pure Chemical Industries), then 1.03 mL of thionyl chloride (Fujifilm Wako Pure Chemical Industries) was added, and the mixture was stirred overnight at an oil bath temperature of 80°C. The following day, after cooling to room temperature, 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. TIFF0007832525000022.tif3680 1 H 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).

[0207] [Compound 8] 10.0 g of stearic acid (Tokyo Chemical Products), 0.429 g of 4,4-dimethylaminopyridine (Fujifilm Wako Pure Chemical Industries), and 5.05 g of glycinamide hydrochloride (Fujifilm Wako Pure Chemical Industries) were dissolved in 100.0 mL of anhydrous dimethylformamide (Fujifilm Wako Pure Chemical Industries). Then, 6.37 mL of triethylamine and 8.76 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (Tokyo Chemical Products) 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, 50 mL of methanol was added, and the mixture was filtered. The solid was washed with methanol and diethyl ether, and after washing, the solid was dried to obtain 7.35 g of compound 7 shown below. TIFF0007832525000023.tif2773 1 H 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).

[0208] 8.5 g of compound 7, 4.61 g of pyridine hydrochloride (Fujifilm Wako Pure Chemical Industries), and 1.05 g of paraformaldehyde (Fujifilm Wako Pure Chemical Industries) were dissolved in 90.0 mL of anhydrous pyridine (Fujifilm Wako Pure Chemical Industries), and the mixture was stirred overnight at an oil bath temperature of 85°C. The next day, the reaction solution was cooled to room temperature, the solid was filtered, and the solid was washed with pyridine and acetone. After washing, the solid was dried to obtain 6.76 g of compound 8 shown below. TIFF0007832525000024.tif3183 1 H 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).

[0209] [Compound 10] 10.0 g of stearic acid (Tokyo Chemical Products), 6.7 g of 4-aminobenzamide (Fujifilm Wako Pure Chemical Industries), and 0.429 g of 4,4-dimethylaminopyridine (Fujifilm Wako Pure Chemical Industries) were dissolved in 100.0 mL of anhydrous dimethylformamide (Fujifilm Wako Pure Chemical Industries). Then, 8.76 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (Tokyo Chemical Products) was 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, 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. TIFF0007832525000025.tif3196

[0210] 7.5 g of compound 9, 3.01 g of pyridine hydrochloride (Fujifilm Wako Pure Chemical Industries), and 0.81 g of paraformaldehyde (Fujifilm Wako Pure Chemical Industries) were dissolved in 90.0 mL of anhydrous pyridine (Fujifilm Wako Pure Chemical Industries), 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, the solid was filtered, and the solid was washed with pyridine and methanol. After washing, the solid was dried to obtain 5.60 g of compound 10 shown below. TIFF0007832525000026.tif3693 1 H 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).

[0211] [Compound 12] First, 10.0 g of stearic acid (Tokyo Chemical Products), 7.4 g of 2-chloroacetamide (Fujifilm Wako Pure Chemical Industries), and 7.0 g of potassium carbonate (Fujifilm Wako Pure Chemical Industries) were dissolved in 60.0 mL of anhydrous dimethylformamide (Fujifilm Wako Pure Chemical Industries), 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, 50 mL of water was added, and the mixture was 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. TIFF0007832525000027.tif2566 1 H 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).

[0212] Next, 11.05 g of compound 11, 5.38 g of pyridine hydrochloride (Fujifilm Wako Pure Chemical Industries), and 1.28 g of paraformaldehyde (Fujifilm Wako Pure Chemical Industries) were dissolved in 70.0 mL of anhydrous pyridine (Fujifilm Wako Pure Chemical Industries), and the mixture was stirred overnight at an oil bath temperature of 83°C. The following day, the reaction solution was cooled to room temperature, the solid was filtered, and the solid was washed with methanol and acetone. After washing, the solid was dried to obtain 5.11 g of compound 12 as shown below. TIFF0007832525000028.tif2975 1 H 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).

[0213] [Compound 13] Compound 13, shown below, was synthesized with reference to Journal of Organic Chemistry (1951), 16, 1111-16. TIFF0007832525000029.tif3364

[0214] <Test Results> Table 1 shows the results of the KIT test, corn oil resistance test, and HD contact angle evaluation.

[0215] [Table 1] TIFF0007832525000030.tif58168

[0216] The results of the mold test are shown in Table 2. The molds were prepared using the following method. Compound 8 was ground into a powder using a mortar and pestle. To 1 g of this powder, 0.1 g of polyoxyethylene (10) oleyl ether and 8.9 g of water were added and mixed in a mix rotor for 6 hours. By stirring in a homogenizer at 10,000 rpm for 20 minutes, an aqueous dispersion of Compound 8 was obtained. Subsequently, the aqueous dispersion of Compound 8 was added to a 0.5 wt% pulp slurry at a ratio of 5 wt% relative to the pulp in terms of solid content to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was put into an automatic mold molding machine to produce a mold.

[0217] Compound 13 was ground into a powder using a mortar and pestle. To 1 g of this powder, 0.1 g of polyoxyethylene (10) oleyl ether and 8.9 g of water were added and mixed in a mix rotor for 6 hours. By stirring in a homogenizer at 10,000 rpm for 20 minutes, an aqueous dispersion of compound 13 was obtained. Subsequently, the aqueous dispersion of compound 13 was added to a 0.5 wt% pulp slurry at a ratio of 10 wt% relative to the pulp in terms of solid content to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was put into an automatic mold molding machine to produce a mold.

[0218] [Table 2] TIFF0007832525000031.tif28155

[0219] The results of the water repellency test are shown in Table 3. A water repellency test was conducted on PET fibers (PET fabric) of compound 3. The adhesion rate of compound 3 to the treated PET fibers was 2.1 wt%.

[0220] [Table 3] TIFF0007832525000032.tif17155

Claims

1. It is an oil-resistant agent, The aforementioned oil-resistant agent is The following formula: [In the formula, Y － It is a counter anion, X is an n+m valency group and is an aromatic group, or has one or more selected from the group consisting of an amide group, a urea group, a urethane group, and an imide group. R is a monovalent hydrocarbon group having 6 to 40 carbon atoms, either linear or branched. Z is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or -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 between 1 and 10, n is an integer between 1 and 3, p is an integer between 0 and 2 (inclusive). It contains a compound represented by, X is, -X １ -, -X １ -X ２ -, -X １ -X ２ -X １ -, -X １ -X ２ (-) ２ , -(X １ ) ２ -X ２ -(where X ２ is trivalent), -(X １ ) ２ X ２ (-) ２ (where X ２ is tetravalent), -X ２ -, -X ２ -X １ -, or -X ２ -X １ -X ２ - [In the formula, X １ but, direct binding, -O-, -O-C(=O)-, -O-C(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)- -C(=O)-O-, -C(=O)-NR'-, or -C(=O)-NR'-C(=O)- [In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.] And, X ２ However, it is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a divalent aromatic group. However, the selection of X1 and X2 is excluded if X is not an aromatic group and does not have one or more selected from the group consisting of amide groups, urea groups, urethane groups, and imides. It is a base represented by, -X-R ｎ It is not -NHC(=O)-R, but an oil-resistant agent.

2. Y － The oil-resistant agent according to claim 1, wherein is at least one selected from the group consisting of halide ions, sulfonate ions, phosphate ions, and carboxylate ions.

3. X ２ The oil-resistant agent according to claim 1 or 2, wherein it is composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a divalent hydrocarbon aromatic ring, and a divalent heterocycle.

4. The oil-resistant agent according to claim 1 or 2, wherein the number of carbon atoms in R is 12 or more.

5. The oil-resistant agent according to claim 1 or 2, wherein the compound has a melting point of 40°C or higher, or has no melting point.

6. The oil-resistant agent according to claim 1 or 2, wherein the n-hexadecane contact angle of the compound is 10° or more.

7. Containing a liquid medium, 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 20°C.

8. The oil-resistant agent according to claim 1 or 2, which is an aqueous dispersion.

9. An oil-resistant agent according to claim 1 or 2, for use with paper.

10. An oil-resistant agent according to claim 1 or 2, which does not contain a fluorine compound.

11. 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 fibers.

12. Oil-resistant paper 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 paper.

13. 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.

14. The oil-resistant paper according to claim 12, which is a food packaging material or food container.

15. A method for producing oil-resistant paper, comprising the step of externally or internally applying an oil-resistant agent according to claim 1 or 2.

16. The following formula: [In the formula, Y － It is a counter anion, R is a monovalent hydrocarbon group having 6 to 40 carbon atoms, either linear or branched. Z is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or -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 between 0 and 2 (inclusive). A compound represented by the formula.

17. A aqueous dispersion, The aqueous dispersion is The following formula: [In the formula, Y － It is a counter anion, X is an n+m valency group and is an aromatic group, or has one or more selected from the group consisting of an amide group, a urea group, a urethane group, and an imide group. R is a monovalent hydrocarbon group having 6 to 40 carbon atoms, either linear or branched. Z is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or -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 between 1 and 10, n is an integer between 1 and 3, p is an integer between 0 and 2 (inclusive). The compound represented by [formula], and at least one selected from the group consisting of nonfluorine surfactants, silicones, waxes, organic acids, and curing agents, X is, -X １ -, -X １ -X ２ -, -X １ -X ２ -X １ -, -X １ -X ２ (-) ２ , -(X １ ) ２ -X ２ - (Here, X ２ (is trivalent), -(X １ ) ２ X ２ (-) ２ (Here, X ２ (It is tetravalent.) -X ２ -, -X ２ -X １ -, or -X ２ -X １ -X ２ - [In the formula, X １ but, direct binding, -O-, -O-C(=O)-, -O-C(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)- -C(=O)-O-, -C(=O)-NR'-, or -C(=O)-NR'-C(=O)- [In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.] And, X ２ However, it is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a divalent aromatic group. However, the selection of X1 and X2 is excluded if X is not an aromatic group and does not have one or more selected from the group consisting of amide groups, urea groups, urethane groups, and imides. A water dispersion of the group represented by [the symbol].

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