Repellent

Abstract

To provide a novel repellent agent that is capable of imparting liquid repellency to a base material (such as fiber or paper).SOLUTION: A repellent agent contains a liquid repellent compound that has an amine skeleton and one or more long-chain hydrocarbon-containing groups represented by formula -X-Rn (where each symbol has the same meaning as described in the specifications), with at least one of the long-chain hydrocarbon-containing groups being bonded to a nitrogen atom in the amine skeleton.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to repellents. [Background technology]

[0002] In recent years, research has been conducted into materials and methods that can impart water repellency, oil repellency, and the like to various substrates. Patent Document 1 discloses that water repellency can be imparted to a fiber substrate by using a non-fluorine-based acrylic polymer that contains a structural unit derived from a (meth)acrylic acid ester monomer and a structural unit derived from a silicone oil having a (meth)acryloyl group. In the invention described in Patent Document 1, the non-fluorine-based acrylic polymer is an essential component. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2016-199712 A Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present disclosure is to provide a novel repellent agent that can impart liquid repellency to a substrate (for example, fiber, paper). [Means for solving the problem]

[0005] The present disclosure includes the following aspects: [Section 1] an amine backbone, and The formula: -XR n [In the formula, X is a direct bond or a 1+n valent group; R is independently in each occurrence a linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent; n is an integer between 1 and 3. The compound has one or more long chain hydrocarbon-containing groups represented by the formula: A liquid repellent comprising a liquid repellent compound, wherein at least one of the long chain hydrocarbon-containing groups is bonded to a nitrogen atom of the amine skeleton. [Section 2] Item 2. The repellent according to item 1, wherein the amine skeleton is composed of a monovalent to trivalent amino group and a linear saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group which may be interrupted by an oxygen atom and / or a sulfur atom. [Section 3] Item 3. The repellent according to item 1 or 2, wherein the molar ratio of carbon atoms to nitrogen atoms (C / N ratio) in the amine skeleton is 8 or less. [Section 4] The liquid repellent compound is The formula: N(-XR n ) p (-H) q -L 1 -[N(-XR n ) r (-H) s -L 1 -] t -N(-XR n ) p (-H) q [In the formula, X is independently in each occurrence a direct bond or a group having a valence of 1+n; R is independently in each occurrence a linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent; L 1 represents, independently in each occurrence, a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by an oxygen atom and / or a sulfur atom; n, independently in each occurrence, is an integer between 1 and 3, inclusive; p, in each occurrence, is an integer greater than or equal to 0 and less than or equal to 2; q, independently in each occurrence, is an integer greater than or equal to 0 and less than or equal to 2; p+q is the sum of each N(-XR n ) p (-H) q In, 2, r is independently in each occurrence 0 or 1; s is independently in each occurrence 0 or 1; r+s is the sum of each N(-XR n ) r (-H) s In, the sum of all p's and all r's is greater than or equal to 1; t is an integer between 0 and 10. or The formula: N(-XR n ) p (-H) q -L 2 (-XR n ) u [In the formula, X is independently in each occurrence a direct bond or a group having a valence of 1+n; R is independently in each occurrence a linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent; L 2 represents an aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms and a valence of 1+u, which may be interrupted by an oxygen atom and / or a sulfur atom, n, independently in each occurrence, is an integer between 1 and 3, inclusive; p is an integer between 0 and 2, q is an integer between 0 and 2, p+q is 2, u is an integer between 1 and 3, The sum of p and u is greater than or equal to 1.] Item 4. The repellent according to any one of items 1 to 3, which is a compound represented by the following formula: [Section 5] Item 5. The repellent according to any one of items 1 to 4, wherein R has 12 or more carbon atoms. [Section 6] X is a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2, a di- to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a di- to tetravalent hydrocarbon aromatic ring, or a di- to tetravalent heterocycle. [In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.] 6. The repellent according to any one of items 1 to 5, wherein the repellent is a 1+n valent group consisting of one or more groups selected from the group consisting of: [Section 7] Item 7. The liquid repellent according to any one of items 1 to 6, wherein the liquid repellent compound has a melting point of 40° C. or higher, or has no melting point. [Section 8] Item 8. The liquid repellent according to any one of items 1 to 7, wherein the liquid repellent compound has a contact angle with n-hexadecane of 10° or more. [Section 9] Item 9. The liquid repellent according to any one of items 1 to 8, wherein the liquid repellent compound has a bio-based content of 30% or more. [Section 10] Item 10. The repellent according to any one of items 1 to 9, wherein the volumetric abundance ratio of particles having a size of 100 μm or more is 25% or less as measured by dynamic light scattering or laser diffraction scattering. [Section 11] Item 11. The repellent according to any one of items 1 to 10, which is an aqueous dispersion. [Section 12] Item 12. The repellent according to item 11, comprising one or more selected from the group consisting of surfactants, silicones, waxes, organic acids, and curing agents. [Section 13] Item 13. The repellent according to any one of items 1 to 12, which is for paper. [Section 14] Item 14. The repellent according to any one of items 1 to 13, which does not contain a fluorine compound. [Section 15] Item 15. A textile product having the liquid repellent compound in the repellent according to any one of items 1 to 14 adhered thereto. [Section 16] Item 15. An oil-resistant or water-repellent paper having the liquid-repellent compound in the repellent agent according to any one of items 1 to 14 attached thereto. [Section 17] Item 15. Glass to which the liquid repellent compound in the liquid repellent according to any one of items 1 to 14 is adhered. [Section 18] Item 17. The grease-resistant or water-repellent paper according to item 16, which is a food packaging material or a food container. [Section 19] Item 15. A method for producing oil-resistant or water-repellent paper, comprising a step of externally or internally treating paper with the repellent according to any one of items 1 to 14. [Section 20] The formula: N(-XR n ) p (-H) q -L 1 -[N(-XR n ) r (-H) s -L 1 -] t -N(-XR n ) p (-H) q [In the formula, X is independently in each occurrence a direct bond or a group having a valence of 1+n; R is independently in each occurrence a linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent; L 1 represents, independently in each occurrence, a divalent aliphatic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by an oxygen atom and / or a sulfur atom; n, independently in each occurrence, is an integer between 1 and 3, inclusive; p, in each occurrence, is an integer greater than or equal to 0 and less than or equal to 2; q, independently in each occurrence, is an integer greater than or equal to 0 and less than or equal to 2; p+q is the sum of each N(-XR n ) p (-H) q In, 2, r is independently in each occurrence 0 or 1; s is independently in each occurrence 0 or 1; r+s is the sum of each N(-XR n ) r (-H) sIn, the sum of all p's and all r's is greater than or equal to 1; t is an integer between 2 and 10. or The formula: N(-XR n ) p (-H) q -L 2 (-XR n ) u [In the formula, X is independently in each occurrence a direct bond or a group having a valence of 1+n; R is independently in each occurrence a linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent; L 2 represents a 1+u-valent aliphatic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by an oxygen atom and / or a sulfur atom, n, independently in each occurrence, is an integer between 1 and 3, inclusive; p is an integer between 0 and 2, q is an integer between 0 and 2, p+q is 2, u is an integer between 1 and 3, The sum of p and u is greater than or equal to 1.] A compound represented by the formula: [Section 21] The formula: TIFF0007648935000001.tif3567[In the formula, R is a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent.] A compound represented by the formula: [Section 22] The formula: TIFF0007648935000002.tif4055[in the formula, R is a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent.] A compound represented by the formula: Effect of the Invention

[0006] The repellent agent of the present disclosure can impart liquid repellency to a substrate (e.g., textile, paper). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

[0008] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, which is a group obtained by removing a hydrogen atom from a hydrocarbon. Such a hydrocarbon group includes, but is not limited to, C 1-20 Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The above-mentioned "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The cyclic group may include a chain structure. The hydrocarbon group may be substituted with one or more substituents.

[0009] In this specification, when a term (symbol) that may occur multiple times in a chemical structure is defined, that definition applies independently to each occurrence, unless otherwise stated, regardless of whether "independently at each occurrence," "independently of each other," "independently of each other," or similar expressions are explicitly stated.

[0010] It should be understood that the chemical structures illustrated herein do not encompass chemical structures that would be recognized by those of ordinary skill in the art as being chemically impossible or extremely unstable.

[0011] <Repellent> The repellent of the present disclosure provides liquid repellency to a substrate (e.g., a fiber substrate, a paper substrate, glass, e.g., fabric, paper, etc.). The repellent of the present disclosure may also function as at least one selected from the group consisting of a water repellent, an oil repellent, an oil-resistant agent, and a water-resistant agent. For example, the repellent of the present disclosure is also useful as an additive for paper products, and the performance (e.g., water resistance, oil resistance, paper strength, etc.) of a paper product obtained from a pulp composition to which the repellent has been added may be improved.

[0012] Due to its structure, the liquid repellent compound, which is the active ingredient in the repellent of the present disclosure, has excellent dispersibility in liquid media, and the performance of the repellent of the present disclosure can be stable.

[0013] Conventional repellents that use polymeric compounds as active ingredients tend to have a broad molecular weight distribution and contain relatively large amounts of impurities, whereas the active ingredient of the repellent of the present invention is a low molecular weight compound, which can narrow (unify) the molecular weight distribution and improve performance.

[0014] The repellent in the present disclosure includes a liquid repellent compound. The repellent in the present disclosure may be the liquid repellent compound alone. The repellent in the present disclosure may include other components such as a liquid medium in addition to the liquid repellent compound.

[0015] The repellent agent in the present disclosure may not contain any compound selected from the group consisting of a compound having a fluoroalkyl group having 8 or more carbon atoms, a compound having a perfluoroalkyl group having 8 or more carbon atoms, a compound having a fluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The repellent agent in the present disclosure can impart liquid repellency to a substrate even if it does not contain these fluorine compounds.

[0016] The volumetric ratio of particles of 100 μm or more in the repellent of the present disclosure measured by dynamic light scattering or laser diffraction scattering may be 25% or less, 20% or less, 15% or less, 10% or less, 5% or less, 3% or less, or 1.5% or less, and is preferably 15% or less, or 5% or less. It is preferable from the viewpoint of coating properties that the volumetric ratio of particles of 100 μm or more is within the above range. There is no limitation on the method for making the volumetric ratio of particles of 100 μm or more measured by dynamic light scattering or laser diffraction scattering 25% or less, but for example, the particles in the raw material and / or dispersion may be finely divided using a grinder, homogenizer, or the like.

[0017] The volume median diameter of the repellent of the present disclosure measured by the dynamic light scattering method or the laser diffraction scattering method may be 10 nm or more, 30 nm or more, 50 nm or more, or 100 nm or more, preferably 150 nm or more or 200 nm or more, and may be 100 μm or less, 90 μm or less, 80 μm or less, 70 μm or less, 60 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, or 10 μm or less, preferably 30 μm or less, or 25 μm or less. In the present disclosure, the volume median diameter refers to the median diameter (D50) in the volume-based particle size distribution measured by the dynamic light scattering method or the laser diffraction scattering method.

[0018] The repellent agent of the present disclosure may be preferably utilized as a dispersion (particularly an aqueous dispersion) together with a liquid medium.

[0019] [Liquid repellent compound] The liquid repellent compound in the present disclosure is capable of adhering to a substrate and imparting liquid repellency to the substrate.

[0020] The HD (n-hexadecane) contact angle of the liquid repellent compound may be 10° or more, 15° or more, 25° or more, 35° or more, 55° or more, 55° or more, or 65° or more, and may be 100° or less, 90° or less, or 75° or less. When the liquid repellent compound has an HD contact angle equal to or greater than the above lower limit, the liquid repellency (especially oil repellency) can be imparted to the substrate satisfactorily. The HD contact angle is the static contact angle of the liquid repellent compound with respect to the spin-coated film as shown in the examples, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle 1 second after the drop lands.

[0021] The water contact angle of the liquid repellent compound may be 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more, and may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When the liquid repellent compound has a water contact angle equal to or greater than the above lower limit, the liquid repellency (particularly water repellency) can be imparted to the substrate satisfactorily. The water contact angle is the static contact angle of the liquid repellent compound with respect to the spin-coated film as shown in the examples, and is obtained by dropping 2 μL of water onto the spin-coated film and measuring the contact angle 1 second after the drop has landed.

[0022] The liquid repellent compound is preferably a compound having carbon of bio-based origin. The bio-based degree is measured in accordance with ASTM D6866. The bio-based degree is preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example 100%. A high bio-based degree means that the amount of fossil resource-based materials, such as petroleum, used is small, and from this perspective, the higher the bio-based degree of the liquid repellent compound, the more preferable it is.

[0023] The melting point of the liquid repellent compound may be 30° C. or more, 40° C. or more, 60° C. or more, 80° C. or more, 100° C. or more, or 120° C. or more, and is preferably 40° C. or more, and may be 200° C. or less, 150° C. or less, 130° C. or less, 120° C. or less, 110° C. or less, 100° C. or less, 80° C. or less, or 50° C. or less. The liquid repellent compound may not have a melting point.

[0024] The biodegradability of the liquid repellent compound after 180 days is preferably 5% or more. Since the environmental load is reduced, the higher the biodegradability, the more preferable. The biodegradability of the liquid repellent compound after 180 days may be, for example, 10% or more, 20% or more, 30% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and most preferably 90% or more. The biodegradability of the liquid repellent compound after 60 days is preferably 5% or more. Since the environmental load is reduced, the higher the biodegradability, the more preferable. The biodegradability of the liquid repellent compound after 60 days may be, for example, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, or 45% or more, preferably 50% or more, more preferably 60% or more. Such biodegradability may be the biodegradability defined in JIS K 6953-1 or ASTM D6400.

[0025] The molecular weight of the liquid repellent compound may be 200 or more, 300 or more, 350 or more, 400 or more, 500 or more, 550 or more, or 750 or more, and may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 900 or less, 800 or less, 750 or less, or 500 or less.

[0026] The liquid repellent compound in the present disclosure may not have any group selected from the group consisting of a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, and a fluorine atom. Even if the liquid repellent compound does not contain these fluorine-containing groups, it can impart liquid repellency to the substrate.

[0027] The liquid repellent compound in the present disclosure may not have an active hydrogen-containing group. Examples of the active hydrogen-containing group include an amino group (an amino group that is not adjacent to a carbonyl group, for example, a primary or secondary amino group), a hydroxyl group, and a carboxyl group. In particular, the liquid repellent compound in the present disclosure may not have a primary or secondary amino group that is not adjacent to a carbonyl group.

[0028] Liquid repellent compounds an amine backbone, and The formula: -XR n [In the formula, X is a direct bond or a 1+n valent group; R is independently in each occurrence a linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent; n is an integer between 1 and 3. The compound has one or more long chain hydrocarbon-containing groups represented by the formula: At least one of the long chain hydrocarbon-containing groups is bonded to a nitrogen atom of the amine backbone.

[0029] [Amine skeleton] The liquid repellent compound in the present disclosure has an amine skeleton. The amine skeleton has one or more amino groups having a predetermined number of bonds (valences) obtained by removing a predetermined number of atoms or atomic groups (e.g., hydrogen) from an amine compound. The amino group in the amine skeleton means a group selected from the group consisting of -NH2, -NH-, and -N(-)2, and also includes amino groups adjacent to carbonyl groups contained in amide groups, urethane groups, urea groups, imides, etc. Note that the amine skeleton may be an aliphatic group or aromatic group having one or more amino groups, and does not exclude the presence of heteroatoms other than nitrogen.

[0030] The molecular weight of the amine skeleton may be 30 or more, 50 or more, 100 or more, 200 or more, 300 or more, 400 or more, or 500 or more, and may be 2800 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 600 or less, 450 or less, 300 or less, or 250 or less.

[0031] The number of carbon atoms in the amine skeleton 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, and may be 100 or less, 80 or less, 60 or less, 40 or less, 30 or less, 20 or less, 10 or less, or 5 or less, preferably 50 or less, and particularly 30 or less.

[0032] The amine skeleton has one or more amino groups. The amino group is a monovalent to trivalent amino group, and is one or more groups selected from the group consisting of -NH2, -NH-, and -N(-)2. The number of amino groups in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and is preferably 2 or more, and may be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0033] The amine skeleton has a hydrocarbon group (an aliphatic hydrocarbon group or an aromatic hydrocarbon group). The hydrocarbon group may be cyclic, branched, or linear. The hydrocarbon group may be saturated or unsaturated (for example, saturated). Here, the hydrocarbon group may be interrupted by an oxygen atom and / or a sulfur atom, or may be composed of only carbon atoms, nitrogen atoms, and hydrogen atoms. The hydrocarbon group may be a hydrocarbon group that may be interrupted by an oxygen atom and / or a sulfur atom (for example, a chain-like saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings), or may be a general hydrocarbon group (for example, a chain-like saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings). When the hydrocarbon group is interrupted by an oxygen atom and / or a sulfur atom, it has an ether, thioether, polyether, or polythioether structure. The number of hydrocarbon groups in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and may be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0034] The amine skeleton may be composed of a monovalent to trivalent amino group and a chain-like saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group which may be interrupted by an oxygen atom and / or a sulfur atom.

[0035] The molar ratio of carbon atoms to nitrogen atoms (C / N ratio) in the amine skeleton may be 1 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, or 4 or more, and may be 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, or 2 or less, and is preferably 6 or less or 4 or less.

[0036] (Raw material amine compound) Examples of the raw material amine compound which is a precursor of the amine skeleton include alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine; alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine, cyclohexanediamine, and methylenebiscyclohexylamine; diethylenetriamine, triethylenetetramine, tris(2-aminoethyl)amine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tris(2-aminopropyl)amine, tetrapropylenepentamine, pentapropylenehexamine, iminobispropylamine, dibutylenetriamine, bis(2-aminoethoxy)ethane, bis(2-aminoethyl)ether, bis[2-(2-aminoethoxy)ethyl]ether, and bis[2-(3-aminoprotoxy)ethyl]. polyalkylenepolyamines such as ether, spermine, and spermidine; oxygen- or sulfur-containing aliphatic amines such as 1-aminopropanediol, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, polyoxypropylenediamine, and polyoxyethylenediamine; aromatic monoamines such as aniline, 1- or 2-naphthylamine, 1-, 2-, or 9-aminoanthracene, 9-aminophenanthracene, and 2-, 3-, or 4-aminobiphenyl; monocyclic aromatic polyamines such as o-, m-, or p-phenylenediamine, o-, m-, or p-xylylenediamine, diaminotoluene, and 2,3-, 2,4-, or 2,5-tolylenediamine;Diaminobiphenyl, bisaminophenoxyphenylpropane, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl sulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenyl ethane, bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, aminophenoxybiphenyl, aminophenoxyphenylketone, bisaminoditrifluoromethylbenzylbenzene, aminophenoxyphenyl sulfone, aminophenoxyphenyl ether, aminophenoxyphenylpropane, bis(aminophenoxybenzoyl)benzene, bis(aminophenoxy-α,α-dimethylbenzyl)benzene, bis[(aminoaryloxy)benzoyl]diphenyl ether, bis(amino-α,α-dimethylbenzylphenoxy)benzophenone, aminophenoxyphenyl sulfide, bis[amino-α, α-dimethylbenzylphenoxy]diphenyl sulfone, 4,4'-bis[aminophenoxyphenoxy]diphenyl sulfone, diaminodiaryloxybenzophenone, Polycyclic aromatic polyamines such as diaminoaryloxybenzophenone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminotriphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenebisaniline, 4,4'-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 4,4'-diaminodiphenyl ether, and 4,4'-bis(aminophenyl)amine; oxygen- or sulfur-containing polycyclic aromatic polyamines such as 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 3,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl sulfide;Examples of hydroxyl group-containing polyamines include 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine.

[0037] [Long-chain hydrocarbon-containing group] The liquid repellent compound in the present disclosure has the following formula: -XR n [In the formula, X is a direct bond or a 1+n valent group; R is independently in each occurrence a linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent; n is an integer between 1 and 3. The compound has one or more long chain hydrocarbon-containing groups represented by the following formula:

[0038] The number of long-chain hydrocarbon-containing groups possessed by the liquid repellent compound may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and is preferably 2 or more, and may be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0039] At least one long-chain hydrocarbon-containing group in the liquid repellent compound is bonded to a nitrogen atom of the amine skeleton. The ratio of the number of long-chain hydrocarbon-containing groups bonded to a nitrogen atom of the amine skeleton to the number of all long-chain hydrocarbon-containing groups in the liquid repellent compound may be 10% or more, 30% or more, 60% or more, 80% or more, or 100%, and may be 75% or less, 50% or less, or 25% or less. The long-chain hydrocarbon-containing groups that are not bonded to a nitrogen atom of the amine skeleton are bonded to other groups (e.g., hydrocarbon groups) of the amine skeleton.

[0040] (X) X is a direct bond or a 1+n-valent group, preferably a 1+n-valent group. X functions as a linker connecting the amine skeleton and n R's.

[0041] n is the number of R bonded to X, and may be an integer of 1 to 3. n may be 1 or more, 2 or more, or 3 or more, and may be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0042] X may be an aliphatic group (unsaturated aliphatic group or saturated aliphatic group) or an aromatic group.

[0043] 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; and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 300 or less.

[0044] X may have a carbonyl group. X may have one or more selected from the group consisting of an amide group, a urea group, a urethane group, and an imide, or X may form one or more selected from the group consisting of an amide group, a urea group, a urethane group, and an imide together with the amino group in the amine skeleton. Examples of such amide groups, urea groups, urethane groups, and imides include: -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'- -C(=O)-NR'- -C(=O)-NR'-C(=O)- -NR'-S(=O)2- [In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.] X is preferably bonded to a nitrogen atom in the amine skeleton via a -(C=O)- group.

[0045] X is a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2, a di- to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a di- to tetravalent hydrocarbon aromatic ring, or a di- to tetravalent heterocycle. [In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.] It may be a 1+n valent group consisting of one or more groups selected from the group consisting of:

[0046] X is X is one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, 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 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, In the present specification, the group represented as X is bonded to the amine skeleton on the left side and to R on the right side.

[0047] X 1 X 1 is a non-hydrocarbon linker.

[0048] X 1 is a direct bond or a divalent or higher group. X 1 The valence of X may be 2 to 4, 2 to 3, or 2. 1 is preferably not only a direct bond.

[0049] 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, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0050] X 1is composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms in each occurrence). X 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' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.] In addition, X 1 is bonded to a nitrogen atom of the amine skeleton, the nitrogen atom is considered to be part of the amine skeleton (amino group).

[0051] X 2 X 2 is a hydrocarbon or aromatic linker.

[0052] X 2 X may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). 2 X may be aliphatic or aromatic, preferably aliphatic.2 X may be linear, branched or cyclic. 2 is preferably linear.

[0053] X 2 is a divalent or higher group. X 2 The valency of may be, for example, 2 to 4, 2 to 3, or 2.

[0054] X 2 may have 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; and 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.

[0055] X 2 is composed of one or more selected from the group consisting of di- to tetravalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, di- to tetravalent aromatic hydrocarbon rings, and di- to tetravalent heterocycles.

[0056] The divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be a cyclic, branched, or straight-chain hydrocarbon group, and is preferably a chain hydrocarbon group (particularly a straight-chain hydrocarbon group). The 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 the aliphatic hydrocarbon group having 1 to 20 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may be 15 or less, 10 or less, or 5 or less.

[0057] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from a hydrocarbon aromatic ring such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The hydrocarbon aromatic ring may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -N(R')2 (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), a hydroxyl group, a carboxyl group, or a halogen atom. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0058] The divalent to tetravalent heterocycle may be an aliphatic group or an aromatic group. Examples of the divalent to tetravalent heterocycle include groups obtained by removing 2 to 4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring-constituting atoms of the heterocycle is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The heterocycle may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -N(R')2 (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), a hydroxyl group, a carboxyl group, a halogen atom, etc. The valence of the heterocycle may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0059] X 2 Examples include: -Ali- -Cy- -Ali(-)2 -Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or heterocycle.] etc.

[0060] X 2 Examples of specific examples include: -(CH2) p - (p is 1 to 20, for example, 1 to 10), a linear hydrocarbon group having 1 to 40 carbon atoms, for example 1 to 10 unsaturated bonds; a hydrocarbon group having a branched structure and having 1 to 40 carbon atoms, for example 1 to 10 carbon atoms; -(CH2) q -Cy-(CH2) r -(q and r each independently represent an integer of 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0061] Example of X Examples of X are described below. In the following, R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms in each occurrence.

[0062] An example of X is -X when X is bivalent. 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 -X1 -, etc.

[0063] An example of X is -X when X is trivalent. 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; -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、 -X2 -X 1 -(X 2 -X 1 -) 2、 -X 2 -(X 1 -X 2 -X 1 -)2 etc.

[0064] An example of X is -X when X is tetravalent. 1 (-)3, -X 1 -X 2 (-)3, -X 1 -(X 2 -)3, -X 1 -X 2 -X 1 (-)3, -X 1 -X 2 (-X 1 -)3, -X 1 -(X 2 -X 1 -)3, -X 1 -X 2 -X 1 -X 2 (-)3, -X 1 -X 2 -X 1 -(X 2 -) 3、 -X 1 -X 2 -(X 1 -X 2 -) 3、 -X 1 -(X 2 -X 1 -X 2 -)3; -X 2 (-)3, -X 2 -X 1 (-)3, -X 2 -(X 1 -)3, -X 2 -X 1 -X 2 (-)3, -X 2 -X 1 (-X 2 -)3, -X 2 -(X 1 -X 2 -)3, -X 2 -X1 -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; etc.

[0065] Preferred examples of X include -X 1 -, -X 1 -X 2 -, -X 1 -X 2 -X 1 -, -X 1 -X 2 (-)2, -X 2 -, -X 2 -X 1 -, -X 2 -X 1 -X 2 -, -X 2 -X 1 (-)2, In the liquid repellent compound, it is preferred that one or more Xs have an amine skeleton side terminal that is -(C=O)- and are bonded to a nitrogen atom in the amine skeleton.

[0066] X is preferably -X 1 -, -X 1 -X 2 -, -X 1 -X 2 -X 1 -, -X 1 -X 2 (-)2, -X 2 -, -X 2 -X 1 -, -X 2 -X 1 -X 2 -, -X2 -X 1 (-)2, [In the formula, X 1 but, independently for each occurrence, 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' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.) and X 2 is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a divalent aromatic group (for example, a divalent phenyl group, a divalent triazole group). This makes it possible to impart good liquid repellency to the substrate.

[0067] Further specific examples of X include: *-(C=O)- -O-(C=O)-NR'- [In the formula, * means bonding to a nitrogen atom of an amine skeleton, R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.] etc.

[0068] (R) R is a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent. R is branched or linear, more preferably linear. R may be saturated or unsaturated. R is preferably a saturated aliphatic hydrocarbon group (alkyl group) or a monovalent to pentavalent (e.g. monovalent) unsaturated aliphatic hydrocarbon group.

[0069] The number of carbon atoms in R may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, preferably 10 or more, and more preferably 12 or more, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, and more preferably 25 or less.

[0070] The valence of the unsaturated aliphatic hydrocarbon group may be pentavalent or less, tetravalent or less, trivalent or less, divalent or less, or monovalent.

[0071] The hydrocarbon group may have a substituent, but is preferably unsubstituted. Examples of the substituent include -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, the hydrocarbon group may have 1 to 3 (for example, 1) -OR' (particularly -OH) as a substituent (for example, other than at the terminal).

[0072] [Examples of liquid repellent compounds] (Example 1 of liquid repellent compound) Examples of liquid repellent compounds include those represented by the following formula: N(-XRn ) p (-H) q -L 1 -[N(-XR n ) r (-H) s -L 1 -] t -N(-XR n ) p (-H) q [In the formula, X is independently in each occurrence a direct bond or a group having a valence of 1+n; R is independently in each occurrence a linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent; L 1 represents, independently in each occurrence, a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by an oxygen atom and / or a sulfur atom; n, independently in each occurrence, is an integer between 1 and 3, inclusive p, in each occurrence, is an integer greater than or equal to 0 and less than or equal to 2; q, independently in each occurrence, is an integer greater than or equal to 0 and less than or equal to 2; p+q is the sum of each N(-XR n ) p (-H) q In, 2, r is independently in each occurrence 0 or 1; s is independently in each occurrence 0 or 1; r+s is the sum of each N(-XR n ) r (-H) s In, the sum of all p's and all r's is greater than or equal to 1; t is an integer between 0 and 10. Examples of the liquid repellent compound include a compound represented by the following formula (Example 1).

[0073] In the liquid repellent compound example 1, the above explanation is incorporated for details of X, R, and n.

[0074] In the liquid repellent compound example 1, L 1 L is a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be interrupted by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched, or straight-chain hydrocarbon group, and is preferably a straight-chain hydrocarbon group or an aromatic hydrocarbon. 1 The hydrocarbon group in the above description of the [amine skeleton] may be used as L, and the hydrocarbon group may be interrupted by oxygen atoms and / or sulfur atoms, or may consist of only carbon atoms, nitrogen atoms, and hydrogen atoms. 1 L may be, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 aromatic hydrocarbon rings. 1 is preferably a cyclic group having both a ring (e.g., an aromatic ring) and a chain structure (e.g., a straight-chain structure, ether oxygen, or thioether sulfur), and specific examples thereof include a 1,3-phenylenebisalkylene group, a 1,4-phenylenebisalkylene group, a diphenyletherdiyl group, and a diphenylthioetherdiyl group. 1 may have 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more carbon atoms; and may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less.

[0075] In the liquid repellent compound example 1, p is independently in each occurrence an integer of 0 to 2, q is independently in each occurrence an integer of 0 to 2, and p+q is each N(-XR n ) p (-H) q In the formula, p is 2. Preferably, p, independently at each occurrence, may be 1 or more, for example 2.

[0076] In the liquid repellent compound example 1, r is independently 0 or 1 in each occurrence, s is independently 0 or 1 in each occurrence, and r+s is each N(-XR n ) r (-H) sIn the formula, p is 1. Preferably, p, independently at each occurrence, may be 1 or more, for example 2.

[0077] The sum of all p's and all r's is 1 or more, that is, the liquid repellent compound example 1 has one or more -XR n The sum of all p's and all r's may be 1 or more, 3 or more, 5 or more, 7 or more, 9 or more, 12 or more (the sum of all q's and all s's may be 0), and may be 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, or 4 or less.

[0078] In the liquid repellent compound example 1, t is an integer of 0 or more and 10 or less. t may be 0 or more, 1 or more, 2 or more, 4 or more, or 6 or more, and is preferably 0 or more or 2 or more, and t may be 8 or less, 6 or less, 4 or less, or 3 or less, for example, 0, 1, or 2, for example, 0 or 1.

[0079] (Example 2 of liquid repellent compound) Other examples of liquid repellent compounds include those represented by the following formula: N(-XR n ) p (-H) q -L 2 (-XR n ) u [In the formula, X is independently in each occurrence a direct bond or a group having a valence of 1+n; R is independently in each occurrence a linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent; L 2 represents an aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms and a valence of 1+u, which may be interrupted by an oxygen atom and / or a sulfur atom, n, independently in each occurrence, is an integer between 1 and 3, inclusive; p is an integer between 0 and 2, q is an integer between 0 and 2, p+q is 2, u is an integer between 1 and 3, The sum of p and u is greater than or equal to 1.] The compound represented by the following formula (liquid repellent compound example 2) is exemplified.

[0080] In the liquid repellent compound example 2, the details of X, R and n are as described above.

[0081] In the liquid repellent compound example 2, L 2 is an aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms and a valence of 1+u, which may be interrupted by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched, or straight-chain hydrocarbon group, and is preferably a straight-chain hydrocarbon group or an aromatic hydrocarbon. 2 The hydrocarbon group in the above description of the [amine skeleton] may be used as L, and the hydrocarbon group may be interrupted by oxygen atoms and / or sulfur atoms, or may consist of only carbon atoms, nitrogen atoms, and hydrogen atoms. 2 L may be, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 aromatic hydrocarbon rings. 2 is preferably a cyclic group having both a ring (e.g., an aromatic ring) and a chain structure (e.g., a straight-chain structure, ether oxygen, or thioether sulfur), and specific examples thereof include a 1,3-phenylenebisalkylene group, a 1,4-phenylenebisalkylene group, a diphenyletherdiyl group, and a diphenylthioetherdiyl group. 2 may have 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more carbon atoms; and may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less.

[0082] In the liquid repellent compound example 2, p is an integer of 0 or more and 2 or less, q is an integer of 0 or more and 2 or less, and p+q is 2. Preferably, p may be 1 or more, for example, 2.

[0083] In the liquid repellent compound example 2, u is an integer of 1 or more and 3 or less. u is 1, 2, or 3, for example, 2 or 3.

[0084] In the liquid repellent compound example 2, the sum of p and u is 1 or more. That is, the liquid repellent compound example 2 has one or more -XR n The sum of all p's and u's may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more (the sum of all q's may be 0), and the sum of p's and u's may be 5 or less, 4 or less, 3 or less, or 2 or less.

[0085] (Specific examples) Specific examples of the liquid repellent compound include compounds represented by the following formula: In the following formula, the above explanations are incorporated for details of X, R, and n.

[0086] TIFF0007648935000003.tif4751

[0087] TIFF0007648935000004.tif3567

[0088] TIFF0007648935000005.tif4055

[0089] TIFF0007648935000006.tif2144

[0090] TIFF0007648935000007.tif2370

[0091] TIFF0007648935000008.tif2359

[0092] TIFF0007648935000009.tif1967

[0093] The liquid repellent compound may be a synthetic wax derived from animal or vegetable oils. The synthetic wax may be obtained by condensing a fatty acid derived from animal or vegetable oils with an aliphatic amine or an amine containing an aromatic group. Examples of synthetic waxes include fatty acid amide compounds such as hydroxy fatty acid amide compounds, palmitic acid amide compounds, octadecanoic acid amide compounds, stearic acid amide compounds, arachidic acid amide compounds, behenic acid amide compounds, lignoceric acid amide compounds, oleic acid amide compounds, linoleic acid amide compounds, α-linolenic acid amide compounds, γ-linolenic acid amide compounds, arachidonic acid amide compounds, icosapentaenoic acid amide compounds, and docosahexaenoic acid amide compounds.

[0094] [Method of manufacturing liquid repellent compound] The method for producing the liquid repellent compound is not limited, but examples thereof include a method of synthesizing the compound by reacting various amines with an R group-containing carboxylic acid, if necessary in the presence of a condensing agent, and a method of synthesizing the compound by reacting various amines with an R group-containing carboxylic acid acid chloride, acid anhydride, isocyanate, etc. The condensing agent may be a known condensing agent, and examples thereof include DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA, Py-Bop, etc.

[0095] [Amount of liquid repellent compound] The amount of the liquid repellent compound in the repellent agent may be 0.01% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, and 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.

[0096] [Liquid medium] The repellent agent of the present disclosure may comprise a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The repellent agent may be a dispersion or a solution.

[0097] Examples of the organic solvent include esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically, naphtha, kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxyl group (e.g., polyhydric alcohols such as alcohols, glycol-based solvents, ethers of polyhydric alcohols (e.g., monoethers), etc.). These may be used alone or in combination of two or more.

[0098] [Amount of liquid medium] The amount of the liquid medium may be 1 part by weight or more, 2 parts by weight or more, 3 parts by weight or more, 4 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, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the liquid repellent compound.

[0099] The amount of water may be 1 part by weight or more, 2 parts by weight or more, 3 parts by weight or more, 4 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, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the liquid repellent compound.

[0100] The amount of the organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the liquid repellent compound.

[0101] [Surfactant] The repellent may include a surfactant. The surfactant may include one or more surfactants selected from a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant. The surfactant may be non-fluorine-containing.

[0102] [Nonionic surfactants] Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides.

[0103] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0104] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a monohydric to hexahydric (particularly dihydric to pentahydric) alcohol (e.g., an aliphatic alcohol) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0105] An example of the ester ether is a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. An example of the alcohol is a monohydric to hexahydric (particularly dihydric to pentahydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0106] An example of an alkanolamide is formed from a fatty acid and an alkanolamine. The alkanolamide may be a monoalkanolamide or a dialkanolamine. An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0107] The polyhydric alcohol may be a dihydric to pentahydric alcohol having 10 to 30 carbon atoms. The amine oxide may be an oxide (eg, having 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0108] The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic surfactant is generally preferably 2 to 100. The nonionic surfactant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides, and is preferably a nonionic surfactant having an oxyalkylene group.

[0109] 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 sorbitan ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a glycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyglycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sucrose 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, and the like. Among these, those in which the structure of the alkylene oxide adduct portion and the polyalkylene glycol portion is polyoxyethylene (POE) or polyoxypropylene (POP) or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Moreover, the nonionic surfactant preferably has a structure that does not contain an aromatic group in view of environmental issues (biodegradability, environmental hormones, etc.).

[0110] 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 or an alkenyl group or acyl group having 2 to 22 carbon atoms, R 2 each is independently the same or different and is an alkylene group having 3 or more carbon atoms (e.g., 3 to 10), R 3is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number equal to or greater than 2, q is a number equal to or greater than 0. The compound may be represented by the formula:

[0111] R 1 R preferably has 8 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms. 1 Preferred specific examples include an octyl group, a nonyl group, a trimethylnonyl group, a lauryl group, a tridecyl group, an oleyl group, and a stearyl group. R 2 Examples of the alkyl group include a propylene group and a butylene group. In the nonionic surfactant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R 2 O) q may form a polyoxyalkylene chain. The nonionic surfactant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly, a polyoxyalkylene chain) in the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, and among these, an oxypropylene chain is preferred.

[0112] Specific examples of nonionic surfactants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkanes (C 12 -C 16 ) Thiol, Sorbitan Mono Fatty Acid (C7-C 19 ) or alkyl(C 12 -C 18) amines, or sorbitan fatty acid esters, glycerin fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, propylene glycol fatty acid esters, and lecithin derivatives.

[0113] The proportion of the polyoxyethylene block may be 5 to 80% by weight, for example 30 to 75% by weight, particularly 40 to 70% by weight, based on the molecular weight of the nonionic surfactant (copolymer). The average molecular weight of the nonionic surfactant is generally 300 to 5,000, for example, 500 to 3,000. The nonionic surfactant may be a single type or a mixture of two or more types. The nonionic surfactant may be a mixture of a compound having an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more.

[0114] [Cationic surfactants] The cationic surfactant is preferably a compound having no amide group.

[0115] The cationic surfactant may be an amine salt, a quaternary ammonium salt, or an oxyethylene adduct ammonium salt.Specific examples of the cationic surfactant include, but are not limited to, amine salt surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, etc., alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl dimethyl benzyl ammonium salts, pyridinium salts, alkyl isoquinolinium salts, benzethonium chloride, benzalkonium chloride, etc., quaternary ammonium salt surfactants.

[0116] Preferred examples of the cationic surfactant are: R 21 -N + (-R 22 )(-R23 )(-R 24 )X - [In the formula, R 21 , R 22 , R 23 and R 24 is a hydrocarbon group having 1 to 40 carbon atoms, X is an anionic group. It is a compound of the formula: R 21 , R 22 , R 23 and -R 24 Specific examples of X include alkyl groups (e.g., methyl, butyl, stearyl, and palmityl groups). Specific examples of X include halogens (e.g., chlorine) and acids (e.g., hydrochloric acid and acetic acid). The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl having 4 to 40 carbon atoms).

[0117] 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 (e.g. C 12 ~C 50 ) linear and / or branched aliphatic (saturated and / or unsaturated) groups, R 2 is H or a C1-4 alkyl group, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50); (CH3, C2H5 are particularly preferred), X is a halogen atom (for example), a C1-C4 fatty acid base, p is 1 or 2, q is 2 or 3, and p+q=4. R 1 may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0118] 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.

[0119] [Anionic surfactants] Examples of anionic surfactants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonic fatty acid salts, N-acylamino acid type surfactants, phosphoric acid mono- or diester type surfactants, and sulfosuccinic acid esters.

[0120] [Amphoteric surfactants] Examples of amphoteric surfactants include alanines, imidazolinium betaines, amido betaines, and betaine acetate. Specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetate betaine, and fatty acid amidopropyl dimethylamino acetate betaine.

[0121] The surfactant may be a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant, each of which may be one type or a combination of two or more types.

[0122] [Amount of surfactant] The amount of the surfactant may be, relative to 100 parts by weight of the liquid repellent compound, 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, and 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.

[0123] 〔silicone〕 The repellent in the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, it is possible to obtain good texture and durability in addition to good liquid repellency.

[0124] As the silicone, known silicones can be used, and examples of silicones include polydimethylsiloxane and modified silicones (amino-modified, epoxy-modified silicone, carboxy-modified silicone, methylhydrogen silicone, etc.). The silicone may be a silicone wax having wax-like properties. These may be used alone or in combination of two or more.

[0125] The weight average molecular weight of the silicone may be 1,000 or more, 10,000 or more, or 50,000 or more, and may be 500,000 or less, 2,500,000 or less, 100,000 or less, or 50,000 or less.

[0126] [Amount of silicone] The amount of silicone may be, relative to 100 parts by weight of the liquid repellent compound, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and 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.

[0127] 〔wax〕 The repellent in the present disclosure may contain a wax. By containing a wax, it is possible to impart good liquid repellency to the substrate.

[0128] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, silicone wax, animal and vegetable wax, mineral wax, etc. Paraffin wax is preferred. Specific examples of compounds constituting the wax include normal alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane), and normal alkenes (e.g., 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane). The carbon number of the compound constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be from 200 to 2000, for example, from 250 to 1500, or from 300 to 1000. These may be used alone or in combination of two or more.

[0129] The melting point of the wax may be 50° C. or higher, 55° C. or higher, 60° C. or higher, 65° C. or higher, or 70° C. or higher, preferably 55° C. or higher, more preferably 60° C. or higher. The melting point of the wax is measured in accordance with JIS K 2235-1991.

[0130] [Amount of wax] The amount of wax may be, relative to 100 parts by weight of the liquid repellent compound, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and 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.

[0131] [Organic acid] The repellent may contain an organic acid. As the organic acid, a known one may be used. As the organic acid, carboxylic acid, sulfonic acid, sulfinic acid, etc. are preferably mentioned, and carboxylic acid is particularly preferable. As the carboxylic acid, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc. are mentioned, and formic acid or acetic acid is particularly preferable. In the present disclosure, the organic acid may be used alone or in combination of two or more kinds. For example, formic acid and acetic acid may be used in combination.

[0132] [Amount of organic acid] The amount of the organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the liquid repellent compound. The amount of the organic acid may be adjusted so that the pH of the repellent is 3 to 10, for example, 5 to 9, particularly 6 to 8. The repellent may be acidic (pH 7 or less, for example 6 or less).

[0133] [Hardening agent] The repellent agent may include a curing agent (an active hydrogen reactive compound or an active hydrogen containing compound).

[0134] The curing agent (crosslinking agent) in the repellent agent can effectively cure the liquid repellent compound. The curing agent may be an active hydrogen reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen reactive group of the liquid repellent compound. Examples of the active hydrogen reactive compound are isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of the active hydrogen-containing compound are hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0135] The curing agent may include an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound acts as a crosslinking agent. Examples of the polyisocyanate compound include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (e.g., a blocked polyisocyanate compound). The blocked isocyanate compound is a compound in which the isocyanate group of the isocyanate compound is masked with a blocking agent to suppress the reaction.

[0136] Examples of aliphatic polyisocyanates are trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-di ... 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, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, etc. These may be used alone or in combination of two or more.

[0137] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used alone or in combination of two or more.

[0138] Examples of the araliphatic polyisocyanate are araliphatic diisocyanate and araliphatic triisocyanate.Specific examples of the araliphatic polyisocyanate are 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene.These may be used alone or in combination of two or more.

[0139] Examples of aromatic polyisocyanates are aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates are m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used alone or in combination of two or more.

[0140] Examples of the polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biurets, allophanates, carbodiimides, uretdione, uretoimine, isocyanurates, iminooxadiazinedione, etc. These may be used alone or in combination of two or more.

[0141] These polyisocyanates can be used alone or in combination of two or more. As the polyisocyanate compound, it is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of the polyisocyanate compound is blocked with a blocking agent. It is preferable to use a blocked polyisocyanate compound because it is relatively stable even in a solution and can be used in the same solution as the repellent.

[0142] The blocking agent blocks free isocyanate groups. When the blocked polyisocyanate compound is heated to, for example, 100°C or higher, for example, 130°C or higher, the isocyanate group is regenerated and can easily react with the hydroxyl group. Examples of the blocking agent include phenol-based compounds, lactam-based compounds, aliphatic alcohol-based compounds, and oxime-based compounds. The polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0143] The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. The chloromethyl group-containing compound is a compound having a chloromethyl group. An example of the chloromethyl group-containing compound is chloromethyl polystyrene. The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound include (poly)acrylic acid and (poly)methacrylic acid.

[0144] Specific examples of the ketone group-containing compound include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of the hydrazide compound include hydrazine, carbohydrazide, adipic acid hydrazide, and the like. Specific examples of the melamine compound include melamine resins and methyl etherified melamine resins.

[0145] [Amount of hardener] The amount of the curing agent may be, relative to 100 parts by weight of the liquid repellent compound, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and 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.

[0146] [Other ingredients] The repellent may contain other components in addition to the above components. Examples of the other components include polysaccharides, paper strength agents, flocculants, retention aids, coagulants, binder resins, slip prevention agents, sizing agents, paper strength agents, fillers, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above-mentioned components, other components include other water and / or oil repellents, dispersants, texture adjusters, softeners, flame retardants, paint fixing agents, anti-wrinkle agents, drying speed adjusters, crosslinking agents, film-forming agents, compatibilizers, antifreeze agents, viscosity adjusters, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrink prevention agents, laundry wrinkle prevention agents, shape retention agents, drape retention agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, dye transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, dirt removers, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Ciba Specialty Chemicals' Chinopearl CBS-X), dye fixatives, and discoloration inhibitors such as 1,4-bis(3-aminopropyl)piperazine. The following can be blended: stain removers, enzymes such as cellulase, amylase, protease, lipase, keratinase, etc. as fiber surface modifiers, foam inhibitors, silk protein powders, their surface modified products or emulsified dispersions (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemicals), hydrolyzed silk liquid (Jomo), Silkgen G Soluble S (Ichimaru Falcos)), stain prevention agents (e.g., nonionic polymer compounds consisting of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by GOO Chemical Industry Co., Ltd., SRC-1 manufactured by Clariant Japan, etc.), etc. These may be used alone or in combination of two or more.

[0147] [Polysaccharide] Examples of polysaccharides include starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, pullulan, etc. The polysaccharide may be a modified polysaccharide having a substitution, in particular a modified polysaccharide having a hydroxyl group or a cationic group introduced therein.

[0148] [Paper strength agents, flocculants, retention aids or coagulants] Examples of paper strength agents, flocculants, retention aids 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, condensates of alkylene dichlorides and polyalkylenepolyamines, dicyandiamide-formaldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0149] [Sizing agent] Examples of sizing agents include cellulose-reactive sizing agents, e.g., rosin-based sizing agents such as rosin-based soaps, rosin-based emulsions / dispersions, cellulose-reactive sizing agents, e.g., emulsions / dispersions of acid anhydrides such as alkyl and alkenyl succinic anhydrides (ASA), alkenyl and alkyl ketene dimers (AKD) and polymers, and anionic, cationic and amphoteric polymers of ethylenically unsaturated monomers, e.g., copolymers of styrene and acrylates.

[0150] [Antistatic agent] Examples of the antistatic agent include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate ester salts, phosphonates, and phosphate ester salts; amphoteric antistatic agents such as alkylbetaine and its derivatives, imidazoline and its derivatives, alanine and its derivatives, nonionic antistatic agents such as aminoalcohol and its derivatives, glycerin and its derivatives, and polyethylene glycol and its derivatives. The antistatic agent may be an ion-conductive polymer obtained by polymerizing or copolymerizing a monomer having an ion-conductive group of these cationic, anionic, or amphoteric ion types. These may be used alone or in combination of two or more.

[0151] [Preservatives] The preservatives are mainly used to enhance the preservative and bactericidal power and maintain the preservative properties during long-term storage. Examples of the preservatives include isothiazolone organic sulfur compounds, benzisothiazolone organic sulfur compounds, benzoic acids, 2-bromo-2-nitro-1,3-propanediol, etc.

[0152] [Ultraviolet absorber] An ultraviolet absorber is a drug that has an ultraviolet protection effect, and is a component that absorbs ultraviolet light and converts it into infrared light, visible light, etc. Examples of ultraviolet absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, 4-t-butyl-4'-methoxybenzoylmethane, etc.

[0153] [Antibacterial agents] Antibacterial agents are components that have the effect of suppressing the growth of bacteria on fibers and further suppressing the generation of unpleasant odors resulting from the decomposition products of microorganisms. Examples of antibacterial agents include cationic bactericides such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide) zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, polylysine, etc.

[0154] [Deodorant] Examples of deodorants include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, and aminocarboxylic acid metal complexes (zinc complex of trisodium methylglycinediacetate described in WO 2012 / 090580).

[0155] [Amount of other ingredients] The amount or total amount of the other components may be, relative to 100 parts by weight of the liquid repellent compound, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and 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.

[0156] <Pulp composition> The pulp composition of the present disclosure includes a liquid repellent compound and a pulp base material. The pulp composition of the present disclosure may have excellent oil and / or water resistance, preferably both.

[0157] The pulp composition in the present disclosure is obtained by adding a liquid repellent compound to a pulp base material. The pulp composition may be obtained by treating the pulp base material with a repellent agent containing a liquid repellent compound, and the amount of the repellent agent added or the composition of the repellent agent may be adjusted so that each component is present in a desired amount. Each component that may be contained in the repellent agent may be added to the pulp composition as a separate additive.

[0158] The pulp composition of the present disclosure may not contain any of the compounds selected from the group consisting of compounds having a fluoroalkyl group with 8 or more carbon atoms, compounds having a perfluoroalkyl group with 8 or more carbon atoms, compounds having a fluoroalkyl group with 4 or more carbon atoms, compounds having a perfluoroalkyl group with 4 or more carbon atoms, compounds having a perfluoroalkyl group, compounds having a fluoroalkyl group, and compounds having a fluorine atom. The pulp composition of the present disclosure can impart liquid repellency to a substrate even if it does not contain these fluorine compounds.

[0159] The pH of the pulp composition may be 3 to 10, for example 5 to 9, particularly 6 to 8, and the amount of each component may be adjusted to achieve such a pH.

[0160] [Pulp base material] The pulp composition includes a pulp base material. The pulp base material is composed of pulp, which may be wood pulp, non-wood pulp, recycled paper pulp, and the like.

[0161] Pulps include coniferous kraft pulp obtained from the fir and pine genus, and hardwood kraft pulp obtained from the Acacia, Eucalyptus, Beech, and Populus genus (e.g., poplar). Examples of coniferous kraft pulp include unbleached coniferous kraft pulp (NUKP), bleached coniferous pulp (NBKP), semi-bleached coniferous kraft pulp (NSBKP), and softwood sulfite pulp. Examples of hardwood kraft pulp include unbleached hardwood kraft pulp (LUKP), bleached hardwood kraft pulp (LBKP), semi-bleached hardwood kraft pulp (LSBKP), and hardwood sulfite pulp. The pulps used may be used alone or in combination. In addition to kraft pulp, there are softwood kraft pulp and hardwood kraft pulp, as well as mechanical pulp such as stone ground pulp (SGP), pressurized stone ground pulp (PGW), refiner ground pulp (RGP), thermo ground pulp (TGP), chemi-ground pulp (CGP), groundwood pulp (GP), thermomechanical pulp (TMP), etc. Furthermore, waste paper pulp includes disintegrated waste paper pulp, disintegrated and deinked waste paper pulp, or disintegrated, deinked and bleached waste paper pulp, which are produced from brown waste paper, waste kraft envelope paper, magazine paper, newspaper paper, flyer paper, office paper, cardboard paper, white waste paper, Kent waste paper, imitation waste paper, and land certificate waste paper. Examples of non-wood pulp include pulp obtained from bagasse, kenaf, bamboo, linter, cotton, linen, hemp, ramie, straw, esparto, Manila hemp, sisal, jute, flax, ramie, mitsumata, paper mulberry, bagasse, and the like.

[0162] From the viewpoint of improving oil resistance, the average fiber length of the pulp is preferably 0.1 mm or more, more preferably 0.3 mm or more, and even more preferably 0.5 mm or more, and from the viewpoint of ease of production, it is preferably 5.0 mm or less, more preferably 4.0 mm or less, even more preferably 3.0 mm or less, particularly preferably 2.0 mm or less, and most preferably 1.0 mm or less.

[0163] [Pulp base material form] The form of the pulp base material when the liquid repellent compound is added may be pulp alone, a pulp slurry, a pulp product, etc., and specific examples include pulps such as bleached or unbleached chemical pulps such as kraft pulp and sulfite pulp, bleached or unbleached high-yield pulps such as groundwood pulp, mechanical pulp and thermomechanical pulp; pulp slurries containing the above pulps; and pulp products such as paper, paper containers, and pulp molded products.

[0164] [Amount of pulp base material] The amount of the pulp base material in the pulp composition may be 0.1% 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, 30% by weight or more, 50% by weight or more, 75% by weight or more, or 90% by weight or more, and may be 99% by weight or less, 75% 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, 4% by weight or less, or 3% by weight or less. For example, when the pulp composition is prepared by internal addition, the amount of the pulp base material in the pulp composition may be 30% by weight or less, and when the pulp composition is prepared by external addition, the amount of the pulp base material in the pulp composition may be 75% by weight or more.

[0165] The amount of the pulp base material may be 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, or 99% by weight or more in the pulp composition excluding the liquid medium, and may be 99.9% by weight or less, 95% by weight or less, 90% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, or 55% by weight or less.

[0166] [Liquid medium] The pulp composition may comprise a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent, typically an aqueous medium, especially water. The liquid medium may comprise a liquid medium derived from a repellent agent.

[0167] [Amount of liquid medium] The amount of the liquid medium in the pulp composition may be 0.1% 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, 30% by weight or more, 50% by weight or more, 75% by weight or more, 90% by weight or more, or 95% by weight or more, and may be 99% by weight or less, 75% 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, 4% by weight or less, or 3% by weight or less. Typically, when the pulp composition is prepared by internal addition, the amount of the liquid medium in the pulp composition may be 50% by weight or more, particularly 90% by weight or more, and when the pulp composition is prepared by external addition, the amount of the liquid medium in the pulp composition may be 30% by weight or less, particularly 10% by weight or less.

[0168] [Liquid repellent compound] The pulp composition contains a liquid repellent compound. For details of the types of liquid repellent compounds, the explanation of the liquid repellent compounds in <Repellent Agent> is incorporated herein by reference.

[0169] [Amount of liquid repellent compound] The amount of the liquid repellent compound may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, preferably 0.5% by weight or more, and may be 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, for example, 15% by weight or less, 5.0% by weight or less, or 3.0% by weight or less.

[0170] The liquid repellent compound may be added to the surface of a pulp substrate (e.g., a pulp product such as paper, a paper container, or a pulp molded product) for external addition treatment. The amount of the liquid repellent compound contained in the coating layer formed by external addition treatment is 0.01 g / m 2 More than 0.03g / m 2 More than 0.05g / m 2 More than 0.1g / m 2More than 0.3g / m 2 More than 0.5g / m 2 or more, or 1.0 g / m 2 or more, and 5.0 g / m 2 Below 4.0g / m 2 Below 3.0g / m 2 Below 2.0g / m 2 Below 1.0g / m 2 Below 0.5g / m 2 Below 0.3g / m 2 or less than 0.1 g / m 2 It may be the following:

[0171] [Dispersant] The pulp composition may contain a dispersant. For details of the types of dispersants, the explanation of dispersants in <Repellent Agent> is incorporated herein by reference.

[0172] [Amount of dispersant] The amount of the dispersant may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, preferably 5.0% by weight or less, and more preferably 3.0% by weight or less.

[0173] [Paper strength agent] The pulp composition may include a strength agent. Examples of strength agents include: Polyacrylamide-based paper strength agents such as cationic polyacrylamide, anionic polyacrylamide, and amphoteric polyacrylamide; polysaccharide-based paper strength agents such as starch, enzyme-modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (e.g., hydroxyethylated starch, etc.), aldehyde starch, cationized starch, starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, chitin nanofiber, cellulose nanofiber, and pullulan, and modified polysaccharides thereof (e.g., modified polysaccharides having hydroxyl groups or cationic groups introduced therein); Polyamide-based paper strength agents such as polyamide resins, polyamine resins, polyamide-polyamine resins, polyamide-epichlorohydrin resins, polyamide-polyamine-epichlorohydrin resins, polyamide-polyurea-formaldehyde resins, and epoxidized polyamide resins; Urea / melamine-based paper strength agents such as urea resin, melamine resin, urea-formaldehyde resin, and melamine-formaldehyde resin; polyvinyl alcohol-based paper strength agents such as polyvinyl alcohol, fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, and terminal alkyl-modified polyvinyl alcohol; These include styrene-butadiene copolymers, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, polyvinyl chloride, polyvinylidene chloride, polyacrylic esters, fatty acid diamides, polyethyleneimine resins, and ketone aldehyde resins. In the present disclosure, the paper strength agent is preferably a polyacrylamide-based paper strength agent, a polysaccharide-based paper strength agent, or a polyamide-based paper strength agent.

[0174] [Amount of paper strength agent] The total amount of the strength agent may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, and is preferably 5.0% by weight or less.

[0175] The amount of the polyacrylamide-based strength agent may be 0.1% by weight or more, 0.2% by weight or more, 0.4% by weight or more, 0.6% by weight or more, 0.8% by weight or more, or 1.0% by weight, and is preferably 0.3% by weight or more, and may be 1.1% by weight or less, 0.9% by weight or less, 0.7% by weight or less, 0.5% by weight or less, or 0.3% by weight or less, based on the pulp.

[0176] The amount of the polysaccharide-based strength agent may be 0.6% by weight or more, 1.0% by weight or more, 1.5% by weight or more, 2.0% by weight or more, 2.5% by weight or more, 3.0% by weight or more, 3.5% by weight or more, 4.0% by weight or more, or 4.5% by weight or more, and is preferably 2.0% by weight or more, and may be 5% by weight or less, 4.7% by weight or less, 4.2% by weight or less, 3.7% by weight or less, 3.2% by weight or less, 2.7% by weight or less, 2.2% by weight or less, or 1.7% by weight or less, based on the pulp.

[0177] The amount of the polyamide-based strength agent may be 0.3% by weight or more, 0.4% by weight or more, 0.5% by weight or more, 0.6% by weight or more, 0.7% by weight or more, or 0.8% by weight or more, and may be 0.9% by weight or less, 0.8% by weight or less, 0.7% by weight or less, 0.6% by weight or less, 0.5% by weight or less, or 0.4% by weight or less, based on the pulp.

[0178] [Sizing Agent] The pulp composition may contain a sizing agent. Examples of the sizing agent include cationic sizing agents, anionic sizing agents, neutral sizing agents, and amphoteric sizing agents, such as rosin-based sizing agents (e.g., acidic rosin-based sizing agents, neutral rosin-based sizing agents), alkyl ketene dimers, and alkenyl succinic anhydrides.

[0179] [Amount of sizing agent] The amount of the sizing agent may be 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, based on the pulp.

[0180] [Other additives] In addition to the above, the pulp composition may contain other additives such as paper-related chemicals used in the manufacture of pulp products, such as fixing agents (e.g., aluminum sulfate), coagulants / flocculants (e.g., polyamine resins), retention aids (e.g., polyacrylamide resins), organic acids (e.g., formic acid, acetic acid), dyes, slime control agents, and defoamers.

[0181] [Amount of other additives] The amount of the other additives may be 0.01% by weight or more, 0.1% by weight or more, 1% by weight or more, 3% by weight or more, or 5% by weight or more, and may be 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 3% by weight or less, or 1% by weight or less, based on the pulp base material.

[0182] <Manufacturing method of treated textile or paper products> The method of making a repellent treated product of the present disclosure includes treating a substrate with the repellent agent described above.

[0183] "Treatment" means that the repellent is applied to the substrate by immersion, spraying, coating, etc. The treatment causes the liquid repellent compound, which is the active ingredient of the repellent, to adhere to the inside and / or surface of the substrate. Here, adhesion may be physical adhesion or chemical adhesion, and for example, the liquid repellent compound may be physically or chemically (by reacting with) modified with a hydroxyl group of the substrate (fiber, paper, glass, etc.).

[0184] [Base material] The substrate to be treated with the repellent of the present disclosure is not limited, but is preferably a textile product or a paper product.

[0185] Examples of the substrate for textile products include natural fibers of animal and vegetable origin such as cotton, hemp, wool, silk, etc., synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, etc., semi-synthetic fibers such as rayon, acetate, etc., inorganic fibers such as glass fiber, carbon fiber, asbestos fiber, etc., or mixtures of these fibers. Textile products include woven fabrics, knitted fabrics and nonwoven fabrics, clothing forms (e.g., water-repellent clothing, e.g., raincoats), and carpets, but the treatment may be performed on fibers, yarns, and intermediate textile products (e.g., slivers or rovings) before being made into cloth.

[0186] Examples of the substrate for paper products include paper made of bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp or thermomechanical pulp, waste paper pulp such as recycled newsprint, recycled magazine paper, recycled corrugated cardboard or deinked recycled paper, containers made of paper, molded articles made of paper, etc. Specific examples of paper products include food packaging materials, food containers, gypsum board base paper, coated base paper, medium-quality paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-proof liners and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral heat-sensitive paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc., and suitable examples include food packaging materials and food containers. By treating a paper substrate with the repellent of the present disclosure, for example, paper products that have been imparted with water repellency, oil repellency, oil resistance, and water resistance (water-repellent paper, oil-repellent paper, grease-resistant paper, water-resistant paper) can be obtained.

[0187] Substrates that can be treated with the repellent of the present disclosure are not limited to textiles or paper products, but also include stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster.

[0188] When the substrate is glass, the glass product to be manufactured may be an optical member. The surface (outermost layer) of the glass substrate may have some layer (or film), such as a hard coat layer or an anti-reflection layer. The anti-reflection layer may be either a single-layer anti-reflection layer or a multi-layer anti-reflection layer. Examples of inorganic substances that can be used for the anti-reflection layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, WO3, etc. These inorganic substances may be used alone or in combination of two or more of them (for example, as a mixture). When a multi-layer anti-reflection layer is used, it is preferable to use SiO2 and / or SiO for the outermost layer. When the product to be manufactured is an optical glass part for a touch panel, a transparent electrode, such as a thin film using indium tin oxide (ITO) or indium zinc oxide, may be provided on a part of the surface of the substrate (glass). In addition, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomizing film layer, a hard coating film layer, a polarizing film, a phase difference film, and a liquid crystal display module, etc., depending on its specific specifications, etc.

[0189] [Processing method] The repellent of the present disclosure can be applied to a substrate as a treatment agent (particularly a surface treatment agent) by a conventionally known method. The treatment method may be a method in which the repellent of the present disclosure is dispersed and diluted in an organic solvent or water as necessary, and attached to the inside and / or surface of the substrate by a known method such as dip coating, spray coating, foam coating, etc., and then dried. After drying, a textile product to which the solid components of the repellent are attached is obtained. If necessary, it may be applied together with a suitable crosslinking agent and cured. The repellent of the present disclosure may be used in combination with various additives such as water and / or oil repellents, slip prevention agents, antistatic agents, texture adjusters, softeners, antibacterial agents, flame retardants, paint fixing agents, anti-wrinkle agents, drying speed adjusters, crosslinking agents, film-forming assistants, compatibilizers, antifreeze agents, viscosity adjusters, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, and defoamers. Examples of various additives may be the same as those described in the "other components" of the water repellent composition above. The concentration of the repellent in the treatment agent to be brought into contact with the substrate may be appropriately changed depending on the application, but may be 0.01 to 10% by weight, for example 0.05 to 5% by weight.

[0190] The repellent can be applied to the substrate by any of the methods known for treating substrates with liquids. The substrate may be immersed in the repellent, or the solution may be applied or sprayed onto the substrate. The treated substrate is preferably dried and cured by heating to develop liquid repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In the present disclosure, good performance can be obtained even with low-temperature heating (for example, 100°C to 140°C). In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes. When the textile product is paper, the paper may be coated with the repellent, or the solution may be applied or sprayed onto the paper, or the paper may be mixed with the pulp slurry before papermaking and treated. The treatment may be an external addition treatment or an internal addition treatment. Alternatively, the repellent may be applied to the textile product by a cleaning method, for example, by washing application or dry cleaning method.

[0191] [Paper substrate processing] Examples of paper substrates (pulp substrates) include paper, paper containers, and paper molded articles (such as pulp molds).

[0192] The paper product (paper) can be produced by a conventionally known papermaking method, either an internal treatment method in which the repellent is added to the pulp slurry before papermaking, or an external treatment method in which the repellent is applied to the paper after papermaking can be used.

[0193] The internal addition treatment method may mean a treatment method of adding a repellent to a pulp slurry before papermaking. The internal addition treatment method may include, but is not limited to, one or more of the steps of adding a repellent to a pulp slurry and stirring and mixing it, suction-dehydrating the pulp composition prepared in the step through a mesh body of a predetermined shape to deposit the pulp composition to form a pulp mold intermediate, and molding and drying the pulp mold intermediate with a heated mold to obtain paper, a paper container, or a paper molded product. The treated paper may be subjected to a heat treatment depending on the properties of the paper after simple drying at room temperature or at a high temperature. The temperature of the heat treatment may be 150°C or higher, 180°C or higher, or 210°C or higher, and may be 300°C or lower, 250°C or lower, or 200°C or lower, and may be particularly 80°C to 180°C. By performing the heat treatment in such a temperature range, excellent oil resistance and water resistance can be exhibited.

[0194] The size press for external additive treatment can be divided into the following types according to the coating method: One application method is a so-called pond-type two-roll size press, in which a coating liquid (size liquid) is supplied to a nip formed by passing paper between two rubber rolls, a coating liquid pool called a pond is created, and the paper is passed through this coating liquid pool to apply the size liquid to both sides of the paper. Other application methods are a gate roll type in which the size liquid is applied by a surface transfer type, and a rod metering size press. In a pond-type two-roll size press, the size liquid is likely to penetrate into the inside of the paper, and in a surface transfer type, the size liquid component is likely to remain on the surface of the paper. In the surface transfer type, the coating layer is more likely to remain on the surface of the paper than in a pond-type two-roll size press, and the coating layer formed on the surface is larger than in a pond-type two-roll size press. In the present disclosure, performance can be imparted to the paper even when the former pond-type two-roll size press is used. The paper thus treated can exhibit excellent oil resistance, water resistance, etc. by optionally accompanying a heat treatment that can take a temperature range of up to 300°C, for example up to 200°C, particularly 80°C to 180°C, depending on the properties of the paper, after simple drying at room temperature or high temperature.

[0195] The present disclosure can be used in gypsum board base paper, coated base paper, medium quality paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-proof liners and metal interleaving paper, kraft paper, etc. It can also be used in neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper.

[0196] Pulp raw materials include bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, groundwood pulp, mechanical pulp, or thermomechanical pulp. Any of bleached or unbleached high-yield pulp, recycled newspaper, magazine, corrugated cardboard, deinked recycled paper, etc. may be used. Mixtures of the above pulp raw materials with synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, polyvinyl alcohol, etc. may also be used.

[0197] The water resistance of paper can be improved by adding a sizing agent. Examples of the sizing agent 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 the sizing agent may be 0.01 to 5% by weight based on the pulp.

[0198] If necessary, the paper may contain additives used in the manufacture of paper, such as paper strength agents such as starch, modified starch, carboxymethyl cellulose, polyamide polyamine-epichlorohydrin resin, flocculants, fixing agents, retention aids, dyes, fluorescent dyes, slime control agents, and defoamers, to the extent that they are commonly used. It is preferable to use starch and / or modified starch. If necessary, a repellent can be applied to the paper using starch, polyvinyl alcohol, dyes, coating colors, anti-slip agents, etc., by a size press, gate roll coater, bill blade coater, calendar, etc.

[0199] In the case of external addition, the amount of the liquid repellent compound contained in the coating layer is 0.01 to 2.0 g / m 2 , especially 0.1 to 1.0 g / m 2 The coating layer is preferably formed from a repellent and starch and / or modified starch. The solid content of the paper repellent in the coating layer is preferably 2 g / m 2 It is preferable that: In the case of internal addition, it is preferable to mix the repellent with the pulp so that the amount of the repellent is 0.01 to 50 parts by weight or 0.01 to 30 parts by weight, for example 0.01 to 10 parts by weight, and particularly 0.2 to 5.0 parts by weight, per 100 parts by weight of the pulp forming the paper.

[0200] In the case of external addition, oil resistance can also be imparted to paper by using a so-called pond-type two-roll size press process in which the treatment solution is pooled between rolls and the base paper is passed through the treatment solution between the rolls at any roll speed and nip pressure.

[0201] In the external addition treatment, the paper substrate may contain additives such as sizing agents, paper strength agents, flocculants, retention agents or coagulants. The additives may be nonionic, cationic, anionic or amphoteric. The ionic charge density of the additives may be -10000 to 10000 μeq / g, preferably -4000 to 8000 μeq / g, more preferably -1000 to 7000 μeq / g. Additives such as sizing agents, paper strength agents, flocculants, retention agents or coagulants (solids 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) based on the pulp. In the case of a paper substrate containing a cationic additive (e.g., sizing agents, paper strength agents, flocculants, retention agents or coagulants), the repellent is preferably anionic.

[0202] In the internal addition treatment, it is preferable to make 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 agents, flocculants, retention agents, coagulants, etc.) and liquid repellent compounds can be added to the pulp slurry. Examples of additives (e.g., sizing agents, paper strength agents, flocculants, retention agents, or coagulants) include alkylketene dimers, alkenyl succinic anhydrides, styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichlorides and polyalkylenepolyamines, dicyandiamide-formaldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0203] [Pretreatment of textile substrates] The fiber substrate (fabric substrate) may be pretreated before being treated with the repellent of the present disclosure. Pretreatment of the fiber substrate can impart excellent fastness to the fiber product after treatment with the repellent.

[0204] Examples of pretreatments of fiber substrates include cationization treatment by reaction with a reactive quaternary ammonium salt, anionization treatment such as sulfonation, carboxylation, and phosphation, and acetylation treatment after anionization treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, and polymer coating treatment.

[0205] The method for pretreating the fiber substrate is not limited, and the fiber substrate can be pretreated by a conventionally known method. The pretreatment liquid may be dispersed and diluted in an organic solvent or water as necessary, and applied to the inside and / or surface of the fiber substrate by a known method such as dip coating, spray coating, foam coating, etc., and then dried. The pH and temperature of the pretreatment liquid may be adjusted depending on the desired degree of treatment. As an example of a method for pretreating the fiber substrate, a method for pretreating the fiber substrate with a hydrocarbon-based water repellent will be described in detail.

[0206] The pretreatment method for the fiber substrate is to add -SO3M to the fiber. 1 (In the formula, M 1 represents a monovalent cation), -COOM 2 (In the formula, M 2 represents a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(wherein, X 1 and X 2 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) (hereinafter, also referred to as "specific functional groups").

[0207] M 1 Examples of M include H, K, Na, and ammonium ion which may have a substituent. 2 Examples of X include H, K, Na, and ammonium ion which may have a substituent. 1 Or X 2 When is an alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms, and more preferably an alkyl group having 4 to 12 carbon atoms.

[0208] The fibers containing the specific functional groups (hereinafter, sometimes referred to as "functional group-containing fibers") can be prepared, for example, by the following method. (i) A compound having the specific functional group is attached to a fiber material. The attachment of the compound may be in a state where a part of the compound is chemically bonded to a part of the fiber to the extent that a sufficient amount of the specific functional group remains. (ii) As a material constituting the fiber, a fiber into which the specific functional group is directly introduced is used.

[0209] In the case of (i), for example, a functional group-containing fiber can be obtained by a functional group introduction step in which a fiber material is treated with a pretreatment liquid containing one or more compounds having the specific functional group.

[0210] The material of the fiber material is not particularly limited, and examples thereof include natural fibers such as cotton, hemp, silk, wool, etc., semi-synthetic fibers such as rayon, acetate, etc., synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, polypropylene, etc., and composite fibers, blended fibers, etc. The form of the fiber material may be any of fibers (tow, sliver, etc.), yarn, knitted fabric (including interwoven fabric), woven fabric (including interwoven fabric), nonwoven fabric, etc.

[0211] In this embodiment, from the viewpoint of improving the water repellency of the obtained textile product, it is preferable to use textile materials containing polyamide and polyester as raw materials, and in particular, it is preferable to use nylons such as nylon 6 and nylon 6,6, polyesters such as polyethylene terephthalate (PET), polytrimethyl terephthalate, and polylactic acid, and mixed fibers containing these.

[0212] Above -SO3M 1 As the compound having the formula (I), a phenol-based polymer can be used. As such a phenol-based polymer, for example, one containing one or more compounds represented by the following general formula can be mentioned.

[0213] TIFF0007648935000010.tif4678 [In the formula, X 2 Ha-SO3M 3 (In the formula, M 3 represents a monovalent cation) or a group represented by the following general formula, and n is an integer of 20 to 3000.

[0214] TIFF0007648935000011.tif2661 [In the formula, M 4 represents a monovalent cation.

[0215] The above M 3 Examples of the cation include H, K, Na, and ammonium ion which may have a substituent.

[0216] The above M 4 Examples of the cation include H, K, Na, and ammonium ion which may have a substituent.

[0217] The compound represented by the above general formula may be, for example, a formalin condensate of phenolsulfonic acid or a formalin condensate of sulfonated bisphenol S.

[0218] Above - COOM 2 Examples of compounds having the formula include polycarboxylic acid polymers.

[0219] As the polycarboxylic acid polymer, for example, a polymer synthesized by a conventionally known radical polymerization method using acrylic acid, methacrylic acid, maleic acid, or the like as a monomer, or a commercially available product can be used.

[0220] Examples of the method for producing a polycarboxylic acid polymer include a method in which a radical polymerization initiator is added to an aqueous solution of the above-mentioned monomer and / or its salt, and the mixture is heated and reacted at 30 to 150° C. for 2 to 5 hours. At this time, an alcohol such as methanol, ethanol, isopropyl alcohol, or an aqueous solvent such as acetone may be added to the aqueous solution of the above-mentioned monomer and / or its salt. Examples of the radical polymerization initiator include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, redox-based polymerization initiators such as combinations of persulfates and sodium bisulfite, hydrogen peroxide, and water-soluble azo-based polymerization initiators. These radical polymerization initiators may be used alone or in combination of two or more. Furthermore, during radical polymerization, a chain transfer agent (e.g., octyl thioglycolate) may be added for the purpose of adjusting the degree of polymerization.

[0221] In addition to the above monomers, copolymerizable monomers can be used in the radical polymerization. Examples of the copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, acrylamide, acrylates, and methacrylates. The acrylates and methacrylates are preferably those having a hydrocarbon group having 1 to 3 carbon atoms which may have a substituent such as a hydroxyl group. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, and propyl methacrylate. These copolymerizable monomers may be used alone or in combination of two or more.

[0222] The carboxyl group in the polycarboxylic acid polymer may be free or may be neutralized with an alkali metal, an amine compound, etc. Examples of the alkali metal include sodium, potassium, and lithium, and examples of the amine compound include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0223] The weight average molecular weight of the polycarboxylic acid polymer is preferably from 1,000 to 20,000, and more preferably from 3,000 to 15,000, from the viewpoint of improving the water repellency of the resulting textile product.

[0224] As the polycarboxylic acid polymer, commercially available products such as "Neocrystal 770" (product name, manufactured by Nicca Chemical Co., Ltd.) and "Ceropol PC-300" (product name, manufactured by Sanyo Chemical Industries, Ltd.) can be used.

[0225] Above -OP(O)(OX 1 )(OX 2 ) is exemplified by a phosphate ester compound represented by the following general formula: TIFF0007648935000012.tif3243[where, X 1 Or X 2 is the same as above, and X 3 represents an alkyl group having 1 to 22 carbon atoms.

[0226] As the phosphate ester compound, phosphate monoesters, diesters and triesters, in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, and mixtures thereof can be used.

[0227] From the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use lauryl phosphate and decyl phosphate.

[0228] As the phosphate ester compound, for example, a commercially available product such as "Phosphanol ML-200" (product name, manufactured by Toho Chemical Industry Co., Ltd.) can be used.

[0229] The pretreatment liquid containing one or more compounds having the specific functional group may be, for example, an aqueous solution of the above-mentioned compounds. The pretreatment liquid may also contain an acid, an alkali, a surfactant, a chelating agent, etc.

[0230] Examples of the method for treating the textile material with the pretreatment liquid include padding, immersion, spraying, and coating. Examples of padding include a method using a padding device described on pages 396-397 of Textile Dyeing and Processing Dictionary (published by Nikkan Kogyo Shimbun, 1963) and pages 256-260 of Color Dyeing Chemistry III (published by Jikkyo Publishing Co., Ltd., 1975). Examples of coating include a method using a coating machine described on pages 473-477 of Dyeing and Finishing Equipment Directory (published by Sen-sha, 1981). Examples of immersion include a method using a batch-type dyeing machine described on pages 196-247 of Dyeing and Finishing Equipment Directory (published by Sen-sha, 1981), and a liquid flow dyeing machine, air flow dyeing machine, drum dyeing machine, winch dyeing machine, washer dyeing machine, cheese dyeing machine, etc. can be used. Examples of the spray treatment include an air spray in which the treatment liquid is sprayed in the form of a mist using compressed air, and a method using an air spray of a liquid pressure atomization type. The treatment conditions, such as the concentration of the treatment liquid and the heat treatment after application, can be appropriately adjusted in consideration of various conditions such as the purpose and performance. In addition, when the pretreatment liquid contains water, it is preferable to dry the pretreatment liquid after it is applied to the fiber material in order to remove the water. There is no particular limit to the drying method, and either a dry heat method or a wet heat method may be used. There is also no particular limit to the drying temperature, and for example, drying may be performed at room temperature to 200°C for 10 seconds to several days. If necessary, heat treatment may be performed at a temperature of 100 to 180°C for about 10 seconds to 5 minutes after drying.

[0231] When the textile material is to be dyed, the treatment with the pretreatment liquid may be carried out before dyeing or in the same bath as the dyeing. However, when reduction soaping is carried out, there is a risk that the compound having the specific functional group (e.g., a phenolic polymer compound, etc.) adsorbed during the process may fall off, so it is preferable to carry out the treatment after reduction soaping after dyeing.

[0232] The treatment temperature in the immersion treatment can be 60 to 130° C. The treatment time can be 5 to 60 minutes.

[0233] In the functional group introduction step using a pretreatment liquid, the amount of the compound having the specific functional group attached is preferably 1.0 to 7.0 parts by weight per 100 parts by weight of the textile material. Within this range, durable water repellency and texture can be simultaneously achieved at high levels.

[0234] The pretreatment liquid is preferably adjusted to a pH of 3 to 5. The pH can be adjusted using a pH adjuster such as acetic acid or malic acid.

[0235] In the pretreatment solution, a salt may be used in combination in order to effectively adsorb the compound having the specific functional group to the fiber material by the salting-out effect. Examples of the salt that can be used include sodium chloride. Examples of suitable salts include sodium carbonate, ammonium sulfate, and sodium sulfate.

[0236] In the functional group introduction step using the pretreatment liquid, it is preferable to remove the compound having the specific functional group that has been treated in excess. An example of a removal method is washing with water. By removing the compound sufficiently, it is possible to prevent the development of water repellency in the subsequent water repellent treatment from being hindered, and in addition, the feel of the resulting textile product is improved. In addition, it is preferable to thoroughly dry the resulting functional group-containing fiber before contacting it with a hydrocarbon-based water repellent.

[0237] (ii) An example of a fiber in which the specific functional group is directly introduced into the material constituting the fiber is cationic dyeable polyester (CD-PET).

[0238] From the viewpoint of improving the water repellency of the resulting textile product, the functional group-containing fiber preferably has a surface zeta potential of −100 to −0.1 mV, more preferably −50 to −1 mV. The zeta potential of the fiber surface can be measured, for example, by a zeta potential / particle size measuring system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0239] The repellent can be applied to a fibrous substrate (e.g., a textile) by any of the methods known for treating textiles with liquids. When the textile is a fabric, the fabric may be immersed in the solution or the solution may be applied or sprayed onto the fabric. The treated textile is dried and preferably heated, e.g., at 80°C to 200°C, to develop the liquid repellency (water and / or oil repellency). Alternatively, the repellent may be applied to the textile by a cleaning process, such as in a laundering application or a dry cleaning process.

[0240] The textile products treated are typically fabrics, including woven, knitted and nonwoven fabrics, apparel fabrics and carpets, but may also be fibers or yarns or intermediate textile products (such as slivers or rovings). The textile material may be natural fibers (such as cotton or wool), chemical fibers (such as viscose rayon or leocell), or synthetic fibers (such as polyester, polyamide or acrylic fibers), or may be a mixture of fibers (such as a mixture of natural and synthetic fibers). The method of the present disclosure also generally renders textile products hydrophobic and water repellent. Alternatively, the fibrous substrate may be leather. The product polymer may be applied to the leather from an aqueous solution or emulsion at various stages of the leather processing, for example during the wet processing of the leather or during the finishing of the leather, to render the leather hydrophobic and oleophobic.

[0241] "Treatment" means that the liquid-repellent compound is applied to the object to be treated by immersion, spray coating, etc. By the treatment, the active ingredient of the liquid- and oil-repellent compound penetrates into the inside of the object to be treated and / or adheres to the surface of the object to be treated.

[0242] Although the embodiments have been described above, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims. EXAMPLES

[0243] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0244] <Test Method> The test procedure is as follows.

[0245] [Making pulp molds] A pulp mold was produced using an automatic molding machine. A mesh-like body was placed on a metal pulp mold forming die with many suction holes at the bottom, and a metal tank was placed on the top, with the pulp slurry being placed in the upper metal tank. The pulp-containing aqueous composition was sucked and dehydrated through the pulp mold forming die and mesh-like body at 0.1 to 1 MPa by a vacuum pump from the side opposite to the side where the mesh-like body was placed in the pulp mold forming die, and the solid content (pulp, etc.) contained in the pulp-containing aqueous composition was deposited on the mesh-like body to obtain a pulp mold intermediate. Next, the obtained pulp mold intermediate was dried under a pressure of 0.1 to 1 MPa from above and below with a male and female metal forming die heated to 60 to 200°C. This produced a pulp mold formed into the shape of a container.

[0246] [Practical oil resistance test - 65℃] The pulp mold was pretreated by storing it under conditions of 23°C and 50% humidity for 12 hours. 100 ml of corn oil at 65°C was poured into the pulp mold and left at room temperature for 45 minutes, after which the corn oil was removed from the pulp mold and the degree of oil staining of the pulp mold was evaluated. The following evaluation values ​​were set according to the degree of staining. 5: No stains on the inside 4: Stain on the inside. No stain on the back. 3: Stain on the inside. Slight seepage on the back. 2: Stain on the inside. Less than 50% of the area has seeped through to the back. 1: Stain on the inside. Stain on the back is 50% or more but less than 100% of the area. 0: Seeping through to the entire back side.

[0247] [Practical oil resistance test - 80℃] The pulp mold was pretreated by storing it for 12 hours under conditions of 23°C and 50% humidity. The same operations and evaluations were carried out as in [Practical oil resistance test - 65°C], except that corn oil at 80°C was used instead of corn oil at 65°C.

[0248] [Practical oil resistance test - 100℃] The pulp mold was pretreated by storing it for 12 hours under conditions of 23°C and 50% humidity. The same operations and evaluations were carried out as in [Practical oil resistance test - 65°C], except that 100°C corn oil was used instead of 65°C corn oil.

[0249] [Practical oil resistance test - 110℃] The pulp mold was pretreated by storing it for 12 hours under conditions of 23°C and 50% humidity. The same operations and evaluations were carried out as in [Practical oil resistance test - 65°C], except that 110°C corn oil was used instead of 65°C corn oil.

[0250] [Practical oil resistance test - 120℃] The pulp mold was pretreated by storing it for 12 hours under conditions of 23°C and 50% humidity. The same operations and evaluations were carried out as in [Practical oil resistance test - 65°C], except that 120°C corn oil was used instead of 65°C corn oil.

[0251] [Practical water resistance test] The pulp mold was pretreated by storing it under conditions of 23°C and 50% humidity for 12 hours. 100 ml of 100°C water was poured into the pulp mold, and after leaving it at room temperature for 30 minutes, the water was removed from the pulp mold and the degree of staining of the pulp mold was evaluated. The following evaluation values ​​were set according to the degree of staining. 5: No stains on the inside 4: Stain on the inside. No stain on the back. 3: Stain on the inside. Slight seepage on the back. 2: Stain on the inside. Less than 50% of the area has seeped through to the back. 1: Stain on the inside. Stain on the back is 50% or more but less than 100% of the area. 0: Seeping through to the entire back side.

[0252] [Preparation of treated paper] Water resistance (Cobb value) 52g / m 2 , basis weight 45g / m 2 , density 0.60g / m 3 For thin paper, 14.9 mg / cm 3 The treated paper was created by applying the liquid repellent compound solution three times using a Baker-type applicator with a gap set to 0 mil, and then annealing at 140°C for 1 minute. Chloroform was used to prepare the coating solution. When the liquid repellent compound was insoluble in chloroform, organic solvents such as toluene and acetone were used.

[0253] [KIT test (oil resistance)] Measurements were made 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 on the surface of treated paper, wiping the test oil off after 15 seconds, and evaluating the presence or absence of oil stains on the treated paper. Tests were performed using test oils with kit numbers 1 to 6, and the highest kit number that showed no stains was used to evaluate the oil resistance.

[0254] [Corn oil resistance test (oil resistance)] Corn oil is placed on the surface of the treated paper, and after 15 seconds the test oil is wiped off. The evaluation is based on whether or not the treated paper is stained with oil. If there is no stain, mark it as a circle; if there is a stain, mark it as an X.

[0255] [HD contact angle] A solution (or dispersion) of a liquid-repellent compound with a solid content concentration of 1.0% was spin-coated on a silicon wafer at 2500 rpm for 25 seconds to obtain a smooth spin-coated film. This was heated at 140°C for 1 minute to produce a compound-treated silicon wafer. Chloroform was used as the solvent or dispersion medium. 2 μL of HD (hexadecane) was dropped onto the compound-treated silicon wafer, and the static contact angle 1 second after the drop landed was taken as the HD contact angle of the liquid-repellent compound.

[0256] [Tensile strength of pulp molded products] The tensile strength of the pulp mold was evaluated by the specific tensile strength in a dry state measured according to JIS P 8113:2006, although there was no particular limitation. A test piece 15 mm wide, 50 mm long, and 0.8 mm thick was cut out from the bottom of the pulp mold and used. The test was performed using an autograph made by Shimadzu Corporation, with a tension interval of 30 mm and a tension speed of 10 mm / min.

[0257] [Fabric water repellency test] A treatment solution with a solid concentration of 16.8 mg / mL was prepared using chloroform as a solvent. The cloth was immersed in this treatment solution and then passed through a mangle. The water repellency of the heat-treated test cloth was evaluated. The water repellency of the treated fabric was evaluated according to the spray method of JIS-L-1092 (AATCC-22). It is expressed by the water repellency number as shown in the table below. The higher the score, the better the water repellency. A "+" next to a number means that it is better than that number, and a "-" means that it is worse than that number. The evaluation was carried out using polyester fabric (PET) or nylon fabric (Ny). TIFF0007648935000013.tif41139

[0258] <Compound 2> 5.57 g of stearic acid (Tokyo Chemical Industry Co., Ltd.), 3.57 g of 2-amino-1,3-propanediol (Fuji Film Wako Pure Chemical Industries, Ltd.), and 0.239 g of 4,4-dimethylaminopyridine (Fuji Film Wako Pure Chemical Industries, Ltd.) were dissolved in 100.0 mL of dehydrated dimethylformamide (Fuji Film Wako Pure Chemical Industries, Ltd.), and 4.50 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (Tokyo Chemical Industry Co., Ltd.) were added in this order and stirred overnight at an oil bath temperature of 100 ° C. The next day, the reaction solution was cooled to 40 ° C., filtered, and the solid was washed with dimethylformamide and water. After washing, the solid was dried to obtain 1.64 g of compound 1 shown below. TIFF0007648935000014.tif2753 1H NMR(CDCl3,400MHz)δ:0.87(t,3H),1.24-1.70(m,30H),2.22(t,2H),3.76-3.96(m,5H),6.16(brd,2H)

[0259] 1.64 g of compound 1 was dissolved in 35.0 mL of dehydrated tetrahydrofuran (Fujifilm Wako Pure Chemicals), and then 2.98 g of octadecyl isocyanate (Fujifilm Wako Pure Chemicals) and 4 drops of dibutyltin dilaurate were added in that order, and the mixture was stirred overnight at an oil bath temperature of 70° C. The next day, the reaction solution was cooled to room temperature, filtered, and the solid was washed with tetrahydrofuran. After washing, the solid was dried to obtain 4.32 g of compound 2 shown below. TIFF0007648935000015.tif4070 1 H NMR(CDCl3,400MHz)δ:0.87(t,9H),1.24-1.75(m,94H),2.15(t,2H),3.00-3.20 (m,4H),4.00-4.25(m,4H),4.30-4.40(m,1H),4.70-4.75(m,2H),6.05(brd,2H)

[0260] <Compound 3> 6.00 g of stearic acid (Tokyo Chemical Industry Co., Ltd.), 0.7 g of N,N'-di(2-aminoethyl)ethylenediamine (Tokyo Chemical Industry Co., Ltd.), and 0.12 g of 4,4-dimethylaminopyridine (Fujifilm Wako Pure Chemical Industries, Ltd.) were dissolved in 60.0 mL of dehydrated chloroform (Fujifilm Wako Pure Chemical Industries, Ltd.), and 4.13 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (Tokyo Chemical Industry Co., Ltd.) were added in this order and stirred overnight at an oil bath temperature of 50 ° C. The next day, the reaction solution was cooled to room temperature, filtered, and the solid was washed with methanol, diethyl ether, and dichloromethane. After washing, the solid was dried to obtain 3.76 g of compound 3 shown below. TIFF0007648935000016.tif5588 1 H NMR(CDCl3,400MHz)δ:0.87(t,12H),1.24-1.70(m,120H),2.20-2.40(m,8H),3.27-4.10(m,12H),6.16(brd,2H)

[0261] <Compound 4> Compound 4 shown below was synthesized with reference to CN109280362A (2019-01-29). TIFF0007648935000017.tif4751 [In the formula, R is a stearyl group.]

[0262] <Examples 1 to 3> Using the compounds 2 to 4 obtained above, a mold test was carried out.

[0263] 2 g of compound 2 was mixed with 0.2 g of polyoxyethylene (10) oleyl ether (HLB14), and the mixture was heated to 140°C to melt. The obtained solid was pulverized in a mortar, 17.8 g of water was added, and the mixture was stirred for 20 minutes at 10,000 rpm with a homogenizer to obtain an aqueous dispersion composition of compound 2. Subsequently, the aqueous dispersion composition of compound 2 was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the pulp to the solid content was 10 wt%, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was put into an automatic molding machine to prepare a pulp mold. The pulp mold was subjected to a practical oil resistance test at -65°C and a practical water resistance test, and the oil resistance and water resistance were 4 points.

[0264] 2 g of compound 3 was mixed with 0.2 g of polyoxyethylene (10) oleyl ether (HLB14), and the mixture was heated to 130°C to melt. The obtained solid was pulverized in a mortar, 17.8 g of water was added, and the mixture was stirred for 20 minutes at 10,000 rpm with a homogenizer to obtain an aqueous dispersion composition of compound 3. Subsequently, the aqueous dispersion composition of compound 3 was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the pulp to the solid content was 10 wt%, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was put into an automatic molding machine to prepare a pulp mold. The pulp mold was subjected to a practical oil resistance test at -65°C and a practical water resistance test, and the oil resistance and water resistance were 4 points.

[0265] 2 g of compound 4 was mixed with 0.2 g of polyoxyethylene (10) oleyl ether (HLB14), and the mixture was heated to 160°C to melt. The obtained solid was pulverized in a mortar, 17.8 g of water was added, and the mixture was stirred for 20 minutes at 10,000 rpm with a homogenizer to obtain an aqueous dispersion composition of compound 4. Subsequently, the aqueous dispersion composition of compound 4 was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the solid content to the pulp was 10 wt%, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was put into an automatic molding machine to prepare a pulp mold. The pulp mold was subjected to a practical oil resistance test at -65°C and a practical water resistance test, and the oil resistance and water resistance were 4 points.

[0266] The test results are summarized in Table 1 below, along with the melting points. [Table 1] TIFF0007648935000018.tif33165

[0267] <Examples 4 to 5> The compounds obtained above were subjected to the KIT test (oil resistance), the corn oil resistance test, and the liquid repellency evaluation. The test results are summarized in Table 2 below. [Table 2] TIFF0007648935000019.tif32166

[0268] <Example 6> 2 g of N,N'-ethylenebisoctadecanamide (biobased content: 97%, melting point: 143°C), 0.2 g of polyethylene glycol trimethylnonyl ether (HLB13), and 17.8 g of water were mixed to obtain an aqueous dispersion composition (volume proportion of particles of 100 μm or more: 3.9%, volume median diameter: 18 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the aqueous dispersion composition to the pulp was 3 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was charged into an automatic molding machine to prepare a pulp mold. The pulp mold was subjected to practical oil resistance tests at -110°C, -65°C, and practical water resistance tests, and was rated 4 points in all cases.

[0269] <Example 7> 2 g of N,N'-ethylene bisoleamide (bio-based content: 96%, melting point: 116°C), 0.2 g of EO / PO polyalkylene glycol alcohol ether, and 17.8 g of water were mixed to obtain an aqueous dispersion composition (volume ratio of particles of 100 μm or more: 0%, volume median diameter: 24 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the aqueous dispersion composition to the pulp was 10 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was charged into an automatic molding machine to prepare a pulp mold. The mold was subjected to a practical oil resistance test at -65°C and received a score of 4, and was subjected to a practical water resistance test and received a score of 4. When N,N'-ethylenebisoleamide was used in the KIT test (oil resistance) and corn oil resistance test, it received a score of 4 in the KIT test and a score of OK in the corn oil resistance test.

[0270] <Example 8> 2 g of N,N'-xylylene-bis-12-hydroxystearylamide (biobased content: 83%, melting point: 124°C), 0.2 g of benzalkonium chloride, and 17.8 g of water were mixed to obtain an aqueous dispersion composition (volume ratio of particles of 100 μm or more: 0%, volume median diameter: 7 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the aqueous dispersion composition to the pulp was 3 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was charged into an automatic molding machine to prepare a pulp mold. When the pulp mold was subjected to a practical oil resistance test at -65°C, it received a score of 4. When N,N'-xylylene-bis-12-hydroxystearylamide was used in the KIT test (oil resistance) and corn oil resistance test, it received a score of 3 in the KIT test and a score of OK in the corn oil resistance test.

[0271] <Example 9> 2 g of N,N'-xylylene-bis-12-hydroxystearylamide (biobased content: 83%), 0.2 g of polyethylene glycol trimethylnonyl ether (HLB13), and 17.8 g of water were mixed to obtain an aqueous dispersion composition (volume ratio of particles of 100 μm or more: 0%, volume median diameter: 9 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the aqueous dispersion composition to the pulp was 10 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was charged into an automatic molding machine to prepare a pulp mold. When subjected to a practical oil resistance test at -65°C, the score was 4 points, when the pulp mold was subjected to a practical oil resistance test at -80°C, the score was 4 points, when the pulp mold was subjected to a practical oil resistance test at -120°C, the score was 4 points, and when subjected to a practical water resistance test, the score was 4 points.

[0272] <Example 10> 2 g of N,N'-xylylene-bis-12-hydroxystearylamide (biobased content: 83%), 0.2 g of potassium oleate, and 17.8 g of water were mixed to obtain an aqueous dispersion composition (volume proportion of particles of 100 μm or more: 0%, volume median diameter: 9 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the aqueous dispersion composition to the pulp was 10 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was charged into an automatic molding machine to prepare a pulp mold. When the pulp mold was subjected to a practical oil resistance test at -65°C, it received a score of 4, and when it was subjected to a practical water resistance test, it received a score of 4.

[0273] <Example 11> 2 g of N,N'-ethylene-bis-12-hydroxystearylamide (biobased content: 95%, melting point: 145°C), 0.2 g of EO / PO polyalkylene glycol natural alcohol ether, and 17.8 g of water were mixed to obtain an aqueous dispersion composition (volume ratio of particles 100 μm or larger: 5%, volume median diameter: 17 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt % so that the ratio of the aqueous dispersion composition to the pulp was 5 wt % in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was charged into an automatic molding machine to prepare a pulp mold. When the pulp mold was subjected to a practical oil resistance test at -65°C, it received a score of 4, and when the pulp mold was subjected to a practical oil resistance test at -110°C, it received a score of 4.

[0274] <Example 12> 2 g of N,N'-ethylene-bis-12-hydroxystearylamide (bio-based content: 95%), 0.2 g of EO / PO polyalkylene glycol natural alcohol ether, and 17.8 g of water were mixed to obtain an aqueous dispersion composition (volume ratio of particles of 100 μm or more: 8.2%). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the aqueous dispersion composition to the pulp was 10 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was charged into an automatic molding machine to prepare a pulp mold. When the pulp mold was subjected to a practical oil resistance test at -80°C, it received a score of 4.

[0275] <Example 13> 2 g of N,N'-ethylene-bis-12-hydroxystearylamide (bio-based content: 95%), 0.2 g of EO / PO polyalkylene glycol natural alcohol ether, and 17.8 g of water were mixed to obtain an aqueous dispersion composition (volume ratio of particles of 100 μm or more: 5%, volume median diameter: 17 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the aqueous dispersion composition to the pulp was 3 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was charged into an automatic molding machine to prepare a pulp mold. The pulp mold was subjected to a practical water resistance test and scored 4 points.

[0276] <Example 14> 2 g of N,N'-hexamethylene-bis-12-hydroxystearylamide (bio-based content: 85%, melting point: 134°C), 0.2 g of EO / PO polyalkylene glycol natural alcohol ether, and 17.8 g of water were mixed to obtain a water dispersion composition (volume ratio of particles of 100 μm or more: 3.5%, volume median diameter: 12 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the aqueous dispersion composition to the pulp was 7 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was charged into an automatic molding machine to prepare a pulp mold. When the pulp mold was subjected to a practical oil resistance test at -65°C, it received a score of 4, when subjected to a practical oil resistance test at -80°C, it received a score of 4, and when subjected to a practical oil resistance test at -100°C, it received a score of 4.

[0277] <Example 15> 2 g of compound 3, 0.2 g of EO / PO polyalkylene glycol natural alcohol ether, and 17.8 g of water were mixed to obtain a water dispersion composition. The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the aqueous dispersion composition to the pulp was 10 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was charged into an automatic molding machine to prepare a pulp mold.

[0278] <Example 16> N(CH2CH2NHCONHR)3 [In the formula, R is a stearyl group.] Compound 5 (2 g) represented by the formula (1) was mixed with 0.2 g of EO / PO polyalkylene glycol natural alcohol ether, the resulting solid was pulverized in a mortar, 17.8 g of water was added, and the mixture was stirred for 20 minutes at 10,000 rpm with a homogenizer to obtain a water dispersion composition of compound 5. (Volume ratio of particles of 100 μm or more: 0%) The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the aqueous dispersion composition to the pulp was 7 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was charged into an automatic molding machine to prepare a pulp mold. The pulp mold was subjected to a practical oil resistance test at -65°C and scored 4 points, subjected to a practical oil resistance test at -80°C and scored 4 points, and subjected to a practical water resistance test and scored 4 points.

[0279] <Example 17> RNHCONHCH2CH2N(CONHR)CH2CH2N(CONHR)CH2CH2NHCONHR [In the formula, R is a stearyl group.] Compound 6 (2 g) was mixed with EO / PO polyalkylene glycol natural alcohol ether (0.2 g), the resulting solid was pulverized in a mortar, 17.8 g of water was added, and the mixture was stirred at 10,000 rpm with a homogenizer for 20 minutes to obtain a water dispersion composition of compound 6. (Volume ratio of particles of 100 μm or more: 25.7%) The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the aqueous dispersion composition to the pulp was 10 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was charged into an automatic molding machine to prepare a pulp mold. When the pulp mold was subjected to a practical oil resistance test at -65°C, it received a score of 5, when subjected to a practical oil resistance test at -80°C, it received a score of 5, and when subjected to a practical water resistance test, it received a score of 5.

[0280] <Example 18> 2 g of N,N'-ethylenebisoctadecanamide, 1.2 g of benzalkonium chloride, 0.8 g of polyethylene glycol trimethylnonyl ether, and 36 g of water were pulverized in a wet-type micronizer under conditions of 150 MPa to obtain an aqueous dispersion composition (volume ratio of particles of 100 μm or more: 0%, volume median diameter: 52 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the aqueous dispersion composition to the pulp was 10 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was charged into an automatic molding machine to prepare a pulp mold. When the pulp mold was subjected to a practical oil resistance test at -65°C, it received a score of 4.

[0281] <Example 19> A biodegradability test was conducted on N,N'-ethylenebisoleamide (biobased content: 96%, melting point: 116°C) based on JIS K 6953-1:2011. After 30 days of testing, the biodegradability was 65%, and after 60 days of testing, the biodegradability was 77%.

[0282] <Example 20> The measurement results of the HD contact angles (n-hexadecane contact angle) of N,N'-ethylenebisoctadecanamide, N,N'-ethylenebisoleamide, N,N'-xylylene-bis-12-hydroxystearylamide, and N,N-ethylene-bis-12-hydroxystearylamide are shown in Table 3.

[0283] [Table 3] TIFF0007648935000020.tif54155

[0284] <<Improvement of paper strength of pulp mold by adding repellent>> <Example 21> The tensile strength of the pulp molds prepared in Example 6 (N,N'-ethylenebisoctadecaneamide), Example 8 (N,N'-xylylene-bis-12-hydroxystearylamide), and Example 12 (N,N-ethylene-bis-12-hydroxystearylamide) was evaluated and the results are shown in Table 4.

[0285] <Comparative Example 1> The pulp-containing aqueous composition without adding the liquid-repellent compound was put into an automatic molding machine to prepare a pulp mold. The tensile strength of the prepared pulp mold was evaluated, and the results are shown in Table 4.

[0286] [Table 4. Evaluation results of tensile test of pulp mold] TIFF0007648935000021.tif60155 From Table 4, it can be seen that the liquid repellent compound has the effect of improving the tensile strength and increasing the paper strength.

[0287] <<Improvement of paper strength of molded pulp by using paper strength agents in combination>> <Example 22> The aqueous dispersion composition of N,N'-xylylene-bis-12-hydroxystearylamide prepared in Example 8 was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the solid content was 3 wt% relative to the pulp, and the mixture was stirred for 30 seconds, after which a polyacrylamide-based paper strength agent was added at 0.1 wt% relative to the pulp and stirred for 30 seconds to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was placed in an automatic molding machine to prepare a pulp mold. The pulp mold was subjected to a practical oil resistance test at -65°C, and the result was 4 points. The results of evaluating the tensile strength of the prepared pulp mold are shown in Table 5.

[0288] <Example 23> The aqueous dispersion composition of N,N'-xylylene-bis-12-hydroxystearylamide prepared in Example 8 was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the solid content was 3 wt% relative to the pulp, and the mixture was stirred for 30 seconds, after which a polyacrylamide-based paper strength agent was added at 0.5 wt% relative to the pulp and stirred for 30 seconds to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was placed in an automatic molding machine to prepare a pulp mold. The pulp mold was subjected to a practical oil resistance test at -65°C, and the result was 4 points. The results of evaluating the tensile strength of the prepared pulp mold are shown in Table 5.

[0289] <Example 24> The aqueous dispersion composition of N,N'-xylylene-bis-12-hydroxystearylamide prepared in Example 8 was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the solid content was 3 wt% relative to the pulp, and the mixture was stirred for 30 seconds, after which a polyacrylamide-based paper strength agent was added at 0.5 wt% relative to the pulp and stirred for 30 seconds to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was placed in an automatic molding machine to prepare a pulp mold. The pulp mold was subjected to a practical oil resistance test at -65°C, and the result was 4 points. The results of evaluating the tensile strength of the prepared pulp mold are shown in Table 5.

[0290] [Table 5. Evaluation results of tensile test of pulp mold] TIFF0007648935000022.tif70155

[0291] <Example 25> The aqueous dispersion composition of N,N'-xylylene-bis-12-hydroxystearylamide prepared in Example 8 was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the solid content was 3 wt% relative to the pulp, and the mixture was stirred for 30 seconds, after which a cationic starch aqueous solution was added to the pulp at 3 wt% relative to the solid content, and the mixture was stirred for 30 seconds to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was placed in an automatic molding machine to produce a pulp mold. The pulp mold was subjected to a practical oil resistance test at -65°C, and scored 4 points.

[0292] <Example 26> The aqueous dispersion composition of N,N'-xylylene-bis-12-hydroxystearylamide prepared in Example 8 was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the solid content was 3 wt% relative to the pulp, and the mixture was stirred for 30 seconds, after which an alkyl ketene dimer dispersion was added as a sizing agent at 0.5 wt% relative to the pulp in solid content, and the mixture was stirred for 30 seconds to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was put into an automatic molding machine to produce a pulp mold. The pulp mold was subjected to a practical oil resistance test at -65°C, and was scored as 4 points.

[0293] <<Fabric Treatment Water Repellency Test>> <Example 27> [Water repellency test] A treatment solution with a solid content of 16.8 mg / mL was prepared using N,N'-xylylene-bis-12-hydroxystearylamide in chloroform as the solvent. PET fabric was immersed in the treatment solution, passed through a mangle, and air-dried at room temperature for 24 hours. It was then heat-treated at 140°C for 5 minutes and cooled to room temperature to prepare a test fabric. The test fabric was evaluated for water repellency. The water repellency test resulted in a score of 90.

[0294] << Extraction of compounds from pulp mold and 1 H NMR measurement>> <Example 28> A pulp mold containing N,N'-ethylenebisoctadecaneamide was prepared in the same manner as in Example 6. Ten pieces each having a diameter of 3 mm were cut out from the bottom of the pulp mold using a 3 mm hole punch. The ten pieces were placed in a 2 mL vial, and 2 g of CDCl3 was added. The vial was then capped and heated at 60°C for 1 hour. The CDCl3 was transferred from the vial to an NMR tube, 1 The H NMR measurement gave the following results: 1 The 1 H NMR spectrum was confirmed. 1 H NMR(CDCl3,400MHz)δ:0.88(t,6H),1.20-1.80(m,60H),2.17(t,2H),2.35(t,1H),3.39(m,2H)

[0295] <Example 29> A pulp mold containing N,N'-ethylenebisoleamide was prepared in the same manner as in Example 7. 1 H NMR measurement gave the following results: 1 The 1 H NMR spectrum was confirmed. 1 H NMR(CDCl3,400MHz)δ:0.88(t,6H),1.20-1.80(m,44H),1.90-2.21(t,12H),3.38(m,4H),5.28-5.42(m,4H)

[0296] <Example 30> A pulp mold containing N,N'-xylylene-bis-12-hydroxystearylamide was prepared in the same manner as in Example 9. 1 H NMR measurement gave the following results: 1 The 1 H NMR spectrum was confirmed. 1 H NMR(CDCl3,400MHz)δ:0.88(m,6H),1.20-1.80(m,64H),2.21(t,3H),4.43(m,4H),7.15-7.21(m,4H)

Claims

1. an amine backbone, and The following formula: -X-R ｎ [In the formula, X is a direct bond or a 1+n-valent group, and is a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O) 2 -, -NR'-, -C(OR')R'-, -C(OR')(-) 2 , -N(-) 2 , a di- to tetravalent aliphatic hydrocarbon group having 1 to 10 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.] is a 1+n valent group consisting of one or more groups selected from the group consisting of R is independently in each occurrence a linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent; n is an integer of 1 to 3. The compound has one or more long chain hydrocarbon-containing groups represented by the formula: A paper repellent comprising a liquid repellent compound, wherein at least one of the long chain hydrocarbon-containing groups is bonded to a nitrogen atom of the amine skeleton, The liquid repellent compound is The following formula: N(-X-R n ) p (-H) q -L 1 -[N(-X-R n ) r (-H) s -L 1 -] t -N(-X-R n ) p (-H) q [In the formula, X is independently in each occurrence a direct bond or a group having a valence of 1+n; R is independently in each occurrence a linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent; L 1 is independently in each occurrence a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be interrupted by oxygen atoms and / or sulfur atoms; n is independently in each occurrence an integer between 1 and 3, inclusive; p, in each occurrence, is an integer between 0 and 2, inclusive; q is independently in each occurrence an integer from 0 to 2, p+q is each N(-XR n ) p (-H) q In the above, r is independently in each occurrence 0 or 1; s is independently in each occurrence 0 or 1; r+s is each N(-XR n ) r (-H) s In the sum of all p's and all r's is greater than or equal to 1; t is an integer of 0 to 10. or The following formula: N(-X-R n ) p (-H) q -L ２ (-X-R n ) u [In the formula, X is independently in each occurrence a direct bond or a group having a valence of 1+n; R is independently in each occurrence a linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent; L ２ represents an aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms and a valence of 1+u, which may be interrupted by an oxygen atom and / or a sulfur atom, n is independently in each occurrence an integer between 1 and 3, inclusive; p is an integer of 0 to 2, q is an integer of 0 to 2, p+q is 2, u is an integer of 1 to 3, The sum of p and u is 1 or more. A compound represented by the formula: The repellent does not contain a fluorine compound.

2. The repellent according to claim 1, wherein the amine skeleton is composed of a monovalent to trivalent amino group and a linear saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group which may be interrupted by an oxygen atom and / or a sulfur atom.

3. The repellent according to claim 1 , wherein the molar ratio of carbon atoms to nitrogen atoms (C / N ratio) in the amine skeleton is 8 or less.

4. The liquid repellent compound is The following formula: [In the formula, R is a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent. or The following formula: [In the formula, R is a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent. A compound represented by The repellent according to claim 1 ,

5. The repellent according to claim 1 , wherein R has 12 or more carbon atoms.

6. The repellent described in claim 1, wherein the carbon number of the divalent to tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms is 5 or less.

7. The liquid repellent according to claim 1 , wherein the liquid repellent compound has a melting point of 40° C. or higher or has no melting point.

8. The liquid repellent according to claim 1, wherein the liquid repellent compound has a contact angle with n-hexadecane of 10° or more.

9. The liquid repellent according to claim 1 , wherein the bio-based content of the liquid repellent compound is 30% or more.

10. The repellent according to claim 1, wherein the volumetric ratio of particles having a size of 100 μm or more is 25% or less as measured by dynamic light scattering or laser diffraction scattering.

11. The repellent according to claim 1 , which is an aqueous dispersion.

12. The repellent of claim 11, comprising one or more selected from the group consisting of surfactants, silicones, waxes, organic acids, and hardeners.

13. An oil-resistant or water-repellent paper having the liquid-repellent compound in the repellent agent according to any one of claims 1 to 12 adhered thereto.

14. 14. The greaseproof or water-repellent paper according to claim 13, which is a food packaging material or food container.

15. A method for producing greaseproof or water-repellent paper, comprising a step of externally or internally treating paper with the repellent according to any one of claims 1 to 12.

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