Polarizing agent

Abstract

Provided is a novel poking agent capable of imparting a liquid-repellent property to a base material (for example, fiber or paper) using the poking agent. The stirring agent contains a liquid-stirring compound having an amine skeleton and one or more of the following formula:-X-Rn [wherein the meaning of each symbol is the same as that described in the description. ] At least one of the long-chain hydrocarbon-containing groups is bonded to a nitrogen atom contained in the amine skeleton.

Description

Technical Field

[0001] The present invention relates to a dispersing agent. Background Art

[0002] In recent years, research has been conducted on materials and methods that can impart water repellency or oil repellency 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 containing a structural unit derived from a (meth)acrylate monomer and a structural unit derived from an organic 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.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2016-199712 Summary of the invention

[0006] Problems to be solved by the invention

[0007] An object of the present invention is to provide a novel repellent agent capable of imparting liquid repellency to a substrate (eg, fiber, paper).

[0008] Technical means to solve problems

[0009] The present invention includes the following aspects.

[0010] [Item 1] A repellent comprising a liquid repellent compound,

[0011] The liquid repellent compound has:

[0012] an amine backbone; and

[0013] One or more of the following formula: -X-R n The long-chain hydrocarbon-containing groups shown,

[0014] At least one of the above long-chain hydrocarbon-containing groups is bonded to the nitrogen atom of the above amine skeleton.

[0015] [Wherein,

[0016] X is a direct bond or a 1+n valent group,

[0017] R, when present, is independently a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent,

[0018] n is an integer of 1 to 3.]

[0019] At least one of the long-chain hydrocarbon-containing groups is bonded to a nitrogen atom of the amine skeleton.

[0020] [Item 2] The expelling agent according to Item 1, wherein the amine skeleton is composed of monovalent to trivalent amino groups and chain-like saturated aliphatic hydrocarbon groups or aromatic hydrocarbon groups which may be interrupted by oxygen atoms and / or sulfur atoms.

[0021] [Item 3] The expelling agent according to Item 1 or 2, wherein the molar ratio of carbon atoms to nitrogen atoms (C / N ratio) in the above-mentioned amine skeleton is 8 or less.

[0022] [Item 4] The expelling agent according to any one of Items 1 to 3, wherein

[0023] The liquid repellent compound is of the following formula:

[0024] N(-XR n ) p (-H) q -L 1 -[N(-XR n ) r (-H) s -L 1 -] t -N(-XR n ) p (-H) q The compound shown, or the following formula:

[0025] N(-XR n ) p (-H) q -L 2 (-XR n ) u The compounds shown.

[0026] [Formula: N(-XR n ) p (-H) q -L 1 -[N(-XR n ) r (-H) s -L 1 -] t -N(-XR n ) p (-H) q middle,

[0027] X is independently a direct bond or a 1+n-valent group at each occurrence,

[0028] R, when present, is independently a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent,

[0029] L 1is independently, at 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,

[0030] n is independently an integer from 1 to 3 at each occurrence,

[0031] p is independently an integer from 0 to 2 at each occurrence,

[0032] q is independently an integer from 0 to 2 at each occurrence,

[0033] p+q in each N(-XR n ) p (-H) q The middle is 2,

[0034] r is independently 0 or 1 at each occurrence,

[0035] s is independently 0 or 1 at each occurrence,

[0036] r+s in each N(-XR n ) r (-H) s The middle is 1,

[0037] The sum of all p's and all r's is greater than 1,

[0038] t is an integer of 0 to 10.]

[0039] [Formula: N(-XR n ) p (-H) q -L 2 (-XR n ) u middle,

[0040] X is independently a direct bond or a 1+n-valent group at each occurrence,

[0041] R, when present, is independently a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent,

[0042] L 2 is a 1+u-valent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by oxygen atoms and / or sulfur atoms,

[0043] n is independently an integer from 1 to 3 at each occurrence,

[0044] p is an integer from 0 to 2,

[0045] q is an integer from 0 to 2,

[0046] p+q is 2,

[0047] u is an integer from 1 to 3,

[0048] The total of p and u is greater than or equal to 1.]

[0049] [Item 5] The expelling agent according to any one of Items 1 to 4, wherein R has 12 or more carbon atoms.

[0050] [Item 6] The expelling agent according to any one of Items 1 to 5, wherein

[0051] X is a 1+n-valent group consisting of a direct bond, one or more selected from -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2, a 2- to 4-valent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a 2- to 4-valent aromatic hydrocarbon ring, and a 2- to 4-valent heterocyclic ring.

[0052] [In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.]

[0053] [Item 7] The 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.

[0054] [Item 8] The repellent according to any one of Items 1 to 7, wherein the liquid repellent compound has a n-hexadecane contact angle of 10° or more.

[0055] [Item 9] The repellent according to any one of Items 1 to 8, wherein the biobased content of the liquid repellent compound is 30% or more.

[0056] [Item 10] The expelling agent according to any one of Items 1 to 9, wherein the volume abundance ratio of particles having a size of 100 μm or more measured by a dynamic light scattering method or a laser diffraction scattering method is 25% or less.

[0057] [Item 11] The expelling agent according to any one of Items 1 to 10, which is an aqueous dispersion.

[0058] [Item 12] The expelling agent as described in Item 11, which contains one or more selected from the group consisting of surfactants, silicones, waxes, organic acids and curing agents.

[0059] [Item 13] The dispersing agent according to any one of Items 1 to 12, which is a dispersing agent for paper.

[0060] [Item 14] The expelling agent according to any one of Items 1 to 13, which does not contain a fluorine compound.

[0061] [Item 15] A fiber product to which the liquid repellent compound in the repellent according to any one of Items 1 to 14 is attached.

[0062] [Item 16] Oil-resistant paper or water-repellent paper, to which the liquid-repellent compound in the repellent according to any one of Items 1 to 14 is attached.

[0063] [Item 17] Glass having the liquid repellent compound in the repellent according to any one of Items 1 to 14 adhered thereto.

[0064] [Item 18] The oil-resistant paper or water-repellent paper as described in Item 16, which is a food packaging material or a food container.

[0065] [Item 19] A method for producing oil-resistant paper or water-repellent paper, comprising the step of subjecting the paper to an external or internal addition treatment using the repellent described in any one of Items 1 to 14.

[0066] [Item 20] A formula:

[0067] N(-XR n ) p (-H) q -L 1 -[N(-XR n ) r (-H) s -L 1 -] t -N(-XR n ) p (-H) q The compound shown, or the following formula:

[0068] N(-XR n ) p (-H) q -L 2 (-XR n ) u The compounds shown.

[0069] [Formula: N(-XR n ) p (-H) q -L 1 -[N(-XR n ) r (-H) s -L 1 -] t -N(-XR n ) p (-H) q middle,

[0070] X is independently a direct bond or a 1+n-valent group at each occurrence,

[0071] R, when present, is independently a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent,

[0072] L 1 is independently, at each occurrence, a divalent aliphatic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by oxygen atoms and / or sulfur atoms,

[0073] n is independently an integer from 1 to 3 at each occurrence,

[0074] p is independently an integer from 0 to 2 at each occurrence,

[0075] q is independently an integer from 0 to 2 at each occurrence,

[0076] p+q in each N(-XR n ) p (-H) q The middle is 2,

[0077] r is independently 0 or 1 at each occurrence,

[0078] s is independently 0 or 1 at each occurrence,

[0079] r+s in each N(-XR n ) r (-H) s The middle is 1,

[0080] The sum of all p's and all r's is greater than 1,

[0081] t is an integer of 2 to 10.]

[0082] [Formula: N(-XR n ) p (-H) q -L 2 (-XR n ) u middle,

[0083] X is independently a direct bond or a 1+n-valent group at each occurrence,

[0084] R, when present, is independently a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent,

[0085] L 2 is a 1+u-valent aliphatic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by oxygen atoms and / or sulfur atoms,

[0086] n is independently an integer from 1 to 3 at each occurrence,

[0087] p is an integer from 0 to 2,

[0088] q is an integer from 0 to 2,

[0089] p+q is 2,

[0090] u is an integer from 1 to 3,

[0091] The total of p and u is greater than or equal to 1.]

[0092] [Item 21] A formula:

[0093] The compounds shown.

[0094] [Wherein,

[0095] R is a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent.]

[0096] [Item 22] A formula:

[0097] The compounds shown.

[0098] [Wherein,

[0099] R is a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent.]

[0100] Effects of the Invention

[0101] The repellent of the present invention can impart liquid repellency to a substrate (eg, fiber, paper). DETAILED DESCRIPTION

[0102] <Definition of terms>

[0103] As used in this specification, "n-valent group" refers to a group having n bonds, i.e., a group forming n bonds. In addition, "n-valent organic group" refers to a carbon-containing n-valent group. Such an organic group is not particularly limited and may be a hydrocarbon group or a derivative thereof. A derivative of a hydrocarbon group refers to a hydrocarbon group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy or the like at the end or in the molecular chain.

[0104] As used in this specification, a "hydrocarbon group" is a group containing carbon and hydrogen, and is a group obtained by removing a hydrogen atom from a hydrocarbon. Such a hydrocarbon group is not particularly limited, and examples thereof include C 1－20Hydrocarbon groups, such as aliphatic hydrocarbon groups, aromatic hydrocarbon groups, etc. The above-mentioned "aliphatic hydrocarbon groups" can be any of linear, branched or cyclic, and can also be any of saturated or unsaturated. The cyclic group can include a chain structure. The hydrocarbon group can be substituted by one or more substituents.

[0105] In the present specification, regardless of whether "independently at each occurrence", "independently of each other", "independently of each other" or equivalent expressions are explicitly stated, unless otherwise specified, when a term (symbol) occurring multiple times is defined in a chemical structure, the definition is applied independently at each occurrence.

[0106] It should be understood that the chemical structures described in this specification do not include chemical structures that are considered chemically impossible or extremely unstable by those skilled in the art.

[0107] <Dipping agent>

[0108] The repellent of the present invention can impart liquid repellency to a substrate (e.g., a fiber substrate, a paper substrate, glass, such as cloth, paper, etc.). The repellent of the present invention can function as at least one of a water repellent, an oil repellent, an oil resistant agent, and a water resistant agent. For example, the repellent of the present invention is 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 is added is improved.

[0109] The liquid-repellent compound as an active ingredient in the repellent of the present invention has excellent dispersibility in a liquid medium due to its structure, and the performance of the repellent of the present invention is stable.

[0110] In the prior art, the expelling agent using polymer compounds as the active ingredient has a wide molecular weight distribution and tends to contain more impurities. However, the active ingredient of the expelling agent of the present invention is low molecular weight, which can narrow the molecular weight distribution (single), and improve the performance.

[0111] The repellent of the present invention contains a liquid repellent compound. The repellent of the present invention may also be a liquid repellent compound alone. In addition to the liquid repellent compound, the repellent of the present invention may also contain other components such as a liquid medium.

[0112] The repellent of the present invention may not contain any one selected from the group consisting of a compound having a fluoroalkyl group with 8 or more carbon atoms, a compound having a perfluoroalkyl group with 8 or more carbon atoms, a compound having a fluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group with 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 of the present invention can impart liquid repellency to the substrate even if it does not contain these fluorine compounds.

[0113] The volume ratio of particles of 100 μm or more measured by the dynamic light scattering method or the laser diffraction scattering method of the present invention is 25% or less, 20% or less, 15% or less, 10% or less, 5% or less, 3% or less or 1.5% or less, preferably 15% or less or 5% or less. From the viewpoint of coverage, the volume ratio of particles of 100 μm or more is preferably within the above range. There is no limitation on the method for making the volume ratio of particles of 100 μm or more measured by the dynamic light scattering method or the laser diffraction scattering method less than 25%, for example, a pulverizer or a homogenizer can be used to refine the particles in the raw material and / or the dispersion.

[0114] The volume median diameter of the dilution agent of the present invention measured by dynamic light scattering or laser diffraction scattering can be 10 nm or more, 30 nm or more, 50 nm or more, 100 nm or more, preferably 150 nm or more or 200 nm or more; and can 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 invention, the volume median diameter refers to the median diameter (D50) in the volume-based particle size distribution obtained by dynamic light scattering or laser diffraction scattering.

[0115] The repellent of the present invention is preferably used in the form of a dispersion (particularly an aqueous dispersion) together with a liquid medium.

[0116] 〔Lyophobic compounds〕

[0117] The liquid repellent compound of the present invention adheres to a substrate and can impart liquid repellency to the substrate.

[0118] 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. The liquid repellent compound having an HD contact angle above the above lower limit can impart liquid repellency (especially oil repellency) to the substrate. The HD contact angle is a static contact angle of a spin-coated film of the liquid repellent compound as shown in the examples, and refers to a value obtained by dropping 2 μL of HD on the spin-coated film and measuring the contact angle after dropping for 1 second.

[0119] The water contact angle of the liquid-repellent compound can 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 can be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. The liquid-repellent compound has a water contact angle above the above lower limit, and liquid repellency (especially water repellency) can be well imparted to the substrate. The water contact angle is a static contact angle of the spin-coated film of the liquid-repellent compound as shown in the examples, and refers to the value obtained by dropping 2 μL of water on the spin-coated film and measuring the contact angle after dripping for 1 second.

[0120] The liquid repellent compound is preferably a compound having carbon of bio-based origin. The bio-based content is measured based on ASTM D6866. The bio-based content is preferably 30% or more, more preferably 50% or more, further preferably 60% or more, further more preferably 70% or more, most preferably 80% or more or 90% or more, for example 100%. A high bio-based content means that the amount of fossil resource materials represented by petroleum is small. From this point of view, the higher the bio-based content of the liquid repellent compound, the better.

[0121] The melting point of the lyophobic compound may be 30° C. or higher, 40° C. or higher, 60° C. or higher, 80° C. or higher, 100° C. or higher, or 120° C. or higher, preferably 40° C. or higher, and may be 200° C. or lower, 150° C. or lower, 130° C. or lower, 120° C. or lower, 110° C. or lower, 100° C. or lower, 80° C. or lower, or 50° C. or lower. The lyophobic compound may not have a melting point.

[0122] Regarding the biodegradability of the liquid-repellent compound at 180 days, it is preferred to have a biodegradability of 5% or more. From the perspective of low environmental burden, the higher the biodegradability, the better. The biodegradability of the liquid-repellent compound at 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, further preferably 80% or more, and most preferably 90% or more. Regarding the biodegradability of the liquid-repellent compound at 60 days, it is preferred to have a biodegradability of 5% or more. From the perspective of low environmental burden, the higher the biodegradability, the better. The biodegradability of the liquid-repellent compound at 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. The biodegradability may be the biodegradability specified in JIS K 6953-1 or ASTM D6400.

[0123] The molecular weight of the lyophobic 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.

[0124] The liquid repellent compound of the present invention 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.

[0125] The liquid repellent compound of the present invention may not have an active hydrogen-containing group. Examples of active hydrogen-containing groups include amino groups (amino groups not adjacent to a carbonyl group, such as primary amino groups or secondary amino groups), hydroxyl groups, and carboxyl groups. In particular, the liquid repellent compound of the present invention may not have a primary amino group or a secondary amino group not adjacent to a carbonyl group.

[0126] The liquid repellent compound has an amine skeleton and one or more of the following formulas:

[0127] -X-R n

[0128] [Wherein,

[0129] X is a direct bond or a 1+n valent group,

[0130] R, when present, is independently a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent,

[0131] n is an integer of 1 to 3.]

[0132] The long-chain hydrocarbon-containing groups shown are at least one of which is bonded to a nitrogen atom of the amine skeleton.

[0133] [Amine skeleton]

[0134] The liquid-repellent compound of the present invention has an amine skeleton. The amine skeleton has one or more amino groups with a specified number of bonds (valence) obtained by removing a specified number of atoms or atomic groups (such as hydrogen) from an amine compound. The amino group in the amine skeleton means a group selected from -NH2, -NH- and -N(-)2, and also includes an amino group adjacent to a carbonyl group contained in an amide group, a carbamate group, a urea group, an imide, etc. Among them, the amine skeleton can be an aliphatic group or an aromatic group having one or more amino groups, and the presence of heteroatoms other than nitrogen is not excluded.

[0135] 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.

[0136] The number of carbon atoms in the amine skeleton can 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 can 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, particularly 30 or less.

[0137] The amine skeleton has one or more amino groups. The amino group is a univalent to trivalent amino group, and is a group having one or more selected from -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, 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 or less.

[0138] The amine skeleton has a hydrocarbon group (aliphatic hydrocarbon group or aromatic hydrocarbon group). The hydrocarbon group may be cyclic, branched or linear. The hydrocarbon group may be saturated or unsaturated (e.g., saturated). Among them, the hydrocarbon group may be interrupted by oxygen atoms and / or sulfur atoms, or may be composed only of carbon atoms, nitrogen atoms and hydrogen atoms. The hydrocarbon group may be a hydrocarbon group that may be interrupted by oxygen atoms and / or sulfur atoms (e.g., a chain saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 aromatic hydrocarbon rings), or may be a common hydrocarbon group (e.g., a chain saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 aromatic hydrocarbon rings). When the hydrocarbon group is interrupted by oxygen atoms and / or sulfur atoms, it has an ether, thioether, polyether or polythioether structure. The number of hydrocarbon groups possessed by 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 or less.

[0139] The amine skeleton may be composed of a monovalent to trivalent amino group and a chain saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group which may be interrupted by oxygen atoms and / or sulfur atoms.

[0140] The molar ratio of carbon atoms to nitrogen atoms in the amine skeleton (C / N ratio) can be greater than 1, greater than 2, greater than 2.5, greater than 3, greater than 3.5 or greater than 4; and can be less than 8, less than 7, less than 6, less than 5, less than 4, less than 3.5, less than 3, less than 2.5 or less, preferably less than 6 or less than 4.

[0141] (Raw material amine compound)

[0142] Examples of the raw material amine compound as a precursor of the amine skeleton include alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine; alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, cyclohexylenediamine, 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, bis[2-(3-aminoethoxy)ethyl]ether,

[0063] polyalkylene polyamines such as [(1-aminopropoxy)ethyl] ether, spermine, spermidine, etc.; oxygen- or sulfur-containing aliphatic amines such as 1-aminopropylene glycol, 2-amino-1,3-propylene glycol, 3-amino-1,2-propylene glycol, polyoxypropylene diamine, polyoxyethylene diamine, etc.; aromatic monoamines such as aniline, 1-naphthylamine or 2-naphthylamine, 1-aminoanthracene, 2-aminoanthracene or 9-aminoanthracene, 9-aminophenanthrene, 2-aminobiphenyl, 3-aminobiphenyl or 4-aminobiphenyl, etc.; monocyclic aromatic polyamines such as o-phenylenediamine, m-phenylenediamine or p-phenylenediamine, o-phenylenediamine, m-phenylenediamine or p-phenylenediamine, diaminotoluene, 2,3-toluenediamine, 2,4-toluenediamine or 2,5-toluenediamine; diaminobiphenyl, bisaminophenoxyphenylpropane, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl sulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenylphenylethane, bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, aminophenoxybiphenyl, aminophenoxyphenyl ketone, bisaminobistrifluoromethylbenzylbenzene, aminophenoxyphenyl sulfone, aminophenoxyphenyl ether, aminophenoxyphenylpropane, bis(aminophenoxybenzoyl)benzene, bis(aminophenoxy-α,a-dimethylbenzyl)benzene, bis[(aminoaryloxy)benzoyl]diphenyl ether, bis( Polycyclic aromatic polyamines such as amino-α,α-dimethylbenzylphenoxy)benzophenone, aminophenoxyphenyl sulfide, bis[amino-α,α-dimethylbenzylphenoxy]diphenyl sulfone, 4,4'-bis[aminophenoxyphenoxy]diphenyl sulfone, diaminodiaryloxybenzophenone, diaminoaryloxybenzophenone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminotriphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenedianiline, 4,4'-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 4,4'-diaminodiphenyl ether, and 4,4'-bis(aminophenyl)amine;2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide and other oxygen- or sulfur-containing polycyclic aromatic polyamines; 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine and other hydroxyl-containing polyamines. ;

[0143] [Groups containing long-chain hydrocarbons]

[0144] The liquid repellent compounds of the present invention have one or more of the following formulas:

[0145] -X-R n

[0146] [Wherein,

[0147] X is a direct bond or a 1+n valent group,

[0148] R, when present, is independently a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent,

[0149] n is an integer of 1 to 3.]

[0150] The long chain hydrocarbon containing groups shown.

[0151] The number of long-chain hydrocarbon-containing groups possessed by the lyophobic compound may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, 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 or less.

[0152] At least one long-chain hydrocarbon-containing group in the lyophobic compound is bonded to a nitrogen atom of the amine skeleton. The ratio of the number of long-chain hydrocarbon-containing groups bonded to the nitrogen atom of the amine skeleton to the number of all long-chain hydrocarbon-containing groups in the lyophobic 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 group not bonded to the nitrogen atom of the amine skeleton is bonded to other groups (e.g., hydrocarbon groups) of the amine skeleton.

[0153] (X)

[0154] X is a direct bond or a 1+n-valent group, preferably a 1+n-valent group. X functions as a linking group that links the amine skeleton to n Rs.

[0155] n is the number of R bound 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.

[0156] X may be an aliphatic group (an unsaturated aliphatic group or a saturated aliphatic group) or an aromatic group.

[0157] 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.

[0158] X may have a carbonyl group. X may have one or more selected from an amide group, a urea group, a carbamate group, and an imide, or X may form one or more selected from an amide group, a urea group, a carbamate group, and an imide together with the amino group in the amine skeleton. Examples of such amide groups, urea groups, carbamate groups, and imides include:

[0159] -O-C(=O)-NR'-,

[0160] -NR'-C(=O)-,

[0161] -NR'-C(=O)-O-,

[0162] -NR'-C(=O)-NR'-

[0163] -C(=O)-NR'-

[0164] -C(=O)-NR'-C(=O)-

[0165] -NR'-S(=O)2-.

[0166] [In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.]

[0167] X is preferably bonded to the nitrogen atom of the amine skeleton via a -(C=O)- group.

[0168] X may be a direct bond, a 1+n-valent group consisting of one or more selected from -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2, a 2-4-valent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a 2-4-valent aromatic hydrocarbon ring, and a 2-4-valent heterocycle [wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms].

[0169] X may be selected from X 1 and X2 A 1+n-valent group composed of one or more of the following.

[0170] X 1 It is composed of a direct bond, one or more selected from -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 at each occurrence),

[0171] X 2 It is composed of one or more selected from a di- to tetra-valent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a di- to tetra-valent aromatic hydrocarbon ring, and a di- to tetra-valent heterocyclic ring.

[0172] In this specification, the left side of a group represented by X is bonded to the amine skeleton, and the right side is bonded to R.

[0173] ·X 1

[0174] X 1 It is a non-hydrocarbon linking group.

[0175] X 1 It is a direct bond or a divalent or higher group. 1 The valence of X may be 2 to 4, 2 to 3 or 2. 1 Not just direct bonding.

[0176] 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.

[0177] X 1 It is composed of one or more selected from the group consisting of 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 at each occurrence). 1 Examples include:

[0178] Direct bonding,

[0179] -O-,

[0180] -O-C(=O)-,

[0181] -O-C(=O)-O-,

[0182] -O-C(=O)-NR'-,

[0183] -NR'-

[0184] -NR'-C(=O)-,

[0185] -NR'-C(=O)-O-,

[0186] -NR'-C(=O)-NR'-,

[0187] -C(=O)-,

[0188] -C(=O)-O-,

[0189] -C(=O)-NR'-,

[0190] -C(=O)-NR'-C(=O)-,

[0191] -C(=NR')-,

[0192] -S-,

[0193] -SO2-,

[0194] -SO2NR'-,

[0195] -C(OR')R'-,

[0196] -C(OR')(-)2,

[0197] -N(-)2, etc.

[0198] [In the formula, R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence.]

[0199] Among them, in X 1 When bonding to a nitrogen atom in the amine skeleton, the nitrogen atom is regarded as a part of the amine skeleton (amino group).

[0200] ·X 2

[0201] X 2 A hydrocarbon or aromatic linker.

[0202] X 2 It can be a hydrocarbon group or a non-hydrocarbon group (containing heteroatoms). 2 It can be aliphatic or aromatic, preferably aliphatic. 2 It can be straight chain, branched chain or cyclic. 2 Preferably, it is in the form of a chain.

[0203] X 2 X is a divalent or higher group. 2The valence of is 2 to 4, 2 to 3 or 2, for example.

[0204] X 2 The number of carbon atoms can 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 can 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.

[0205] X 2 It is composed of one or more selected from a di- to tetra-valent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a di- to tetra-valent aromatic hydrocarbon ring, and a di- to tetra-valent heterocyclic ring.

[0206] The divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be a cyclic, branched or linear hydrocarbon group, and is preferably a chain hydrocarbon group (particularly a linear 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 aliphatic hydrocarbon group having 1 to 20 carbon atoms may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more carbon atoms, and may be 15 or less, 10 or less, or 5 or less.

[0207] Examples of divalent to tetravalent aromatic hydrocarbon rings include groups obtained by removing 2 to 4 hydrogen atoms from aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthoacene), pentacene, pyrene and hexabenzone. The number of ring atoms of the aromatic hydrocarbon ring is 3 to 20, 4 to 16 or 5 to 12, preferably 5 to 12. The aromatic hydrocarbon 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 aromatic hydrocarbon ring may be 2 or more, 3 or more or 4, and may be 4 or less, 3 or less or 2.

[0208] The divalent to tetravalent heterocyclic ring may be an aliphatic group or an aromatic group. Examples of the divalent to tetravalent heterocyclic ring 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, benzotriazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazoline, thiazoline, etc. The number of ring atoms of the heterocyclic ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The heterocyclic 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 heterocyclic ring may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0209] As X 2 Examples include:

[0210] -Ali-

[0211] -Cy-

[0212] -Ali(-)2

[0213] -Cy(-)2

[0214] -Ali-Cy-

[0215] -Cy-Ali-

[0216] -Cy-Ali-Cy-

[0217] -Ali-Cy-Ali-etc.

[0218] [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is an aromatic hydrocarbon ring or a heterocyclic ring.]

[0219] As X 2 Specific examples include:

[0220] -(CH2) p - (p is 1 to 20, for example, 1 to 10),

[0221] a linear hydrocarbon group having 1 to 40 carbon atoms, for example 1 to 10 carbon atoms, and having an unsaturated bond;

[0222] A hydrocarbon group having 1 to 40 carbon atoms, for example, 1 to 10 carbon atoms, having a branched structure,

[0223] -(CH2) q -Cy-(CH2) r-(q and r are each independently 0 to 20, for example, 1 to 10, and Cy is an aromatic hydrocarbon ring or a heterocyclic ring) and the like.

[0224] Example of X

[0225] Examples of X are described below. Here, R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence.

[0226] Examples of X include: -X 1 -, -X 1 -X 2 -, -X 1 -X 2 -X 1 -, -X 1 -X 2 -X 1 -X 2 -, -X 2 -, -X 2 -X 1 -, -X 2 -X 1 -X 2 -, -X 2 -X 1 -X 2 -X 1 -wait.

[0227] Examples of X include: -X 1 (-)2, -X 1 -X 2 (-)2, -X 1 -(X 2 -)2. -X 1 -X 2 -X 1 (-)2, -X 1 -X 2 (-X 1 -)2. -X 1 -(X 2 -X 1 -)2. -X 1 -X 2 -X 1 -X 2 (-)2, -X 1 -X 2 -X 1 -(X 2 -) 2、 -X 1 -X 2 -(X 1 -X 2 -)2、 -X 1 -(X 2 -X 1 -X 2 -)2;

[0228] -X 2 (-)2, -X 2 -X 1 (-)2, -X 2 -(X 1 -)2. -X 2 -X 1 -X 2 (-)2, -X 2 -X 1 (-X 2 -)2. -X 2 -(X 1 -X 2 -)2. -X 2 -X 1 -X 2 -X 1 (-)2, -X 2 -X 1 -X 2 -(X 1 -)2. -X 2 -X 1 -(X 2 -X 1 -)2. -X 2 -(X 1 -X 2 -X 1 -)2, etc.

[0229] Examples of X include: -X 1 (-)3, -X 1 -X 2 (-)3, -X 1 -(X 2 -)3. -X 1 -X 2 -X 1 (-)3, -X 1 -X 2 (-X 1 -)3. -X 1 -(X 2 -X 1 -)3. -X 1 -X 2 -X 1 -X 2 (-)3, -X 1 -X 2 -X 1-(X 2 -)3. -X 1 -X 2 -(X 1 -X 2 -)3. -X 1 -(X 2 -X 1 -X 2 -)3;

[0230] -X 2 (-)3, -X 2 -X 1 (-)3, -X 2 -(X 1 -)3. -X 2 -X 1 -X 2 (-)3, -X 2 -X 1 (-X 2 -)3. -X 2 -(X 1 -X 2 -)3. -X 2 -X 1 -X 2 -X 1 (-)3, -X 2 -X 1 -X 2 -(X 1 -)3. -X 2 -X 1 -(X 2 -X 1 -)3. -X 2 -(X 1 -X 2 -X 1 -)3, etc.

[0231] 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, etc. In the lyophobic compound, it is preferred that at least one X is -(C=O)- at the amine skeleton side terminal and is bonded to a nitrogen atom of the amine skeleton.

[0232] 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 -, -X 2 -X 1 (-)2 represented by the group.

[0233] [Wherein,

[0234] X 1 Independently at each occurrence is:

[0235] Direct bonding,

[0236] -O-,

[0237] -O-C(C=O)-,

[0238] -O-C(C=O)-O-,

[0239] -O-C(C=O)-NR'-,

[0240] -NR'-

[0241] -NR'-C(C=O)-,

[0242] -NR'-C(C=O)-O-,

[0243] -NR'-C(C=O)-NR'-,

[0244] -C(C=O)-,

[0245] -C(C=O)-O-, or

[0246] -C(C=O)-NR'-

[0247] -C(C=O)-NR'-C(C=O)-,

[0248] (In the formula, R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence.)

[0249] X 2 It is a divalent to tetravalent aliphatic hydrocarbon group or a divalent aromatic group (e.g., a divalent phenyl group or a divalent triazole group) having 1 to 10 carbon atoms.]

[0250] Thereby, liquid repellency can be imparted to the base material satisfactorily.

[0251] As further specific examples of X, there can be listed:

[0252] *-(C=O)-

[0253] -O-(C=O)-NR'-, etc.

[0254] [wherein, * means bonding to the nitrogen atom of the amine skeleton,

[0255] R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.]

[0256] (R)

[0257] R is a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms and 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) or a 1-5 valent (e.g., 1-valent) unsaturated aliphatic hydrocarbon group.

[0258] The number of carbon atoms of R can be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more or 18 or more, preferably 10 or more, more preferably 12 or more; and can be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less or 10 or less, preferably 30 or less, more preferably 25 or less.

[0259] The valence number of the unsaturated aliphatic hydrocarbon group may be 5 or less, 4 or less, 3 or less, 2 or less, or 1.

[0260] The hydrocarbon group may also have a substituent, but preferably no substitution. Examples of substituents 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 have active hydrogen or may not have it. The number of 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' (especially -OH) as a substituent (for example, other than the terminal).

[0261] [Examples of liquid repellent compounds]

[0262] (Example 1 of liquid repellent compound)

[0263] Examples of lyophobic compounds include the following:

[0264] N(-XR n ) p (-H) q -L 1 -[N(-XR n ) r (-H) s -L 1 -] t -N(-XR n ) p (-H) q The compound shown (lyophobic compound example 1).

[0265] [Wherein,

[0266] X is independently a direct bond or a 1+n-valent group at each occurrence,

[0267] R, when present, is independently a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent,

[0268] L 1 is independently, at 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,

[0269] n is independently an integer from 1 to 3 at each occurrence,

[0270] p is independently an integer from 0 to 2 at each occurrence,

[0271] q is independently an integer from 0 to 2 at each occurrence,

[0272] p+q in each N(-XR n ) p (-H) q The middle is 2,

[0273] r is independently 0 or 1 at each occurrence,

[0274] s is independently 0 or 1 at each occurrence,

[0275] r+s in each N(-XR n ) r (-H) s The middle is 1,

[0276] The sum of all p's and all r's is greater than 1,

[0277] t is an integer of 0 to 10.]

[0278] In the liquid repellent compound example 1, the detailed information of X, R and n is the same as that described above.

[0279] In Example 1 of the liquid repellent compound, L 1 It is a divalent aliphatic hydrocarbon group 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 linear hydrocarbon group, and is preferably a chain hydrocarbon group or an aromatic hydrocarbon group. 1 The hydrocarbon group in the above description of the [amine skeleton] may be used, and the hydrocarbon group may be interrupted by oxygen atoms and / or sulfur atoms, or may be composed only of carbon atoms, nitrogen atoms, and hydrogen atoms. 1 For example, it may be a saturated or unsaturated (for example, saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 aromatic hydrocarbon rings. 1 It is preferably a cyclic group having both a ring (e.g., an aromatic ring) and a chain structure (e.g., a linear structure, ether oxygen, thioether sulfur), and specific examples thereof include 1,3-phenylenebisalkylene, 1,4-phenylenebisalkylene, diphenyl ether diyl, and diphenyl thioether diyl. 1 The number of carbon atoms can be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and can 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.

[0280] In Example 1 of the liquid repellent compound, p is independently an integer of 0 to 2 at each occurrence, q is independently an integer of 0 to 2 at each occurrence, and p+q is an integer of 0 to 2 at each occurrence. n ) p (-H) q Preferably, p is independently 1 or more, for example, 2, at each occurrence.

[0281] In Example 1 of the liquid repellent compound, r is independently 0 or 1 at each occurrence, s is independently 0 or 1 at each occurrence, and r+s is independently 0 or 1 at each N(-XR n ) r (-H) s Preferably, p is independently 1 or more, for example, 2, at each occurrence.

[0282] The total of all p's and all r's is 1 or more, that is, the liquid repellent compound example 1 has one or more -X-R n The sum of all p and all r can be greater than 1, greater than 3, greater than 5, greater than 7, greater than 9, greater than 12 (the sum of all q and all s can be 0), and can be less than 14, less than 12, less than 10, less than 8, less than 6, or less than 4.

[0283] In liquid repellent compound example 1, t is an integer of 0 to 10. t may be 0 to 1, 2 to 4, or 6 to 6, preferably 0 to 2; and t may be 8 to 6, 4 to 3, for example 0, 1 or 2, for example 0 or 1.

[0284] (Example 2 of liquid repellent compound)

[0285] As another example of the liquid repellent compound, the following formula can be mentioned:

[0286] N(-XR n ) p (-H) q -L 2 (-XR n ) u The compound shown (Example 2 of liquid-repellent compound).

[0287] [Wherein,

[0288] X is independently a direct bond or a 1+n-valent group at each occurrence,

[0289] R, when present, is independently a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent,

[0290] L 2is a 1+u-valent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by oxygen atoms and / or sulfur atoms,

[0291] n is independently an integer from 1 to 3 at each occurrence,

[0292] p is an integer from 0 to 2,

[0293] q is an integer from 0 to 2,

[0294] p+q is 2,

[0295] u is an integer from 1 to 3,

[0296] The total of p and u is greater than or equal to 1.]

[0297] In the liquid repellent compound example 2, the detailed information of n of X and R is the same as the above description.

[0298] In Example 2 of the liquid repellent compound, L 2 It is a 1+u-valent aliphatic hydrocarbon group 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 linear hydrocarbon group, preferably a chain hydrocarbon group or an aromatic hydrocarbon group. 2 The hydrocarbon group in the above description of [amine skeleton] may be used, and the hydrocarbon group may be interrupted by oxygen atoms and / or sulfur atoms, or may be composed only of carbon atoms, nitrogen atoms and hydrogen atoms. 2 For example, it may be a saturated or unsaturated (for example, saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 aromatic hydrocarbon rings. 2 It is preferably a cyclic group having both a ring (e.g., an aromatic ring) and a chain structure (e.g., a linear structure, ether oxygen, thioether sulfur), and specific examples thereof include 1,3-phenylenebisalkylene, 1,4-phenylenebisalkylene, diphenyl ether diyl, and diphenyl thioether diyl. 2 The number of carbon atoms can be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and can 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.

[0299] In the liquid repellent compound example 2, p is an integer of 0 to 2, q is an integer of 0 to 2, and p+q is 2. Preferably, p is 1 or more, and is 2, for example.

[0300] In the liquid repellent compound example 2, u is an integer of 1 to 3. u may be 1, 2 or 3, for example, 2 or 3.

[0301] In Example 2 of the liquid repellent compound, the total of p and u is 1 or more, that is, Example 2 of the liquid repellent compound has one or more -X-Rn The total of all p and u is greater than 1, greater than 2, greater than 3, greater than 4, or greater than 5 (the total of all q may be 0), and the total of p and u may be less than 5, less than 4, less than 3, or less than 2.

[0302] (specific example)

[0303] Specific examples of the liquid repellent compound include compounds represented by the following formula: In the following formula, the detailed information of X, R and n is the same as that described above.

[0304]

[0305]

[0306] The liquid-repellent compound can be a synthetic wax derived from animal-vegetable oils and fats. Synthetic wax can be obtained by condensing fatty acids derived from animal-vegetable oils and fats with aliphatic amines or aromatic amines. As examples of synthetic waxes, 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, tetracosanoic 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, eicosapentaenoic acid amide compounds, and docosahexaenoic acid amide compounds can be cited.

[0307] [Method for producing lyophobic compound]

[0308] There are no limitations on the method for producing the liquid repellent compound, and examples thereof include: a method of synthesizing by reacting a carboxylic acid having an R group with various amines in the presence of a condensing agent as required; a method of synthesizing by reacting an acid chloride, anhydride, isocyanate, etc. of a carboxylic acid having an R group with various amines, 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.

[0309] [Amount of liquid repellent compound]

[0310] In the repellent, the amount of the repellent compound can 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 can 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.

[0311] 〔Liquid medium〕

[0312] The dispersing agent of the present invention may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The dispersing agent may be a dispersion or a solution.

[0313] Examples of organic solvents include esters (e.g., esters having 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically methyl ethyl ketone and 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 and 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., polyols such as alcohols and glycol solvents, ethers of polyols (e.g., monoethers), etc.). They may be used alone or in combination of two or more.

[0314] [Amount of liquid medium]

[0315] The amount of the liquid medium relative to 1 part by weight of the lyophobic compound 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, or 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be less than 3000 parts by weight, less than 2000 parts by weight, less than 1000 parts by weight, less than 500 parts by weight, less than 200 parts by weight, less than 175 parts by weight, less than 150 parts by weight, less than 125 parts by weight, less than 100 parts by weight, less than 80 parts by weight, less than 60 parts by weight, less than 40 parts by weight, less than 20 parts by weight, or less than 10 parts by weight.

[0316] The amount of water relative to 1 part by weight of the lyophobic compound 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.

[0317] The amount of the organic solvent relative to 1 part by weight of the lyophobic compound 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.

[0318] 〔Surfactant〕

[0319] The expelling agent may contain a surfactant. The surfactant may contain one or more surfactants selected from nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants. The surfactant may be a non-fluorinated surfactant.

[0320] [Nonionic surfactant]

[0321] Examples of the nonionic surfactant include ethers, esters, ester ethers, alkanolamides, polyols and amine oxides.

[0322] Examples of ethers include compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0323] Examples of esters include esters of alcohols and fatty acids. Examples of alcohols include monovalent to hexavalent (particularly divalent to pentavalent) alcohols (e.g., aliphatic alcohols) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). Examples of fatty acids include saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0324] Examples of ester ethers include compounds obtained by adding an alkylene oxide (particularly ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols include monovalent to hexavalent (particularly divalent to pentavalent) alcohols (e.g., aliphatic alcohols) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). Examples of fatty acids include saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0325] Examples of alkanolamides are formed from fatty acids and alkanolamines. Alkanolamides may be monoalkanolamides or dialkanolamides. Examples of fatty acids include saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. Alkanolamines may be alkanols having 1 to 3 amino groups and 1 to 5 hydroxyl groups and having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0326] The polyol may be a di- to penta-valent alcohol having 10 to 30 carbon atoms.

[0327] The amine oxide may be an oxide of an amine (secondary amine or preferably tertiary amine) (for example, having 5 to 50 carbon atoms).

[0328] The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The carbon number of the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic surfactant is usually preferably 2 to 100.

[0329] The nonionic surfactant is selected from ethers, esters, ester ethers, alkanolamides, polyols and amine oxides, and is preferably a nonionic surfactant having an oxyalkylene group.

[0330] 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 glycerol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyglycerol 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 an acetylene glycol, and the like. Among these, the structure of the alkylene oxide addition part and the polyalkylene glycol part is preferably polyoxyethylene (POE), polyoxypropylene (POP), or a POE / POP copolymer (which may be a random copolymer or a block copolymer).

[0331] Furthermore, the nonionic surfactant preferably has a structure without an aromatic group in view of environmental issues (biodegradability, environmental hormones, etc.).

[0332] The nonionic surfactant may be of the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 The compounds shown.

[0333] [Where R 1 is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or an acyl group having 2 to 22 carbon atoms,

[0334] Each R 2 are independent, may be the same or different, and are alkylene groups having 3 or more carbon atoms (e.g., 3 to 10),

[0335] R 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, and p is a number greater than or equal to 2.

[0336] q is a number greater than or equal to 0 or 1.]

[0337] R 1 The number of carbon atoms is preferably 8 to 20, particularly preferably 10 to 18. 1 Preferred specific examples include octyl, nonyl, trimethylnonyl, lauryl, tridecyl, oleyl and stearyl.

[0338] R 2 Examples of are propylene, butylene.

[0339] In the nonionic surfactant, p may be a number greater than or equal to 3 (e.g., 5 to 200). q may be a number greater than or equal to 2 (e.g., 5 to 200). That is, -(R 2 O) q -Polyoxyalkylene chains can be formed.

[0340] The nonionic surfactant may be a polyoxyethylene alkylene alkyl ether having a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) at the center. Examples of the hydrophobic oxyalkylene chain include oxypropylene chains, oxybutylene chains, and styrene chains, among which oxypropylene chains are preferred.

[0341] Specific examples of nonionic surfactants include ethylene oxide and hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkane (C 12 -C 16 ) mercaptan, sorbitan monofatty acid (C7-C 19 ) or alkyl (C 12 -C 18 ) amine or the like, or sorbitan fatty acid esters, glycerol fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, propylene glycol fatty acid esters, lecithin derivatives.

[0342] The proportion of the polyoxyethylene block may be 5 to 80% by weight, for example, 30 to 75% by weight, and particularly 40 to 70% by weight, based on the molecular weight of the nonionic surfactant (copolymer).

[0343] The average molecular weight of the nonionic surfactant is usually 300 to 5,000, for example, 500 to 3,000.

[0344] The nonionic surfactant may be a single species or a mixture of two or more species. 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.

[0345] [Cationic surfactant]

[0346] The cationic surfactant is preferably a compound having no amide group.

[0347] The cationic surfactant may be an amine salt, a quaternary ammonium salt, or an ethylene oxide addition type ammonium salt. Specific examples of the cationic surfactant are not particularly limited, and include: amine salt-type surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines; quaternary ammonium salt-type surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, and benzalkonium chloride.

[0348] A preferred example of the cationic surfactant is R 21 -N + (-R 22 )(-R 23 )(-R 24 )X － of compounds.

[0349] [Where R 21 , R 22 , R 23 and R 24 is a hydrocarbon group having 1 to 40 carbon atoms,

[0350] X is an anionic group.]

[0351] R 21 , R 22 , R 23 and -R 24 Specific examples of are alkyl groups (eg, methyl, butyl, stearyl, palmityl). Specific examples of X are halogens (eg, chlorine) and acids (eg, hydrochloric acid, acetic acid).

[0352] The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (the alkyl group has 4 to 40 carbon atoms).

[0353] The cationic surfactant is preferably an ammonium salt. The cationic surfactant may be of the formula: R 1 p -N + R 2 q X － The ammonium salts shown.

[0354] [Where R 1 C12 or above (e.g. C 12 ~C 50 ) a straight-chain and / or branched aliphatic (saturated and / or unsaturated) group,

[0355] R 2 is H or a C1-4 alkyl group, benzyl, or polyoxyethylene (the number of ethylene groups is, for example, 1 (particularly 2, and especially 3) to 50) (particularly preferably CH3 or C2H5),

[0356] X is a halogen atom (e.g., ), a C1-C4 fatty acid salt group,

[0357] p is 1 or 2, q is 2 or 3, p+q=4.]

[0358] R 1 The number of carbon atoms in can be 12-50, for example 12-30.

[0359] Specific examples of cationic surfactants include: dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydroxypolyoxyethylene)ammonium chloride, benzyldodecyldi(hydroxypolyoxyethylene)ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0360] [Anionic surfactant]

[0361] Examples of anionic surfactants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-fatty sulfonates, N-acylamino acid type surfactants, phosphoric acid monoester or diester type surfactants and sulfosuccinates.

[0362] [Amphoteric surfactants]

[0363] Examples of the amphoteric surfactant include alanines, imidazolinium betaines, amidobetaines, betaine acetate, and the like. Specifically, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetic acid betaine, and fatty acid amide propyl dimethylaminoacetic acid betaine can be mentioned.

[0364] The surfactant may be one kind each of a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant, or a combination of two or more kinds thereof.

[0365] [Amount of surfactant]

[0366] The amount of the surfactant can be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and can 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.

[0367] 〔Organic Silicone〕

[0368] The repellent in the present invention may contain silicone (polyorganosiloxane). By containing silicone, in addition to good liquid repellency, good feel and durability can be achieved.

[0369] As the organosilicon, known organosilicon can be used, and examples of organosilicon include polydimethylsiloxane, modified organosilicon (amino-modified, epoxy-modified organosilicon, carboxyl-modified organosilicon, methyl hydrogen organosilicon, etc.). The organosilicon can be a silicone wax having waxy properties. These can be used alone or in combination of two or more.

[0370] 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.

[0371] [Amount of silicone]

[0372] The amount of the silicone can 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 can be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, based on 100 parts by weight of the liquid repellent compound.

[0373] 〔wax〕

[0374] The repellent of the present invention may contain wax. By containing wax, liquid repellency can be imparted to the substrate well.

[0375] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, silicone wax, animal and plant wax, and mineral wax. Paraffin wax is preferred. Specific examples of compounds constituting waxes include normal alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontan, undecane, dotriacontan, tritriacontan, tetratriacontan, pentacontan, and hexatriacontan), normal olefins (e.g., 1-eicosene ... The number of carbon atoms of the compound constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be 200 to 2000, for example, 250 to 1500, 300 to 1000. These may be used alone or in combination of two or more.

[0376] The melting point of the wax may be 50° C. or higher, 55° C. or higher, 60° C. or higher, 65° C. or higher, or 70° C. or higher, preferably 55° C. or higher, and more preferably 60° C. or higher. The melting point of the wax is measured in accordance with JIS K2235-1991.

[0377] [Amount of wax]

[0378] The amount of the wax may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, 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, based on 100 parts by weight of the liquid repellent compound.

[0379] 〔Organic acid〕

[0380] The dispersing agent may contain an organic acid. As the organic acid, a known organic acid may be used. As the organic acid, carboxylic acid, sulfonic acid, sulfinic acid, etc. are preferably listed, and carboxylic acid is particularly preferred. As the carboxylic acid, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid may be listed, and formic acid or acetic acid is particularly preferred. In the present invention, the organic acid may be used alone or in combination of two or more. For example, formic acid and acetic acid may be used in combination.

[0381] [Amount of organic acid]

[0382] 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, and particularly 6 to 8. The repellent may be acidic (pH 7 or less, for example, 6 or less).

[0383] 〔Curing agent〕

[0384] The exfoliant may contain a curing agent (an active hydrogen-reactive compound or a compound containing active hydrogen).

[0385] The curing agent (crosslinking agent) in the repellent can cure the liquid-repellent compound well. The curing agent can be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen-reactive group possessed by the liquid-repellent compound. Examples of active hydrogen-reactive compounds include isocyanate compounds, epoxy compounds, chloromethyl-containing compounds, carboxyl-containing compounds, and hydrazide compounds. Examples of active hydrogen-containing compounds include hydroxyl-containing compounds, amino-containing compounds, carboxyl-containing compounds, keto-containing compounds, hydrazide compounds, and melamine compounds.

[0386] The curing agent may contain an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. A polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound acts as a crosslinking agent. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (e.g., a blocked polyisocyanate compound). The blocked isocyanate compound is a compound in which the isocyanate group of the isocyanate compound is masked by a blocking agent to inhibit the reaction.

[0387] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanato aliphatic triisocyanates such as methyl hexanoate and lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatodecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, etc. These can be used alone or in combination of two or more.

[0388] 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 can be used alone or in combination of two or more.

[0389] Examples of aromatic aliphatic polyisocyanates include aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of aromatic aliphatic polyisocyanates include 1,3- or 1,4-phenylenediisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylphenylenediisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used alone or in combination of two or more.

[0390] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include 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-toluene diisocyanate or a mixture thereof, triphenylmethane-4,4',4"-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These can be used alone or in combination of two or more.

[0391] Examples of the polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biuret, allophanate, carbodiimide, uretdione, ureaimines, isocyanurates, and iminooxadiazinediones. These can be used alone or in combination of two or more.

[0392] These polyisocyanates may be used alone or in combination of two or more.

[0393] As the polyisocyanate compound, a compound in which the isocyanate group of the polyisocyanate compound is blocked using a blocking agent, i.e., a blocked polyisocyanate compound (blocked isocyanate) is preferably used because it is relatively stable in solution and can be used in the same solution as the dispersant.

[0394] The blocking agent is a substance that blocks the chain of 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 blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, oxime compounds, etc. The polyisocyanate compound can be used alone or in combination of two or more.

[0395] 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.

[0396] The chloromethyl group-containing compound is a compound having a chloromethyl group. Examples of the chloromethyl group-containing compound include chloromethyl polystyrene and the like.

[0397] The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound include (poly)propylene, (poly)methacrylic acid, and the like.

[0398] Specific examples of the ketone group-containing compound include (poly) diacetone acrylamide and diacetone alcohol.

[0399] Specific examples of the hydrazide compound include hydrazine, carbohydrazide, adipic acid hydrazide and the like.

[0400] Specific examples of the melamine compound include melamine resins and methyl etherified melamine resins.

[0401] [Amount of curing agent]

[0402] The amount of the curing agent can be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and can be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, based on 100 parts by weight of the liquid repellent compound.

[0403] 〔Other ingredients〕

[0404] The expelling agent may contain other ingredients in addition to the above ingredients. Examples of other ingredients include polysaccharides, paper strength strengthening agents, agglutinating agents, yield improving agents, coagulants, adhesive resins, anti-slip agents, sizing agents, paper strength strengthening agents, fillers, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, fragrances, etc. These may be used alone or in combination of two or more.

[0405] In addition to the above-mentioned components, other components may be added, such as water-repellent and / or oil-repellent, dispersant, feel modifier, softener, flame retardant, paint fixative, wrinkle-proof agent, drying speed modifier, crosslinking agent, film-forming aid, solubilizer, antifreeze agent, viscosity modifier, ultraviolet absorber, antioxidant, pH modifier, insect repellent, defoamer, shrinkage-proof agent, anti-wrinkle agent, shape retaining agent, drape-maintaining agent, ironing property enhancing agent, whitening agent, whitening agent, fabric softening clay, anti-staining agent such as polyvinyl pyrrolidone, polymer dispersant, dirt release agent, scum dispersant, 4,4-bis(2-sulfonylphenyl)biphenyl disodium (TINOPAL manufactured by Ciba Specialty Chemicals Co., Ltd.) CBS-X), dye fixing agents, anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine, bleaching agents, enzymes such as cellulase, amylase, protease, lipase, cutinase, etc. as fiber surface modifiers, foam inhibitors, silk protein powder as an additive that can impart the feel / function of silk such as moisture absorption and release, their surface modified products or emulsified dispersions (for example, K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk solution (Shangmao), SILKGEN G Soluble S (Ichimaru PHARCOS Co., Ltd.)), anti-fouling agents (for example, nonionic polymer compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (for example, FR627 manufactured by Huying Chemical Industry Co., Ltd., SRC-1 manufactured by Clarion Japan, etc.), etc. These may be used alone or in combination of two or more.

[0406] [Polysaccharides]

[0407] Examples of polysaccharides include starch, xanthan gum, karaya gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean, cellulose, alginic acid, agar, dextran, and pullulan. The polysaccharide may also be a substituted modified polysaccharide, in particular, a modified polysaccharide into which a hydroxyl group or a cationic group is introduced.

[0408] [Paper strength enhancer, agglutinating agent, yield enhancer or coagulant]

[0409] Examples of paper strengthening agents, aggregating agents, yield enhancing agents 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 polyalkylene polyamines, dicyandiamide-aldehyde condensates, dimethyldiallylammonium chloride polymers and olefin / maleic anhydride polymers.

[0410] [Gluing agent]

[0411] Examples of sizing agents include cellulose-reactive sizing agents, rosin-based sizing agents such as rosin-based soaps, rosin-based emulsions / dispersions, cellulose-reactive sizing agents, 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, such as copolymers of styrene and acrylates.

[0412] [Antistatic Agent]

[0413] Examples of antistatic agents include: quaternary ammonium salts, pyridinium salts, cationic antistatic agents with cationic functional groups such as primary amino groups, secondary amino groups, and tertiary amino groups; anionic antistatic agents with anionic functional groups such as sulfonates or sulfates, phosphonates, and phosphates; amphoteric antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, alanine and their derivatives, amino alcohols and their derivatives, glycerol and their derivatives, polyethylene glycol and their derivatives, and other nonionic antistatic agents. It can also be an ion conductive polymer obtained by polymerizing or copolymerizing these cationic, anionic, and zwitterionic monomers with ion conductive groups. They can be used alone or in combination of two or more.

[0414] [preservative]

[0415] Preservatives are mainly used to enhance the antiseptic power and bactericidal power and ensure the antiseptic property during long-term storage. Examples of preservatives include isothiazolinone-based organic sulfur compounds, benzisothiazolinone-based organic sulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol.

[0416] [Ultraviolet light absorber]

[0417] Ultraviolet light absorbers are agents that have the effect of protecting against ultraviolet light, and are components that absorb ultraviolet light and convert it into infrared light or visible light for release. Examples of ultraviolet light absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, and 4-tert-butyl-4'-methoxybenzoylmethane.

[0418] [Antibacterial agent]

[0419] The antimicrobial agent is a component that has the effect of inhibiting the proliferation of bacteria on the fiber and inhibiting the generation of odor by the decomposition products of microorganisms. Examples of the antimicrobial agent include cationic fungicides such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide) zinc, polyhexamethylene biguanide hydrochloride, 8-oxoquinoline, polylysine, and the like.

[0420] [Deodorant]

[0421] Examples of deodorants include highly branched cyclodextrin (Cluster Dextrin), methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyl dimethylamine oxide, and aminocarboxylic acid-based metal complexes (zinc complex of trisodium methylglycine diacetate described in International Publication No. 2012 / 090580).

[0422] [Amount of other ingredients]

[0423] The amount of each of the other components or the total amount 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, based on 100 parts by weight of the liquid-repellent compound.

[0424] <Pulp composition>

[0425] The pulp composition of the present invention contains a liquid-repellent compound and a pulp base material. The pulp composition of the present invention is excellent in oil resistance and / or water resistance, preferably excellent in both.

[0426] The pulp composition of the present invention is obtained by adding a liquid-repellent compound to a pulp base material. The pulp composition can be obtained by treating a pulp base material with a liquid-repellent agent containing a liquid-repellent compound, wherein the amount of the liquid-repellent agent added and the composition of the liquid-repellent agent can be adjusted so that each component reaches a desired amount. Each component that can be contained in the liquid-repellent agent can also be added to the pulp composition as an additive.

[0427] The pulp composition of the present invention may not contain any one selected from the group consisting of a compound having a fluoroalkyl group with 8 or more carbon atoms, a compound having a perfluoroalkyl group with 8 or more carbon atoms, a compound having a fluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group with 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 pulp composition of the present invention can impart liquid repellency to a substrate even if it does not contain these fluorine compounds.

[0428] The pH of the pulp composition may be 3 to 10, for example 5 to 9, particularly 6 to 8, and the amounts of the components may be adjusted so as to achieve such a pH.

[0429] 〔Pulp base material〕

[0430] The pulp composition contains a pulp base material. The pulp base material is composed of pulp, and the pulp may be wood pulp, non-wood pulp, waste paper pulp, or the like.

[0431] As pulp, there are coniferous tree sulfate pulp obtained from the genera of fir, pine, etc., and broadleaf tree sulfate pulp obtained from the genera of acacia, eucalyptus, beech, poplar (for example, poplar), etc. As coniferous tree sulfate pulp, for example, coniferous tree unbleached sulfate pulp (NUKP), coniferous tree bleached pulp (NBKP), coniferous tree semi-bleached sulfate pulp (NSBKP), coniferous tree sulfite pulp, etc. can be mentioned. In addition, as broadleaf tree sulfate pulp, for example, broadleaf tree unbleached sulfate pulp (LUKP), broadleaf tree bleached sulfate pulp (LBKP), broadleaf tree semi-bleached sulfate pulp (LSBKP), broadleaf tree sulfite pulp, etc. can be mentioned. And, the pulp used can be used alone or in combination. In addition to kraft pulp, there are also coniferous kraft pulp and broadleaf kraft pulp, as well as mechanical pulps such as stone-ground pulp (SGP), pressurized stone-ground pulp (PGW), woodchip pulp (RGP), thermogrind pulp (TGP), chemical-ground pulp (CGP), groundwood pulp (GP), and thermomechanical pulp (TMP). In addition, as waste paper pulp, there are debonded waste paper pulp, debonded-deinked waste paper pulp, or debonded-deinked-bleached waste paper pulp made from waste tea paper, waste kraft envelope waste paper, waste magazine paper, waste newspaper, waste flyer paper, waste office paper, waste corrugated paper, waste white paper, waste drawing paper, waste handmade paper, waste title paper, and the like. Examples of non-wood pulp include pulp obtained from bagasse, kenaf, bamboo, cotton linter, kapok, linen, hemp, ramie, rice straw, thatch, abaca, sisal, jute, flax, goose skin, balsam, paper mulberry, bagasse, and the like.

[0432] 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 further preferably 0.5 mm or more. From the viewpoint of ease of production, it is preferably 5.0 mm or less, more preferably 4.0 mm or less, further preferably 3.0 mm or less, particularly preferably 2.0 mm or less, and most preferably 1.0 mm or less.

[0433] [Form of pulp substrate]

[0434] The form of the pulp base material when adding the liquid-repellent compound can be a single pulp, a pulp slurry, a pulp product, etc. Specific examples include: bleached or unbleached chemical pulp such as sulfate pulp or sulfite pulp, bleached or unbleached high-yield pulp such as wood pulp, mechanical pulp or thermomechanical pulp; pulp slurries containing the above pulps; pulp products such as paper, paper containers, and pulp molded products.

[0435] [Amount of pulp base material]

[0436] In the pulp composition, the amount of the pulp base material may be 0.1 wt% or more, 0.5 wt% or more, 1 wt% or more, 3 wt% or more, 5 wt% or more, 10 wt% or more, 20 wt% or more, 30 wt% or more, 50 wt% or more, 75 wt% or more, or 90 wt% or more, and may be 99 wt% or less, 75 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, 5 wt% or less, 4 wt% or less, or 3 wt% or less. For example, in the case of preparing the pulp composition by internal addition, the amount of the pulp base material in the pulp composition may be 30 wt% or less; in the case of preparing the pulp composition by external addition, the amount of the pulp base material in the pulp composition may be 75 wt% or more.

[0437] In the pulp composition excluding the liquid medium, the amount of pulp substrate may be 50 wt % or more, 60 wt % or more, 70 wt % or more, 80 wt % or more, 90 wt % or more, 95 wt % or more or 99 wt % or more, and may be 99.9 wt % or less, 95 wt % or less, 90 wt % or less, 85 wt % or less, 75 wt % or less, 65 wt % or less or 55 wt % or less.

[0438] 〔Liquid medium〕

[0439] The pulp composition may contain 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, in particular water. The liquid medium may contain a liquid medium derived from a diluent.

[0440] [Amount of liquid medium]

[0441] In the pulp composition, the amount of the liquid medium may be 0.1 wt% or more, 0.5 wt% or more, 1 wt% or more, 3 wt% or more, 5 wt% or more, 10 wt% or more, 20 wt% or more, 30 wt% or more, 50 wt% or more, 75 wt% or more, 90 wt% or more, or 95 wt% or more, and may be 99 wt% or less, 75 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, 5 wt% or less, 4 wt% or less, or 3 wt% or less. Typically, in the case of preparing the pulp composition by internal addition, the amount of the liquid medium in the pulp composition may be 50 wt% or more, particularly 90 wt% or more; in the case of preparing the pulp composition by external addition, the amount of the liquid medium in the pulp composition may be 30 wt% or less, particularly 10 wt% or less.

[0442] 〔Lyophobic compounds〕

[0443] The pulp composition contains a liquid-repellent compound. The details of the type of the liquid-repellent compound are the same as those described for the liquid-repellent compound in <Repellent>.

[0444] [Amount of liquid repellent compound]

[0445] The amount of the liquid-repellent compound can 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, relative to the pulp substrate; and can 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.

[0446] The liquid-repellent compound can be added to the surface of a pulp substrate (such as paper, paper containers, pulp products, etc.), and the amount of the liquid-repellent compound contained in the coating layer formed by the external addition treatment can be 0.01 g / m 2 Above, 0.03g / m 2 Above, 0.05g / m 2 Above, 0.1g / m 2 Above, 0.3g / m 2 Above, 0.5g / m 2 Above or 1.0g / m 2 Above, and can be 5.0g / 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 Below or 0.1g / m 2 the following.

[0447] 〔Dispersant〕

[0448] The pulp composition may contain a dispersant. The details of the type of the dispersant are the same as those described for the dispersant in <Dispersant>.

[0449] [Amount of dispersant]

[0450] The amount of the dispersant can 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 relative to the pulp substrate; and can 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.

[0451] 〔Paper strength agent〕

[0452] The pulp composition may contain a paper strength agent. Examples of paper strength agents include:

[0453] Cationic polyacrylamide, anionic polyacrylamide, amphoteric polyacrylamide and other polyacrylamide paper strength agents;

[0454] Polysaccharide-based paper strength agents such as starch, enzyme-modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (e.g., hydroxyethylated starch), aldehyde-modified starch, cationized starch, starch, xanthan gum, karaya gum, Brunei gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean, cellulose, alginic acid, agar, dextran, cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, chitin nanofibers, cellulose nanofibers, and pullulan, and modified polysaccharides thereof (e.g., modified polysaccharides into which cyano groups or cationic groups are introduced);

[0455] Polyamide paper strength agents such as polyamide resin, polyamine resin, polyamide-polyamine resin, polyamide-epichlorohydrin resin, polyamide-polyamine-epichlorohydrin resin, polyamide-polyurea-formaldehyde resin, and epoxidized polyamide resin;

[0456] Urea resin, melamine resin, urea-formaldehyde resin, melamine-formaldehyde resin and other urea / melamine paper strength agents;

[0457] Polyvinyl alcohol paper strength agents such as polyvinyl alcohol, completely 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;

[0458] Styrene-butadiene copolymer, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyacrylate, fatty acid diamide, polyethyleneimine resin, ketone-aldehyde resin, etc.

[0459] As the paper strength agent of the present invention, a polyacrylamide-based paper strength agent, a polysaccharide-based paper strength agent or a polyamide-based paper strength agent is preferred.

[0460] [Amount of paper strength agent]

[0461] The total amount of the paper strength agent can 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 relative to the pulp; and can 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.

[0462] The amount of polyacrylamide-based paper strength agent can 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% relative to the pulp; preferably 0.3% by weight or more; and can 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 relative to the pulp.

[0463] The amount of the polysaccharide paper strength agent can 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, preferably 2.0% by weight or more, and can 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, relative to the pulp.

[0464] The amount of the polyamide-based paper strength agent relative to the pulp can 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 can 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.

[0465] 〔Gluing agent〕

[0466] 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 ketone dimers, and alkenyl succinic anhydride acids.

[0467] [Amount of sizing agent]

[0468] The amount of the sizing agent can 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 can 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.

[0469] 〔Other additives〕

[0470] In addition to the above-mentioned components, the pulp composition may also contain other additives such as fixing agents (aluminum sulfate, etc.), coagulants-flocculating agents (polyamine resins, etc.), yield improvers (polyacrylamide resins, etc.), organic acids (formic acid, acetic acid, etc.), dyes, viscosity control agents, defoaming agents, and other paper-related reagents that can be used when manufacturing pulp products.

[0471] [Amount of other additives]

[0472] The amount of other additives relative to the pulp base material can be 0.01 weight %, 0.1 weight %, 1 weight %, 3 weight %, 5 weight % or more, and can be 30 weight %, 20 weight %, 10 weight %, 5 weight %, 3 weight % or less, or 1 weight % or less.

[0473] <Method for producing treated fiber or paper products>

[0474] The method for manufacturing the product treated with a dispersing agent of the present invention comprises a treatment step of treating a substrate with the dispersing agent.

[0475] "Treatment" means applying the repellent to the substrate by dipping, spraying, coating, etc. Through the treatment, the liquid repellent compound as the active ingredient of the repellent is attached to the inside and / or surface of the substrate. Here, the attachment can be physical attachment or chemical attachment. For example, the liquid repellent compound can be physically modified or (reacted) chemically modified by the hydroxyl groups possessed by the substrate (fiber, paper, glass, etc.).

[0476] [Base material]

[0477] The substrate treated with the expelling agent of the present invention is not limited, but is preferably a fiber product or a paper product.

[0478] Examples of the base material of fiber products include natural fibers of plants and animals such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber; or mixed fibers thereof. Fiber products include knitted fabrics, woven fabrics, and non-woven fabrics, cloth in the form of clothing (e.g., water-repellent clothing, such as raincoats), and carpets, but fibers, silk, and intermediate fiber products (e.g., yarn or filaments) in a state before being made into cloth may also be processed.

[0479] Examples of substrates for paper products include bleached or unbleached chemical pulps such as sulfate pulp or sulfite pulp, bleached or unbleached high-yield pulps such as wood pulp, mechanical pulp or thermomechanical pulp, waste paper pulps such as waste newspapers, waste magazine paper, waste corrugated paper or deinked waste paper, etc., paper formed by waste paper pulp, containers formed by paper, and molded bodies formed by paper. Specific examples of paper products include food packaging materials, food containers, gypsum board base paper, coated base paper, medium-quality paper, ordinary lining and core, neutral pure white roll paper, neutral lining, rust-proof lining and metal composite paper, kraft paper, etc., neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper, molded paper (molded container), etc. As preferred examples, food packaging materials and food containers can be listed. By treating a paper substrate with the repellent of the present invention, a paper product imparted with, for example, water repellency, oil repellency, oil resistance, and water resistance (water repellent paper, oil repellent paper, oil-resistant paper, water-resistant paper) can be obtained.

[0480] The substrates treated with the release agent of the present invention are not limited to fiber products or paper products. In addition to these, stone, filters (such as electrostatic filters), dust masks, fuel cell components (such as gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, bricks, cement, metals and oxides, kiln products, plastics, coatings and plaster can also be listed.

[0481] In the case where the substrate is glass, the manufactured glass product can be an optical component. The surface (outermost layer) of the glass substrate may be formed with certain layers (or films), such as a hard coating or an anti-reflection layer. The anti-reflection layer may use any of a single-layer anti-reflection layer and 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 can be used alone, or two or more of them can be used in combination (for example, in the form of a mixture). In the case of making a multi-layer anti-reflection layer, it is preferred that SiO2 and / or SiO be used in the outermost layer. In the case where the article to be manufactured is an optical glass component for a touch panel, a portion of the surface of the substrate (glass) may have a transparent electrode, such as a thin film of indium tin oxide (ITO) or indium zinc oxide. In addition, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating layer, a polarizing film, a phase difference film, and a liquid crystal display module, etc., depending on its specific style.

[0482] [Handling method]

[0483] The dispersing agent of the present invention can be applied to a substrate as a treatment agent (particularly a surface treatment agent) by an existing known method. As a method of treatment, the dispersing agent of the present invention can be dispersed in an organic solvent or water as required for dilution, and then attached to the inside and / or surface of the substrate by known methods such as dip coating, spray coating, and foam coating, and then dried. After drying, a fiber product with a solid component of the dispersing agent can be obtained. In addition, it can also be applied together with a suitable cross-linking agent as required to solidify. The dispersing agent of the present invention can also be further used with various additives such as water-repellent and / or oil-repellent, anti-slip agent, antistatic agent, feel regulator, softener, antibacterial agent, flame retardant, paint fixative, wrinkle-proof agent, drying speed regulator, cross-linking agent, film-forming aid, solubilizer, antifreeze agent, viscosity regulator, ultraviolet light absorber, antioxidant, pH regulator, insect repellent, defoamer, etc. as required. Examples of various additives include the same substances as those described in the "other components" in the water repellent composition. The concentration of the repellent in the treatment agent in contact with the substrate can be appropriately changed according to the application, and can be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0484] The repellent can be applied to the substrate by any known method for treating the substrate with a liquid. The substrate can be immersed in the repellent, or the solution can be attached or sprayed on the substrate. In order to make the treated substrate exhibit liquid repellency, it is preferably dried and cured by heating. The heating temperature is, for example, 100°C to 200°C, 100°C to 170°C or 100°C to 120°C. In the present invention, good performance can be obtained even with low-temperature heating (for example, 100°C to 140°C). In the present invention, the heating time can be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes. When the fiber product is paper, it can be coated on the paper, or the solution can be attached or sprayed on the paper, or it can be mixed with the pulp slurry before papermaking for treatment. The treatment can be an external addition treatment or an internal addition treatment. Alternatively, the repellent can also be applied to the fiber product by a cleaning method, for example, it can be applied by washing or applied to the fiber product by a dry cleaning method.

[0485] [Paper substrate treatment]

[0486] Examples of the paper substrate (pulp substrate) include paper, containers made of paper, and molded articles made of paper (eg, pulp molded products).

[0487] Paper products (paper) can be produced by conventionally known papermaking methods, which can be an internal addition method of adding a repellent to pulp slurry before papermaking or an external addition method of applying a repellent to paper after papermaking.

[0488] The internal addition treatment method may refer to a treatment method of adding a dispersing agent to the pulp slurry before papermaking. As an internal addition treatment method, it may include a process of adding a dispersing agent to the pulp slurry for stirring and mixing; a process of using a mesh body of a specified shape to attract and dehydrate the pulp composition obtained in the process to accumulate the pulp composition to form a pulp molding intermediate; and one or more of the processes of forming and drying the pulp molding intermediate by using a heated molding mold to obtain paper, a container formed by paper, and a molded body formed by paper, but is not limited to this. After the treated paper is simply dried at room temperature or high temperature, it can be optionally subjected to heat treatment according to the properties of the paper. The temperature of the heat treatment can be above 150°C, above 180°C, or above 210°C; and can be below 300°C, below 250°C, or below 200°C, and in particular can be 80°C to 180°C. By performing heat treatment within such a temperature range, excellent oil resistance and water resistance can be displayed.

[0489] The sizing of the external addition treatment method can also be classified as follows according to the coating method.

[0490] One of the coating methods is to pass the paper between two rubber rollers, supply the coating liquid (gluing liquid) to the formed clamping part, form a coating liquid storage part called a glue pool, and pass the paper through the coating liquid storage part to coat the glue liquid on both sides of the paper, which is the so-called glue pool type double roller sizing. Other coating methods include gate roller type and film transfer sizing that use a surface transfer mold to apply the glue liquid. In the glue pool type double roller sizing, the glue liquid easily penetrates into the inside of the paper; in the surface transfer type, the glue liquid components easily stay on the surface of the paper. Compared with the glue pool type double roller sizing, the coating layer of the surface transfer type easily stays on the surface of the paper, and the coating layer formed on the surface is more than that of the glue pool type double roller sizing. In the present invention, even when the former glue pool type double roller sizing is used, it is also possible to impart properties to the paper. The paper treated in this way can exhibit excellent oil resistance and water resistance by simply drying at room temperature or high temperature and then optionally subjecting it to heat treatment at a temperature below 300°C, for example below 200°C, particularly within a temperature range of 80°C to 180°C, depending on the properties of the paper.

[0491] The present invention can be used in gypsum board base paper, coated base paper, medium-quality paper, ordinary lining and core, neutral pure white roll paper, neutral lining, anti-rust lining and metal composite paper, kraft paper, etc. In addition, 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.

[0492] As the pulp raw material, any waste paper pulp such as bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as ground wood pulp, mechanical pulp or thermomechanical pulp, and waste newspaper, waste magazine paper, waste corrugated paper, deinked waste paper, etc. can be used. In addition, a mixture of the above pulp raw materials and synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, polyvinyl alcohol, etc. can also be used.

[0493] Adding a sizing agent can improve the water resistance of paper. Examples of sizing agents include cationic sizing agents, anionic sizing agents, and rosin-based sizing agents (e.g., acidic rosin-based sizing agents, neutral rosin-based sizing agents). The amount of the sizing agent can be 0.01 to 5% by weight relative to the pulp.

[0494] Paper can use the paper strength strengthening agent such as starch, modified starch, carboxymethyl cellulose, polyamide polyamine-epichlorohydrin resin as the papermaking reagent of the degree of common use, agglutinating agent, fixing agent, yield rate improving agent, dye, fluorescent dye, viscosity control agent, defoamer etc. additives used in papermaking as required. Starch and / or modified starch are preferably used. As required, starch, polyvinyl alcohol, dye, coating colorant, anti-slip agent etc. can be used, and the dilating agent is coated on paper using a sizing machine, gate roller coater, Bill blade coater, calender etc.

[0495] When added externally, the amount of the liquid repellent compound contained in the coating layer is preferably 0.01 to 2.0 g / m 2 , especially 0.1 to 1.0 g / m 2 The coating layer is preferably formed of a paper dispersing agent and starch and / or modified starch. The solid content of the paper dispersing agent in the coating layer is preferably 2 g / m 2 the following.

[0496] When added internally, the expelling agent is preferably mixed with the pulp in an amount of 0.01 to 50 parts by weight or 0.01 to 30 parts by weight, for example 0.01 to 10 parts by weight, particularly 0.2 to 5.0 parts by weight, based on 100 parts by weight of pulp forming paper.

[0497] When adding external sizing, oil resistance can also be imparted to paper by using a so-called glue pool type double roll sizing treatment in which a treatment liquid is retained between the rolls and the base paper is passed through the treatment liquid between the rolls at an arbitrary roll speed and nip pressure.

[0498] In the external addition treatment, the paper substrate may contain additives such as sizing agents, paper strengthening agents, coagulants, yield enhancers or coagulants. The additives may be nonionic, cationic, anionic or amphoteric. The ionic charge density of the additive may be -10000 to 10000 μeq / g, preferably -4000 to 8000 μeq / g, and more preferably -1000 to 7000 μeq / g. The amount of additives such as sizing agents, paper strengthening agents, coagulants, yield enhancers or coagulants (solid components or active components) relative to the pulp is usually 0.1 to 10% by weight (e.g., 0.2 to 5.0% by weight). In the case of a paper substrate containing a cationic additive (e.g., sizing agents, paper strengthening agents, coagulants, yield enhancers or coagulants), the expelling agent is preferably anionic.

[0499] In the internal addition treatment, it is preferred to make paper from a pulp slurry having a pulp concentration of 0.5 to 5.0 wt % (e.g., 2.5 to 4.0 wt %). Additives (e.g., sizing agents, paper strengthening agents, coagulants, yield improvers, or coagulants, etc.) and liquid-repellent compounds may be added to the pulp slurry. Examples of additives (e.g., sizing agents, paper strengthening agents, coagulants, yield improvers, or coagulants, etc.) include alkyl ketene 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 polyalkylene polyamines, dicyandiamide-aldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0500] [Pretreatment of fiber substrate]

[0501] The fiber substrate (cloth substrate) may be pretreated before being treated with the repelling agent of the present invention. By pretreating the fiber substrate, excellent firmness can be imparted to the fiber product treated with the repelling agent.

[0502] Examples of pretreatment of the fiber substrate include cationization treatment by reaction with a reactive quaternary ammonium salt, anionization treatment by sulfonation, carboxylation, phosphation, acetylation after anionization treatment, benzoylation, carboxymethylation, grafting, tannic acid treatment, polymer coating, etc.

[0503] There is no limitation on the method for pre-treating the fiber substrate, and the fiber substrate can be pre-treated by a conventionally known method. The pre-treatment liquid can be dispersed in an organic solvent or water as required, diluted, attached to the inside and / or surface of the fiber substrate by a known method such as dip coating, spray coating, foam coating, and then dried. The pH and temperature of the pre-treatment liquid can be adjusted according to the desired degree of treatment. As an example of a method for pre-treating the fiber substrate, a method for pre-treating the fiber substrate using a hydrocarbon-based water-repellent agent is described in detail.

[0504] The pretreatment method of the fiber substrate may include imparting to the fiber a 1 (Where M 1 represents a monovalent cation) represented by a univalent group, -COOM 2 (Where M 2 represents a monovalent cation) and -O-P(O)(OX 1 )(OX 2 )(where X 1 and X 2 A step of each independently representing one or more functional groups (hereinafter sometimes referred to as "specific functional groups") in a monovalent group represented by a hydrogen atom or an alkyl group having 1 to 22 carbon atoms.

[0505] As M 1 , H, K, Na or an ammonium ion which may have a substituent can be mentioned. 2 , H, K, Na or an ammonium ion which may have a substituent may be mentioned. 1 or X 2 In the case of an alkyl group, an alkyl group having 1 to 22 carbon atoms is preferred, and an alkyl group having 4 to 12 carbon atoms is more preferred.

[0506] The fiber containing the above-mentioned specific functional group (hereinafter sometimes referred to as "functional group-containing fiber") can be produced, for example, by the following method.

[0507] (i) The compound having the specific functional group is attached to the fiber material, wherein the compound may be attached in a state where a part of the compound is chemically bonded to a part of the fiber within a range where a sufficient amount of the specific functional group remains.

[0508] (ii) As a material constituting the fiber, a fiber into which the above-mentioned specific functional group is directly introduced is used.

[0509] In the case of (i), for example, the fiber material is treated with a pretreatment solution containing one or more compounds having the above-mentioned specific functional groups, and through such a functional group introduction step, fibers containing functional groups can be obtained.

[0510] The raw materials of the fiber material are not particularly limited, and examples thereof include natural fibers such as cotton, linen, silk, and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene, and composite fibers and blended fibers thereof. The fiber material may be in any form such as fiber (tow, yarn, etc.), silk, braid (including blended), woven (including blended), and non-woven.

[0511] In the present embodiment, from the viewpoint of good water repellency of the obtained fiber product, it is preferred to use a fiber material containing polyamide and polyester as raw materials, and it is particularly preferred to use nylon 6, nylon 6,6 and other nylons, polyethylene terephthalate (PET), polytrimethylene terephthalate, polyesters such as polylactic acid, and mixed fibers containing them.

[0512] As a having the above-mentioned -SO3M 1 As a compound, a phenolic polymer can be used. As such a phenolic polymer, for example, a substance containing one or more compounds represented by the following general formula can be cited.

[0513]

[0514] [Wherein, X 2 Representation - SO3M 3 (Where M 3 represents a monovalent cation) or a group represented by the following general formula, wherein n is an integer of 20 to 3000.]

[0515]

[0516] [Wherein, M 4 Indicates a monovalent cation.]

[0517] As the above M 3 , H, K, Na or an ammonium ion which may have a substituent may be mentioned.

[0518] As the above M4 , H, K, Na or an ammonium ion which may have a substituent may be mentioned.

[0519] 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.

[0520] As a company with the above-mentioned 2 The compound includes polycarboxylic acid polymers.

[0521] As the polycarboxylic acid-based polymer, for example, a polymer synthesized by using acrylic acid, methacrylic acid, maleic acid, or the like as a monomer according to a conventionally known radical polymerization method, or a commercially available product can be used.

[0522] As a method for producing a polycarboxylic acid polymer, for example, a method of adding a free radical polymerization initiator to an aqueous solution of the above-mentioned monomer and / or its salt, and heating the reaction at 30 to 150° C. for 2 to 5 hours can be cited. At this time, an alcohol such as methanol, ethanol, isopropanol or an aqueous solvent such as acetone can also be added to the aqueous solution of the above-mentioned monomer and / or its salt. As a free radical polymerization initiator, for example, persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, redox polymerization initiators using a combination of persulfate and sodium bisulfite, hydrogen peroxide, and water-soluble azo polymerization initiators can be cited. These free radical polymerization initiators can be used alone or in combination of two or more. In addition, during free radical polymerization, a chain transfer agent (such as octyl thioglycolate) can be added to adjust the degree of polymerization.

[0523] In addition to the above-mentioned monomers, copolymerizable monomers can also be used during free radical polymerization. Examples of copolymerizable monomers include: vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate; acrylamide, acrylates, methacrylates, and the like. Acrylates and methacrylates preferably have a hydrocarbon group having 1 to 3 carbon atoms which may have a substituent such as a hydroxyl group. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, propyl methacrylate, and the like. These copolymerizable monomers can be used alone or in combination of two or more.

[0524] The carboxyl groups in the polycarboxylic acid polymer may be free or neutralized by an alkali metal or 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.

[0525] The weight average molecular weight of the polycarboxylic acid polymer is preferably 1,000 to 20,000, more preferably 3,000 to 15,000, from the viewpoint of good water repellency of the obtained fiber product.

[0526] As the polycarboxylic acid-based polymer, commercially available products such as "NEOCRYSTAL 770" (trade name, manufactured by Nikka Chemical Co., Ltd.) and "Celopol PC-300" (trade name, manufactured by Sanyo Chemical Industries, Ltd.) can be used.

[0527] As the above-mentioned -O-P(O)(OX 1 )(OX 2 ) compounds, for example, the phosphate compounds represented by the following general formula can be cited.

[0528]

[0529] [Wherein, X 1 or X 2 The meaning is the same as above, X 3 represents an alkyl group having 1 to 22 carbon atoms.]

[0530] As the phosphoric acid ester compound, phosphoric acid monoesters, diesters and triesters in which the alkyl ester portion is an alkyl group having 1 to 22 carbon atoms, and mixtures thereof can be used.

[0531] From the viewpoint of good water repellency of the obtained fiber product, lauryl phosphate and decyl phosphate are preferably used.

[0532] As the phosphoric acid ester compound, for example, a commercially available product such as "PHOSPHANOL ML-200" (trade name, manufactured by Toho Chemical Industry Co., Ltd.) can be used.

[0533] The pretreatment solution containing one or more compounds having the above-mentioned specific functional groups can be prepared, for example, as an aqueous solution of the above-mentioned compounds. In addition, the pretreatment solution can also contain an acid, an alkali, a surfactant, a chelating agent, and the like.

[0534] As a method for treating the fiber material with the above-mentioned pretreatment liquid, for example, pad dyeing, dipping, spraying, and coating can be cited. As a pad dyeing, for example, the method using a pad dyeing device described on pages 396 to 397 of the Dictionary of Fiber Dyeing Processing (published by Nikkan Kogyo Shimbun in 1975) or pages 256 to 260 of Color Dyeing Chemistry III (published by Jikyo Publishing Co., Ltd. in 1975) can be cited. As a coating, for example, the method using a coating machine described on pages 473 to 477 of the Overview of Dyeing and Finishing Equipment (published by Textile Company in 1975) can be cited. As an immersion treatment, for example, the method using a batch dyeing machine described on pages 196 to 247 of the Overview of Dyeing and Finishing Equipment (published by Textile Company in 1975) can be cited. Liquid flow dyeing machines, air flow dyeing machines, drum dyeing machines, hank dyeing machines, washing dyeing machines, and bobbin dyeing machines can also be used. As a spray treatment, for example, a method of using compressed air to spray the treatment liquid into a mist-like gas spray, or a method of using a hydraulic atomization method to spray the gas can be cited. The concentration of the treatment liquid at this time and the treatment conditions such as the heat treatment after the treatment can be appropriately adjusted in consideration of various conditions such as its purpose and performance. In addition, when the pre-treatment liquid contains water, it is preferably dried to remove the water after adhering to the fiber material. There is no particular restriction on the drying method, and any method of dry heat method and wet heat method can be used. There is no particular restriction on the drying temperature, for example, it can be dried at room temperature to 200°C for 10 seconds to several days. If necessary, it can also be heated at a temperature of 100 to 180°C for about 10 seconds to 5 minutes after drying.

[0535] Among them, when the fiber material is the dyed material, the treatment with the pretreatment liquid can be carried out before dyeing or in the same bath as dyeing. However, in the case of reduction soaping, since the adsorbed compounds having the above-mentioned specific functional groups (such as phenolic polymer compounds, etc.) can fall off during the process, it is preferably carried out after the reduction soaping after dyeing.

[0536] The treatment temperature in the immersion treatment can be set to 60 to 130° C. The treatment time can be set to 5 to 60 minutes.

[0537] In the functional group introduction step using the pretreatment liquid, the compound having the specific functional group is preferably treated in an amount of 1.0 to 7.0 parts by weight relative to 100 parts by weight of the fiber material. Within this range, both durable water repellency and hand feel can be achieved at a high level.

[0538] The pH of the pretreatment liquid is preferably adjusted to 3 to 5. A pH adjuster such as acetic acid or malic acid can be used for pH adjustment.

[0539] In the pretreatment solution, a salt may be used to more effectively adsorb the compound having the specific functional group to the fiber material by the salting-out effect. Examples of the salt include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate.

[0540] In the functional group introduction step using the pretreatment liquid, it is preferred to remove the compound having the above-mentioned specific functional group that has been overtreated. As a removal method, a method using water washing can be cited. By performing sufficient removal, it is possible to suppress the inhibition of the development of water repellency in the subsequent water repellent processing, and the feel of the obtained fiber product is good. In addition, the obtained functional group-containing fiber is preferably fully dried before contacting with the hydrocarbon-based water repellent agent.

[0541] (ii) Examples of fibers in which the above-mentioned specific functional groups are directly introduced into the material constituting the fibers include cationic dyeable polyester (CD-PET).

[0542] From the viewpoint of good water repellency of the obtained fiber product, the zeta potential of the surface of the functional group-containing fiber is preferably -100 to -0.1 mV, more preferably -50 to -1 mV. The zeta potential of the fiber surface can be measured, for example, using a zeta potential / particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0543] The repellent can be applied to a fibrous substrate (e.g., a fiber product) by any known method for treating a fiber product with a liquid. When the fiber product is a cloth, the cloth can be immersed in the solution or the solution can be attached to or sprayed on the cloth. In order to make the treated fiber product exhibit liquid repellency (water repellency and / or oil repellency), it can be dried, preferably heated at 80°C to 200°C, for example.

[0544] Alternatively, the repellent may be applied to the fabric by a cleaning process, for example, by washing or by dry cleaning.

[0545] The treated fiber products are typically cloth, including knitted fabrics, woven fabrics and non-woven fabrics, cloth in the form of clothing and carpets, and may also be fibers, silk or intermediate fiber products (such as yarn or raw silk, etc.). The fiber product material may be natural fiber (such as cotton or wool, etc.), chemical fiber (such as viscose rayon or lyocell, etc.) or synthetic fiber (such as polyester, polyamide or acrylic fiber, etc.), or may also be a mixture of fibers (such as a mixture of natural fibers and synthetic fibers, etc.). In addition, the method of the present invention can generally make the fiber product hydrophobic and water-repellent.

[0546] Alternatively, the fibrous substrate may be leather. In order to render the leather hydrophobic and oleophobic, the polymer produced may be applied to the leather from an aqueous solution or an aqueous emulsion at various stages of leather processing, such as during the wet processing of the leather or during the finishing of the leather.

[0547] "Treatment" means applying a liquid repellent compound to the object to be treated by dipping, spray coating, etc. Through the treatment, the active ingredient of the liquid repellent and oil repellent compound penetrates into the interior of the object to be treated and / or adheres to the surface of the object to be treated.

[0548] Although the embodiments are described above, it should be understood that various changes in mode and detail may be made without departing from the spirit and scope of the scope of the claims.

[0549] Example

[0550] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0551] <Test method>

[0552] The steps of the experiment are as follows.

[0553] [Manufacturing of pulp molded body]

[0554] A pulp molded body is made using an automatic molding machine. A mesh body is arranged on the lower part of a metal pulp molded body forming mold with multiple suction holes, and a metal groove is arranged on the upper part, and pulp slurry is added to the upper metal groove. From the side of the pulp molded body forming mold opposite to the side where the mesh body is arranged, a vacuum pump is used to suck and dehydrate the pulp-containing aqueous composition through the pulp molded body forming mold and the mesh body at 0.1 to 1 MPa, so that the solid components (pulp, etc.) contained in the pulp-containing aqueous composition are accumulated on the mesh body to obtain a pulp molded body intermediate. Then, the obtained pulp molded body intermediate is dried from top to bottom at a pressure of 0.1 to 1 MPa using a metal male and female mold forming mold heated to 60 to 200°C. In this way, a pulp molded body formed into a container shape is produced.

[0555] [Practical oil resistance test - 65°C]

[0556] The pulp molded body was stored at 23°C and 50% humidity for 12 hours to perform pretreatment. 100 ml of corn oil at 65°C was injected into the pulp molded body and left at room temperature for 45 minutes. The corn oil was then removed from the pulp molded body to evaluate the degree of oil stains on the pulp molded body. The evaluation score was set as follows according to the degree of oil stain penetration.

[0557] 5: No oil stains on the inside.

[0558] 4: There are oil stains on the inside, but no oil stains on the back.

[0559] 3: There are oil stains on the inside and a little oil seepage on the back.

[0560] 2: There are oil stains on the inside, and the oil seepage to the back is less than 50% of the area.

[0561] 1: There is oil stain on the inner side, and the oil stain seeps onto the back side over 50% or more and less than 100% of the area.

[0562] 0: Oil seepage occurs on the entire back side.

[0563] [Practical oil resistance test - 80℃]

[0564] The pulp molded body was pretreated by storing it at 23°C and 50% humidity for 12 hours. The same operation and evaluation as in [Practical Oil Resistance Test - 65°C] were performed except that 80°C corn oil was used instead of 65°C corn oil.

[0565] [Practical oil resistance test - 100°C]

[0566] The pulp molded body was pretreated by storing it at 23°C and 50% humidity for 12 hours. The same operation and evaluation as in [Practical Oil Resistance Test - 65°C] were performed except that 100°C corn oil was used instead of 65°C corn oil.

[0567] [Practical oil resistance test - 110℃]

[0568] The pulp molded body was pretreated by storing it at 23°C and 50% humidity for 12 hours. The same operation and evaluation as in [Practical Oil Resistance Test - 65°C] were performed except that 110°C corn oil was used instead of 65°C corn oil.

[0569] [Practical oil resistance test - 120℃]

[0570] The pulp molded body was pretreated by storing it at 23°C and 50% humidity for 12 hours. The same operation and evaluation as in [Practical Oil Resistance Test - 65°C] were performed except that 120°C corn oil was used instead of 65°C corn oil.

[0571] [Practical water resistance test]

[0572] The pulp molded body was stored at 23°C and 50% humidity for 12 hours to perform pretreatment. 100 ml of 100°C water was injected into the pulp molded body, and after standing at room temperature for 30 minutes, the water was removed from the pulp molded body to evaluate the degree of water stains on the pulp molded body. The evaluation score was set as follows according to the degree of water stain penetration.

[0573] 5: No water stains on the inside.

[0574] 4: There are water stains on the inside, but no water stains on the back.

[0575] 3: There are water stains on the inside and slight water seepage on the back.

[0576] 2: There are water stains on the inside, and the water stains seeping to the back are less than 50% of the area.

[0577] 1: There is water stain on the inside, and the water stain has seeped onto the back side over 50% or more and less than 100% of the area.

[0578] 0: Water seepage occurs on the entire back side.

[0579] [Production of treated paper]

[0580] Using a BAKER applicator with the gap set to 0 mil, the water resistance (Cobb value) was 52 g / m 2 , Weight per unit area 45g / m 2 , density 0.60g / m 3 14.9mg / cm2 was applied on thin paper 3 The solution of the liquid repellent compound was coated three times, and then annealed at 140° C. for 1 minute to prepare a treated paper. Chloroform was used to prepare the solution of the coating liquid. When the liquid repellent compound was insoluble in chloroform, an organic solvent such as toluene or acetone was used.

[0581] [KIT test (oil resistance)]

[0582] The test was performed using the 3M test kit (TAPPI T-559cm-02). In the 3M test kit method, a test oil mixed with castor oil, toluene, and heptane is placed on the surface of the treated paper, and the test oil is wiped off after 15 seconds. Evaluation is performed based on whether there is oil stain on the treated paper at this time. The test was performed using test oils of test numbers 1 to 6, and the largest test oil number with no oil stain was used as the evaluation result of oil resistance.

[0583] [Corn oil resistance test (oil resistance)]

[0584] Corn oil was placed on the surface of the treated paper, and the test oil was wiped off after 15 seconds. Evaluation was performed based on whether there was oil stain on the treated paper at this time.

[0585] The evaluation was 0 when there was no oil stain, and × when oil stain was visible.

[0586] [HD contact angle]

[0587] A solution (or dispersion) of a liquid repellent compound with a solid content concentration of 1.0% is spin-coated on a silicon wafer at 2500 rpm for 25 seconds to obtain a smooth spin-coated film. The film is heated at 140°C for 1 minute to prepare a silicon wafer treated with the compound. Chloroform is used as a solvent or dispersion medium. 2 μL of HD (hexadecane) is dripped onto the silicon wafer treated with the compound, and the static contact angle after dripping for 1 second is taken as the HD contact angle of the liquid repellent compound.

[0588] [Tensile strength of pulp molded products]

[0589] The tensile strength of the pulp molded article was evaluated by relative tensile strength in a dry state measured in accordance with JIS P 8113: 2006, but is not particularly limited. A test piece having a width of 15 mm, a length of 50 mm, and a thickness of 0.8 mm was cut out from the bottom surface of the pulp molded article and used. A universal testing machine manufactured by Shimadzu Corporation was used as the apparatus, and the test was conducted under the conditions of a tensile interval of 30 mm and a tensile speed of 10 mm / min.

[0590] [Water repellency test of fabric]

[0591] A treatment solution having a solid content concentration of 16.8 mg / mL was prepared using chloroform as a solvent, and the cloth was immersed in the treatment solution and then passed through a cloth mangle. The water repellency was evaluated using the heat-treated test cloth.

[0592] The water repellency of the treated fabric was evaluated by the spray method according to JIS-L-1092 (AATCC-22). As shown in the table below, it is represented by the water repellency No. The higher the score, the better the water repellency. A number with a "+" means better than the number, and a "-" means worse than the number. Polyester cloth (PET) or nylon cloth (Ny) was used for evaluation.

[0593] Water repellency No. status

[0594]

[0595] <Compound 2>

[0596] 5.57 g of stearic acid (Tokyo Chemical Industry Co., Ltd. product), 3.57 g of 2-amino-1,3-propanediol (Fujifilm Wako Pure Chemical Industry Co., Ltd. product), and 0.239 g of 4,4-dimethylaminopyridine (Fujifilm Wako Pure Chemical Industry Co., Ltd. product) were dissolved in 100.0 mL of dehydrated dimethylformamide (Fujifilm Wako Pure Chemical Industry Co., Ltd. product), and 4.50 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (Tokyo Chemical Industry Co., Ltd. product) were added in sequence, and stirred overnight at an oil bath temperature of 100°C. The next day, the reaction solution was cooled to 40°C and filtered, and the solid was washed with dimethylformamide and water. After washing, the solid was dried to obtain 1.64 g of the compound 1 shown below.

[0597]

[0598] 1 H 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)

[0599] After dissolving 1.64 g of compound 1 in 35.0 mL of dehydrated tetrahydrofuran (product of Fujifilm Wako Pure Chemical Industries, Ltd.), 2.98 g of octadecyl isocyanate (product of Fujifilm Wako Pure Chemical Industries, Ltd.) and 4 drops of dibutyltin dilaurate were added in sequence, and stirred overnight at an oil bath temperature of 70°C. The next day, the reaction solution was cooled to room temperature and filtered, and the solid was washed with tetrahydrofuran. After washing, the solid was dried to obtain 4.32 g of compound 2 shown below.

[0600]

[0601] 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)

[0602] <Compound 3>

[0603] After dissolving 6.00 g of stearic acid (Tokyo Chemical Industry Co., Ltd. product), 0.7 g of N,N'-di(2-aminoethyl)ethylenediamine (Tokyo Chemical Industry Co., Ltd. product), and 0.12 g of 4,4-dimethylaminopyridine (Fujifilm Wako Pure Chemical Industry Co., Ltd. product) in 60.0 mL of dehydrated chloroform (Fujifilm Wako Pure Chemical Industry Co., Ltd. product), 4.13 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (Tokyo Chemical Industry Co., Ltd. product) was added in sequence, and stirred overnight at an oil bath temperature of 50°C. The next day, the reaction solution was cooled to room temperature and 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.

[0604]

[0605] 1 H NMR (CDCl3, 400 MHz) 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) <Compound 4>

[0606] The compound 4 shown below was synthesized with reference to CN109280362A (2019-01-29).

[0607]

[0608] [Wherein, R is stearyl.]

[0609] <Examples 1 to 3>

[0610] Using the compounds 2 to 4 obtained above, a molding test was carried out.

[0611] With respect to 2g of compound 2, 0.2g of polyoxyethylene (10) oleyl ether (HLB14) was mixed and heated to 140°C to melt it. The obtained solid was crushed in a mortar, and after adding 17.8g of water, it was stirred at 10000rpm for 20 minutes using a homogenizer to obtain an aqueous dispersion composition of compound 2. Next, the aqueous dispersion composition of compound 2 was added to a pulp slurry with a concentration of 0.5wt% in a manner to achieve a ratio of 10wt% relative to the pulp in terms of solid content conversion to prepare an aqueous composition containing pulp. The aqueous composition containing pulp was put into an automatic molding machine to prepare a pulp molded body. The pulp molded body was subjected to a practical oil resistance test at -65°C and a practical water resistance test, and the results showed that the oil resistance and water resistance were 4 points.

[0612] With respect to 2g of compound 3, 0.2g of polyoxyethylene (10) oleyl ether (HLB14) was mixed and heated to 130°C to melt it. The obtained solid was crushed in a mortar, and after adding 17.8g of water, it was stirred at 10000rpm for 20 minutes using a homogenizer to obtain an aqueous dispersion composition of compound 3. Next, the aqueous dispersion composition of compound 3 was added to a pulp slurry with a concentration of 0.5wt% in a manner to achieve a ratio of 10wt% relative to the pulp in terms of solid content conversion to prepare an aqueous composition containing pulp. The aqueous composition containing pulp was put into an automatic molding machine to prepare a pulp molded body. The pulp molded body was subjected to a practical oil resistance test at -65°C and a practical water resistance test, and the results showed that the oil resistance and water resistance were 4 points.

[0613] With respect to 2g of compound 4, 0.2g of polyoxyethylene (10) oleyl ether (HLB14) was mixed and heated to 160°C to melt it. The obtained solid was crushed in a mortar, and after adding 17.8g of water, it was stirred at 10000rpm for 20 minutes using a homogenizer to obtain a water-dispersible composition of compound 4. Next, the water-dispersible composition of compound 4 was added to a pulp slurry with a concentration of 0.5wt% in a manner to achieve a ratio of 10wt% relative to the pulp in terms of solid content conversion to prepare an aqueous composition containing pulp. The aqueous composition containing pulp was put into an automatic molding machine to prepare a pulp molded body. The pulp molded body was subjected to a practical oil resistance test at -65°C and a practical water resistance test, and the results showed that the oil resistance and water resistance were 4 points.

[0614] The test results are summarized in Table 1 below, with the melting points also shown for the general formulae.

[0615] [Table 1]

[0616]

[0617] <Examples 4 and 5>

[0618] The compounds obtained above were used to carry out KIT test (oil resistance), corn oil resistance test, and evaluation of liquid repellency. The test results are summarized in Table 2 below.

[0619] [Table 2]

[0620]

[0621] <Example 6>

[0622] 2 g of N,N'-ethylenebisoctadecanoic acid amide (bio-based content: 97%, melting point: 143°C), 0.2 g of polyethylene glycol trimethyl nonyl ether (HLB13), and 17.8 g of water were mixed to obtain a water-dispersible composition (volume ratio of particles larger than 100 μm: 3.9%, volume median diameter: 18 μm).

[0623] The water dispersion composition was added to a pulp slurry having a concentration of 0.5 wt % at a ratio of 3 wt % based on the solid content of the pulp to prepare an aqueous composition containing pulp. The aqueous composition containing pulp was placed in an automatic molding machine to prepare a pulp molded body.

[0624] The pulp molded body was subjected to a practical oil resistance test at -110°C, a practical oil resistance test at -65°C, and a practical water resistance test, and the evaluation results were all 4 points.

[0625] <Example 7>

[0626] 2 g of N,N'-ethylenebisoleamide (biobased content: 96%, melting point: 116°C), 0.2 g of EO / PO polyalkylene glycol ether, and 17.8 g of water were mixed to obtain a water-dispersible composition (volume ratio of particles larger than 100 μm: 0%, volume median diameter: 24 μm).

[0627] The water dispersion composition was added to a pulp slurry having a concentration of 0.5 wt % at a ratio of 10 wt % based on the solid content of the pulp to prepare an aqueous composition containing pulp. The aqueous composition containing pulp was placed in an automatic molding machine to prepare a pulp molded body.

[0628] The molded body was subjected to a practical oil resistance test at -65°C, and the result was 4 points; the molded body was subjected to a practical water resistance test, and the result was 4 points.

[0629] The KIT test (oil resistance) and corn oil resistance test were conducted using N,N'-ethylenebisoleamide. The results were 4 points in the KIT test and 0 in the corn oil resistance test.

[0630] <Example 8>

[0631] 2 g of N,N'-xylylene-bis-12-hydroxystearamide (bio-based content: 83%, melting point: 124°C), 0.2 g of benzalkonium chloride, and 17.8 g of water were mixed to obtain a water-dispersible composition (volume abundance ratio of particles larger than 100 μm: 0%, volume median diameter: 7 μm).

[0632] The water dispersion composition was added to a pulp slurry having a concentration of 0.5 wt % at a ratio of 3 wt % based on the solid content of the pulp to prepare an aqueous composition containing pulp. The aqueous composition containing pulp was placed in an automatic molding machine to prepare a pulp molded body.

[0633] The pulp molded body was subjected to a practical oil resistance test at -65°C and the result was 4 points.

[0634] The KIT test (oil resistance) and corn oil resistance test were conducted using N,N'-xylylene-bis-12-hydroxystearamide. The results were 3 points in the KIT test and 0 in the corn oil resistance test.

[0635] <Example 9>

[0636] 2 g of N,N'-xylylene-bis-12-hydroxystearamide (biobased content: 83%), 0.2 g of polyethylene glycol trimethyl nonyl ether (HLB13), and 17.8 g of water were mixed to obtain a water-dispersible composition (volume ratio of particles larger than 100 μm: 0%, volume median diameter: 9 μm).

[0637] The water dispersion composition was added to a pulp slurry having a concentration of 0.5 wt % at a ratio of 10 wt % based on the solid content of the pulp to prepare an aqueous composition containing pulp. The aqueous composition containing pulp was placed in an automatic molding machine to prepare a pulp molded body.

[0638] A practical oil resistance test was conducted at -65°C, and the result was 4 points; a practical oil resistance test was conducted on the pulp molded body at -80°C, and the result was 4 points; a practical oil resistance test was conducted on the pulp molded body at -120°C, and the result was 4 points; a practical water resistance test was conducted, and the result was 4 points.

[0639] <Example 10>

[0640] 2 g of N,N'-xylylene-bis-12-hydroxystearamide (biobased content: 83%), 0.2 g of potassium oleate, and 17.8 g of water were mixed to obtain a water-dispersible composition (volume abundance ratio of particles larger than 100 μm: 0%, volume median diameter: 9 μm).

[0641] The water dispersion composition was added to a pulp slurry having a concentration of 0.5 wt % at a ratio of 10 wt % based on the solid content of the pulp to prepare an aqueous composition containing pulp. The aqueous composition containing pulp was placed in an automatic molding machine to prepare a pulp molded body.

[0642] The pulp molded body was subjected to a practical oil resistance test at -65°C, and the result was 4 points; the practical water resistance test was also conducted, and the result was 4 points.

[0643] <Example 11>

[0644] 2 g of N,N'-ethylene-bis-12-hydroxystearamide (bio-based 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 a water-dispersible composition (volume ratio of particles larger than 100 μm: 5%, volume median diameter: 17 μm).

[0645] The water dispersion composition was added to a pulp slurry having a concentration of 0.5 wt % at a ratio of 5 wt % based on the solid content of the pulp to prepare an aqueous composition containing pulp. The aqueous composition containing pulp was placed in an automatic molding machine to prepare a pulp molded body.

[0646] The pulp molded body was subjected to a practical oil resistance test at -65°C, and the result was 4 points; the pulp molded body was subjected to a practical oil resistance test at -110°C, and the result was 4 points.

[0647] <Example 12>

[0648] 2 g of N,N'-ethylene-bis-12-hydroxystearamide (biobased content: 95%), 0.2 g of EO / PO polyalkylene glycol natural alcohol ether, and 17.8 g of water were mixed to obtain a water-dispersible composition (volume ratio of particles of 100 μm or more: 8.2%).

[0649] The water dispersion composition was added to a pulp slurry having a concentration of 0.5 wt % at a ratio of 10 wt % based on the solid content of the pulp to prepare an aqueous composition containing pulp. The aqueous composition containing pulp was placed in an automatic molding machine to prepare a pulp molded body.

[0650] The pulp molded body was subjected to a practical oil resistance test at -80°C and the result was 4 points.

[0651] <Example 13>

[0652] 2 g of N,N'-ethylene-bis-12-hydroxystearamide (biobased content: 95%), 0.2 g of EO / PO polyalkylene glycol natural alcohol ether, and 17.8 g of water were mixed to obtain a water-dispersible composition (volume ratio of particles larger than 100 μm: 5%, volume median diameter: 17 μm).

[0653] The water dispersion composition was added to a pulp slurry having a concentration of 0.5 wt % at a ratio of 3 wt % based on the solid content of the pulp to prepare an aqueous composition containing pulp. The aqueous composition containing pulp was placed in an automatic molding machine to prepare a pulp molded body.

[0654] The pulp molded body was subjected to a practical water resistance test and the result was 4 points.

[0655] <Example 14>

[0656] 2 g of N,N'-hexamethylene-bis-12-hydroxystearamide (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-dispersible composition (volume ratio of particles larger than 100 μm: 3.5%, volume median diameter: 12 μm).

[0657] The water dispersion composition was added to a pulp slurry having a concentration of 0.5 wt % at a ratio of 7 wt % based on the solid content of the pulp to prepare an aqueous composition containing pulp. The aqueous composition containing pulp was placed in an automatic molding machine to prepare a pulp molded body.

[0658] The pulp molded body was subjected to a practical oil resistance test at -65°C, with a result of 4 points; the practical oil resistance test was conducted at -80°C, with a result of 4 points; the practical oil resistance test was conducted at -100°C, with a result of 4 points.

[0659] <Example 15>

[0660] 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-dispersible composition.

[0661] The water dispersion composition was added to a pulp slurry having a concentration of 0.5 wt % at a ratio of 10 wt % based on the solid content of the pulp to prepare an aqueous composition containing pulp. The aqueous composition containing pulp was placed in an automatic molding machine to prepare a pulp molded body.

[0662] <Example 16>

[0663] Mix 2 g of compound 5 represented by N(CH2CH2NHCONHR)3 [wherein R is stearyl] and 0.2 g of EO / PO polyalkylene glycol natural alcohol ether, grind the obtained solid in a mortar, add 17.8 g of water, and stir at 10000 rpm for 20 minutes using a homogenizer to obtain a water-dispersible composition of compound 5 (volume existence ratio of particles larger than 100 μm: 0%).

[0664] The water dispersion composition was added to a pulp slurry having a concentration of 0.5 wt % at a ratio of 7 wt % based on the solid content of the pulp to prepare an aqueous composition containing pulp. The aqueous composition containing pulp was placed in an automatic molding machine to prepare a pulp molded body.

[0665] The pulp molded body was subjected to a practical oil resistance test at -65°C, and the result was 4 points; the practical oil resistance test was conducted at -80°C, and the result was 4 points; the practical water resistance test was conducted, and the result was 4 points.

[0666] <Example 17>

[0667] Mix 2 g of compound 6 represented by RNHCONHCH2CH2N(CONHR)CH2CH2N(CONHR)CH2CH2NHCONHR [wherein R is stearyl] and 0.2 g of EO / PO polyalkylene glycol natural alcohol ether, grind the obtained solid in a mortar, add 17.8 g of water, and stir at 10000 rpm for 20 minutes using a homogenizer to obtain a water-dispersible composition of compound 6 (volume ratio of particles larger than 100 μm: 25.7%).

[0668] The water dispersion composition was added to a pulp slurry having a concentration of 0.5 wt % at a ratio of 10 wt % based on the solid content of the pulp to prepare an aqueous composition containing pulp. The aqueous composition containing pulp was placed in an automatic molding machine to prepare a pulp molded body.

[0669] The pulp molded body was subjected to a practical oil resistance test at -65°C, with a result of 5 points; a practical oil resistance test at -80°C, with a result of 5 points; and a practical water resistance test, with a result of 5 points.

[0670] <Example 18>

[0671] 2 g of N,N'-ethylenebisoctadecanoic acid amide, 1.2 g of benzalkonium chloride, 0.8 g of polyethylene glycol trimethyl nonyl ether, and 36 g of water were pulverized at 150 MPa using a wet micronizer to obtain a water-dispersible composition (volume ratio of particles larger than 100 μm: 0%, volume median diameter: 52 μm).

[0672] The water dispersion composition was added to a pulp slurry having a concentration of 0.5 wt % at a ratio of 10 wt % based on the solid content of the pulp to prepare an aqueous composition containing pulp. The aqueous composition containing pulp was placed in an automatic molding machine to prepare a pulp molded body.

[0673] The pulp molded body was subjected to a practical oil resistance test at -65°C and the result was 4 points.

[0674] <Example 19>

[0675] The biodegradability test of N,N'-ethylenebisoleamide (biobased content: 96%, melting point: 116°C) was carried out in accordance with JIS K 6953-1: 2011. The biodegradability was 65% at 30 days within the test period, and 77% at 60 days within the test period.

[0676] <Example 20>

[0677] Table 3 shows the measurement results of the HD contact angles (n-hexadecane contact angles) of N,N'-ethylenebisoctadecanoic acid amide, N,N'-ethylenebisoleic acid amide, N,N'-xylylene-bis-12-hydroxystearic acid amide, and N,N-ethylene-bis-12-hydroxystearic acid amide.

[0678] [Table 3]

[0679]

[0680] <<Improvement of paper strength of pulp molded articles by adding a dispersing agent>>

[0681] <Example 21>

[0682] The tensile strength of the pulp molded body made from Example 6 (N,N'-ethylenebisoctadecanoic acid amide), the pulp molded body made from Example 8 (N,N'-xylylene-bis-12-hydroxystearic acid amide), and the pulp molded body made from Example 12 (N,N-ethylene-bis-12-hydroxystearic acid amide) were evaluated. The results are shown in Table 4.

[0683] <Comparative Example 1>

[0684] The aqueous composition containing pulp was put into an automatic molding machine without adding a liquid-repellent compound to produce a pulp molded body. The tensile strength of the produced pulp molded body was evaluated. The results are shown in Table 4.

[0685] [Table 4. Evaluation results of tensile test of pulp molded body]

[0686]

[0687] As can be seen from Table 4, the liquid-repellent compound has the effect of increasing the tensile strength and improving the strength of the paper.

[0688] <<Improvement effect of paper strength of pulp molded article obtained by combined use of paper strength agent>>

[0689] <Example 22>

[0690] The aqueous dispersion composition of N,N'-xylylene-bis-12-hydroxystearamide prepared in Example 8 is added to a pulp slurry with a concentration of 0.5wt% at a ratio of 3wt% calculated as solid content relative to the pulp, and after stirring for 30 seconds, 0.1wt% of a polyacrylamide-based paper strength agent is added to the pulp and stirred for 30 seconds to prepare an aqueous composition containing pulp. The aqueous composition containing pulp is put into an automatic molding machine to prepare a pulp molded body. The pulp molded body was subjected to a practical oil resistance test at -65°C, and the result was 4 points. The tensile strength of the prepared pulp molded body was evaluated, and the results are shown in Table 5.

[0691] <Example 23>

[0692] The aqueous dispersion composition of N,N'-xylylene-bis-12-hydroxystearamide prepared in Example 8 is added to a pulp slurry with a concentration of 0.5wt% at a ratio of 3wt% calculated as solid content relative to the pulp, and after stirring for 30 seconds, 0.5wt% of a polyacrylamide-based paper strength agent is added to the pulp and stirred for 30 seconds to prepare an aqueous composition containing pulp. The aqueous composition containing pulp is put into an automatic molding machine to prepare a pulp molded body. The pulp molded body was subjected to a practical oil resistance test at -65°C, and the result was 4 points. The tensile strength of the prepared pulp molded body was evaluated, and the results are shown in Table 5.

[0693] <Example 24>

[0694] The aqueous dispersion composition of N,N'-xylylene-bis-12-hydroxystearamide prepared in Example 8 is added to a pulp slurry with a concentration of 0.5wt% at a ratio of 3wt% calculated as solid content relative to the pulp, and after stirring for 30 seconds, 0.5wt% of a polyacrylamide-based paper strength agent is added to the pulp and stirred for 30 seconds to prepare an aqueous composition containing pulp. The aqueous composition containing pulp is put into an automatic molding machine to prepare a pulp molded body. The pulp molded body was subjected to a practical oil resistance test at -65°C, and the result was 4 points. The tensile strength of the prepared pulp molded body was evaluated, and the results are shown in Table 5.

[0695] [Table 5. Evaluation results of tensile test of pulp molded body]

[0696]

[0697] <Example 25>

[0698] The aqueous dispersion composition of N,N'-xylene-bis-12-hydroxystearamide prepared in Example 8 was added to a pulp slurry with a concentration of 0.5wt% at a ratio of 3wt% in terms of solid content relative to the pulp, and stirred for 30 seconds. Then, a cationic starch aqueous solution was added at a solid content of 3wt% relative to the pulp and stirred for 30 seconds to prepare an aqueous composition containing pulp. The aqueous composition containing pulp was put into an automatic molding machine to prepare a pulp molded body. The pulp molded body was subjected to a practical oil resistance test at -65°C, and the result was 4 points.

[0699] <Example 26>

[0700] The water-dispersible composition of N,N'-xylene-bis-12-hydroxystearamide prepared in Example 8 was added to a pulp slurry with a concentration of 0.5wt% at a ratio of 3wt% in terms of solid content relative to the pulp, and stirred for 30 seconds. Then, 0.5wt% of alkyl ketene dimer as a sizing agent was added in terms of solid content relative to the pulp, and stirred for 30 seconds to prepare an aqueous composition containing pulp. The aqueous composition containing pulp was put into an automatic molding machine to prepare a pulp molded body. The pulp molded body was subjected to a practical oil resistance test at -65°C, and the result was 4 points.

[0701] <<Water repellency test of fabric treatment>>

[0702] <Example 27>

[0703] [Water repellency test]

[0704] Using N,N'-xylylene-bis-12-hydroxystearamide, chloroform was used as a solvent to prepare a treatment solution with a solid content concentration of 16.8 mg / mL. The PET cloth was immersed in the treatment solution and then passed through a cloth mangle to air-dry at room temperature for 24 hours. After that, it was heat-treated at 140°C for 5 minutes and cooled to room temperature to prepare a test cloth. The test cloth was used to evaluate water repellency. The result of the water repellency test showed that the water repellency was 90 points.

[0705] <<Extraction of compounds from pulp molded bodies and 1 H NMR measurement >>

[0706] <Example 28>

[0707] A pulp molded body to which N,N'-ethylenebisoctadecanoic acid amide was added was prepared in the same manner as in Example 6. Ten slices with a diameter of 3 mm were cut from the bottom surface of the pulp molded body using a 3 mm diameter drilling punch. The ten slices were placed in a 2 mL reagent bottle, 2 g of CDCl3 was added, the lid was closed, and the mixture was heated at 60°C for 1 hour. CDCl3 was transferred from the reagent bottle into an NMR tube and measured. 1 H NMR results were as follows: 1 H NMR spectrum.

[0708] 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)

[0709] <Example 29>

[0710] A pulp molded body to which N,N'-ethylenebisoleamide was added was prepared in the same manner as in Example 7. 1 H NMR measurement gave the following results. 1 H NMR spectrum.

[0711] 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)

[0712] <Example 30>

[0713] A pulp molded body to which N,N'-xylylene-bis-12-hydroxystearamide was added was prepared in the same manner as in Example 9. 1 H NMR measurement gave the following results. 1 H NMR spectrum.

[0714] 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. A dilution agent, characterized in that: It contains liquid-repellent compounds, The liquid repellent compound has: an amine backbone; and One or more of the following formula: -X-R n The long-chain hydrocarbon-containing groups shown, In the formula, X is a direct bond or a 1+n valent group, R, when present, is independently a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, n is an integer from 1 to 3, At least one of the long-chain hydrocarbon-containing groups is bonded to a nitrogen atom possessed by the amine skeleton.

2. The dilution agent according to claim 1, characterized in that The amine skeleton is composed of monovalent to trivalent amino groups and chain-like saturated aliphatic hydrocarbon groups or aromatic hydrocarbon groups which may be interrupted by oxygen atoms and / or sulfur atoms.

3. The dilution agent according to claim 1 or 2, characterized in that: The molar ratio of carbon atoms to nitrogen atoms (C / N ratio) in the amine skeleton is 8 or less.

4. The expelling agent according to any one of claims 1 to 3, characterized in that The liquid repellent compound is of the following formula: N(-XR n ) p (-H) q -L 1 -[N(-XR n ) r (-H) s -L 1 -] t -N(-XR n ) p (-H) q The compound shown, or the following formula: N(-XR n ) p (-H) q -L 2 (-XR n ) u The compounds shown, Formula: N(-XR n ) p (-H) q -L 1 -[N(-XR n ) r (-H) s -L 1 -] t -N(-XR n ) p (-H) q middle, X is independently a direct bond or a 1+n-valent group at each occurrence, R, when present, is independently a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, L 1 is independently, at 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 an integer from 1 to 3 at each occurrence, p is independently an integer from 0 to 2 at each occurrence, q is independently an integer from 0 to 2 at each occurrence, p+q in each N(-XR n ) p (-H) q The middle is 2, r is independently 0 or 1 at each occurrence, s is independently 0 or 1 at each occurrence, r+s in each N(-XR n ) r (-H) s The middle is 1, The sum of all p's and all r's is greater than 1, t is an integer greater than or equal to 0 and less than or equal to 10; Formula: N(-XR n ) p (-H) q -L 2 (-XR n ) u middle, X is independently a direct bond or a 1+n-valent group at each occurrence, R, when present, is independently a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, L 2 is a 1+u-valent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by oxygen atoms and / or sulfur atoms, n is independently an integer from 1 to 3 at each occurrence, p is an integer from 0 to 2, q is an integer from 0 to 2, p+q is 2, u is an integer from 1 to 3, The total of p and u is 1 or more.

5. The expelling agent according to any one of claims 1 to 4, characterized in that The number of carbon atoms in R is 12 or more.

6. The expelling agent according to any one of claims 1 to 5, characterized in that X is a direct bond, a 1+n-valent group consisting of one or more selected from -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2, a 2- to 4-valent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a 2- to 4-valent aromatic hydrocarbon ring, and a 2- to 4-valent heterocyclic ring, In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

7. The expelling agent according to any one of claims 1 to 6, characterized in that The lyophobic compound has a melting point of 40° C. or higher or has no melting point.

8. The expelling agent according to any one of claims 1 to 7, characterized in that The liquid repellent compound has a n-hexadecane contact angle of 10° or more.

9. The expelling agent according to any one of claims 1 to 8, characterized in that The bio-based content of the liquid repellent compound is greater than 30%.

10. The expelling agent according to any one of claims 1 to 9, characterized in that The volume abundance ratio of particles having a size of 100 μm or more measured by a dynamic light scattering method or a laser diffraction scattering method is 25% or less.

11. The expelling agent according to any one of claims 1 to 10, characterized in that It is an aqueous dispersion.

12. The dilution agent according to claim 11, characterized in that: It contains at least one selected from a surfactant, silicone, wax, organic acid and curing agent.

13. The expelling agent according to any one of claims 1 to 12, characterized in that It is a paper exfoliant.

14. The expelling agent according to any one of claims 1 to 13, characterized in that It contains no fluorinated compounds.

15. A fiber product, characterized in that: The liquid repellent compound in the repellent according to any one of claims 1 to 14 is adhered thereto.

16. An oil-resistant paper or water-repellent paper, characterized in that: The liquid repellent compound in the repellent according to any one of claims 1 to 14 is adhered thereto.

17. A glass, characterized in that: The liquid repellent compound in the repellent according to any one of claims 1 to 14 is adhered thereto.

18. The oil-resistant paper or water-repellent paper according to claim 16, characterized in that: It is a food packaging material or a food container.

19. A method for producing oil-resistant paper or water-repellent paper, characterized in that: The method comprises the step of using the expelling agent according to any one of claims 1 to 14 to perform an external addition treatment or an internal addition treatment on paper.

20. A formula: N(-XR n ) p (-H) q -L 1 -[N(-XR n ) r (-H) s -L 1 -] t -N(-XR n ) p (-H) q The compound shown, or the following formula: N(-XR n ) p (-H) q -L 2 (-XR n ) u The compounds shown, Formula: N(-XR n ) p (-H) q -L 1 -[N(-XR n ) r (-H) s -L 1 -] t -N(-XR n ) p (-H) q middle, X is independently a direct bond or a 1+n-valent group at each occurrence, R, when present, is independently a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, L 1 is independently, at each occurrence, a divalent aliphatic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by oxygen atoms and / or sulfur atoms, n is independently an integer from 1 to 3 at each occurrence, p is independently an integer from 0 to 2 at each occurrence, q is independently an integer from 0 to 2 at each occurrence, p+q in each N(-XR n ) p (-H) q The middle is 2, r is independently 0 or 1 at each occurrence, s is independently 0 or 1 at each occurrence, r+s in each N(-XR n ) r (-H) s The middle is 1, The sum of all p's and all r's is greater than 1, t is an integer greater than or equal to 2 and less than or equal to 10; Formula: N(-XR n ) p (-H) q -L 2 (-XR n ) u middle, X is independently a direct bond or a 1+n-valent group at each occurrence, R, when present, is independently a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, L 2 is a 1+u-valent aliphatic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by oxygen atoms and / or sulfur atoms, n is independently an integer from 1 to 3 at each occurrence, p is an integer from 0 to 2, q is an integer from 0 to 2, p+q is 2, u is an integer from 1 to 3, The total of p and u is 1 or more.

21. A formula: The compounds shown, In the formula, R is a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent.

22. A formula: The compounds shown, In the formula, R is a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent.

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