Applicator

Abstract

Provided is a novel agent for imparting liquid repellency, which imparts liquid repellency to a substrate (e.g., a fiber product and / or a pulp product) and contains a liquid repellency-imparting compound having a moiety derived from a compound (a) having a structure in which a carbon atom or a nitrogen atom of an amide group or a urea group is bonded to a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms that can have a substituent and 1 or more reactive groups, and a moiety derived from a compound (b) having 2 or more reactive groups and not having a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms.

Description

Technical Field

[0001] This invention relates to dispensing agents. Background Technology

[0002] In recent years, non-fluorinated repellents have been developed that can impart liquid-repellent properties (water repellency, oil repellency, oil resistance and / or water resistance) to various substrates.

[0003] Existing technical documents Patent documents Patent Document 1: Japanese Patent Publication No. 2016-524628 Summary of the Invention

[0004] The problem that the invention aims to solve The inventors conducted in-depth research to determine whether there was still room for development in imparting liquid-repellent properties to substrates. The results showed that there is still room for development in imparting liquid-repellent properties to substrates using novel liquid-repellent compounds that differ from previous methods.

[0005] The object of this invention is to provide a novel repellent that can impart repellency to substrates (e.g., fiber products and / or pulp products).

[0006] Technical solutions for solving the problem This invention includes the following methods: [Item 1] A repellent agent comprising a repellent compound having portions derived from compound (a) and portions derived from compound (b). The above compound (a) has a structure in which a monovalent hydrocarbon group with 6 to 40 carbon atoms, which may have substituents, is bonded to the carbon or nitrogen atom of the amide or urea group, and has one or more reactive groups. The above compound (b) does not have a monovalent hydrocarbon group with 6 to 40 carbon atoms that can have substituents, but has two or more reactive groups.

[0007] [Item 2] The dissolving agent as described in item 1, wherein the portion from compound (a) and the portion from compound (b) are bonded together by groups or direct bonds as shown in the following formula, -X 1 -CO-X 2 - [In the formula,] X 1 and X 2 Each group is independently directly bonded and consists of one or more groups selected from -O- and -NH-. [Item 3] The dispensing agent as described in item 2, wherein X1 and X 2 One of them is -NH-.

[0008] [Item 4] The dispensing agent as described in any one of items 1 to 3, wherein the compound (a) comprises at least one group selected from the groups represented by the following formulas respectively. -NR 1 -CO-R 2 , -CO-NR 1 -R 2 , -NH-CO-NR 1 -R 2 ,and -NR 1 -CO-NH-R 2 [In the formula,] R 1 Each is independently a hydrogen atom or a monovalent hydrocarbon group with 1 to 20 carbon atoms that may have substituents. R 2 Each can be independently a monovalent hydrocarbon group with 6 to 40 carbon atoms, which may have substituents. [Item 5] The dissolving agent as described in any one of items 1 to 4, wherein the compound (a) is a polyamine modifier, which is formed by modifying the amino group of the polyamine with a monovalent hydrocarbon group having a substituent of 6 to 40 carbon atoms, and having one or more amino groups or derivatives thereof.

[0009] [Item 6] The repellent as described in item 5, wherein the polyamine modifier is a compound represented by the following formula. N(R 3 ) l (-H) m -L 1 - [NR] 1 -L 1 -] t -N(-CO-R) 2 ) p (-H) q [In the formula,] L 1 Each can be an aliphatic or aromatic hydrocarbon group with 2 to 20 carbon atoms and may have substituents. R 1 Each is independently a hydrogen atom or a monovalent aliphatic hydrocarbon group with 1 to 20 carbon atoms that may have substituents. R 2Each can be independently a monovalent hydrocarbon group with 6 to 40 carbon atoms that can have substituents. R 3 Each is independently a hydrogen atom, a monovalent aliphatic hydrocarbon group with 1 to 20 carbon atoms that may have substituents, or -CO-R. 2 , t is an integer greater than 0 and less than 10. p is an integer greater than 1 and less than 2. q is an integer greater than 0 and less than 2. p + q = 2 l is an integer greater than 0 and less than 2. m is an integer greater than 0 and less than 2. l + m equals 2. [Item 7] The dispensing agent as described in any one of items 1 to 4, wherein the compound (a) is a polycarboxylic acid modified body, which is formed by modifying the carboxyl group of the polycarboxylic acid with a monovalent hydrocarbon group having a substituent of 6 to 40 carbon atoms, and has one or more carboxyl groups or derivatives thereof.

[0010] [Item 8] The dispensing agent as described in item 7, wherein the aforementioned polycarboxylic acid modified body comprises a compound represented by the following formula. A{-CONR 1 -R 2} n {-COOH} m [In the formula,] A is an aliphatic hydrocarbon group with 1 to 20 carbon atoms in the range of 2 to 4 valences, or an aromatic hydrocarbon group in the range of 2 to 4 valences. R 1 Each is an aliphatic hydrocarbon group, consisting independently of one or more hydrogen atoms or fewer than 20 carbon atoms, either straight-chain or branched. R 2 Each can be independently a monovalent hydrocarbon group with 6 to 40 carbon atoms that can have substituents. n is an integer greater than 1 and less than 4. m is an integer greater than 1 and less than 4. [n + m is an integer greater than 2 and less than 4.] [Item 9] The repellent as described in any one of items 1 to 8, wherein the aforementioned repellent compound further comprises a portion derived from compound (c). The above compound (c) is Monocarboxylic acids and their derivatives having a monovalent hydrocarbon group having 6 to 40 carbon atoms that can have substituents. Monoamines and their derivatives having a monovalent hydrocarbon group with 6 to 40 carbon atoms that can have substituents.

[0011] [Item 10] As described in item 1, wherein compound (a) is a polyamine modified by having a monovalent hydrocarbon group with 6 to 40 carbon atoms that can be substituented by modifying the amino group of the polyamine, and compound (b) is a polycarboxylic acid without a monovalent hydrocarbon group with 6 to 40 carbon atoms that can be substituented. The portions from compound (a) and compound (b) are bonded together by the groups shown in the following formula. -X 1 -CO-X 2 - [In the formula,] X 1 and X 2 Each group is independently directly bonded and consists of one or more groups selected from -O- and -NH-. [Item 11] The dispensing agent as described in any one of items 1 to 10, wherein the compounds (a) and (b) are compounds other than sugar alcohols.

[0012] [Item 12] The repellent as described in any one of items 1 to 11, wherein the aforementioned repellent compound does not have fluorine atoms.

[0013] [Item 13] The dispensing agent as described in any one of items 1 to 12, wherein it is an organic solvent solution, an organic solvent dispersion, or an aqueous dispersion.

[0014] [Item 14] A method for manufacturing a fiber product includes a step of applying the agent described in any one of items 1 to 13 to a fiber substrate.

[0015] [Item 15] A fiber article having a repellent compound of any one of the repellents described in claims 1 to 13 attached to a fiber substrate.

[0016] Invention Effects The present invention provides a novel repellent agent capable of imparting liquid-repellent properties to a substrate. Detailed Implementation

[0017] <Definition of Terms> When used in this specification, "n-valent group" refers to a group having n bonding hands, that is, a group forming n bonds. Additionally, "n-valent organic group" refers to an n-valent group containing carbon. There is no particular limitation on such organic groups; they can be hydrocarbon groups or their derivatives. Derivatives of hydrocarbon groups refer to groups having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, or other atoms at the end of the hydrocarbon group or in the molecular chain.

[0018] When used in this specification, "hydrocarbon group" refers to a group containing carbon and hydrogen, specifically a group formed by the removal of a hydrogen atom from a hydrocarbon. There are no particular limitations on what constitutes such a hydrocarbon group; examples include C. 1－20 Hydrocarbon groups, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The aforementioned "aliphatic hydrocarbon group" can be any type of linear, branched, or cyclic structure, and can be any type of saturated or unsaturated structure. Furthermore, a hydrocarbon group can also contain one or more ring structures. Where explicitly stated, a hydrocarbon group can be substituted by one or more substituents.

[0019] In this specification, whether or not expressions such as "independently in each occurrence," "independently each other," "independently each other," or the like are explicitly stated, unless otherwise stated, when defining terms (symbols) that may appear multiple times in a chemical structure, each occurrence is defined independently.

[0020] The chemical structures described in this specification should be understood to exclude chemical structures that are chemically impossible or extremely unstable in the view of those skilled in the art.

[0021] <Dispensing Agent> The repellent of the present invention adheres to a substrate (particularly a fiber substrate and / or pulp substrate) and imparts liquid-repellent properties, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the substrate. It can also function as a water-resistant agent, oil-resistant agent, water-repellent agent, oil-repellent agent, and / or stain-resistant agent. The repellent of the present invention is particularly suitable as an oil-resistant agent for imparting oil resistance to a substrate (particularly a fiber substrate and / or pulp substrate).

[0022] The repellent of the present invention contains a liquid-repellent compound having a portion from compound (a) and a portion from compound (b). Compound (a) has a structure in which a monovalent hydrocarbon group with 6 to 40 carbon atoms that may have substituents is bonded to a carbon atom or nitrogen atom of an amide or urea group, and has one or more reactive groups. Compound (b) does not have a monovalent hydrocarbon group with 6 to 40 carbon atoms that may have substituents, but has two or more reactive groups.

[0023] The repellent of the present invention can adhere to a substrate (especially fiber products and / or pulp products) and impart good liquid repellency to the substrate.

[0024] The repellent of the present invention may not contain any of the following: compounds selected from fluoroalkyl compounds having 8 or more carbon atoms, perfluoroalkyl compounds having 8 or more carbon atoms, fluoroalkyl compounds having 4 or more carbon atoms, perfluoroalkyl compounds having 4 or more carbon atoms, perfluoroalkyl compounds, fluoroalkyl compounds, and compounds containing fluorine atoms. Even without these fluorine compounds, the repellent of the present invention can impart liquid-repellent properties to the substrate.

[0025] The volume fraction of particles larger than 100 μm, as measured by laser diffraction scattering, in the dispersant of the present invention can be 0.1% or more, 0.3% or more, 0.5% or more, 1% or more, 1.5% or more, 3% or more, 4% or more, 5% or more, or 10% or more, and can be less than 50%, less than 30%, less than 20%, less than 15%, less than 10%, less than 5%, less than 3%, or less than 1.5%, preferably less than 20%, and more preferably less than 5%. The method for achieving such a particle volume fraction within the above range is not limited; for example, the particles in the raw material and / or dispersion can be fined using a pulverizer or homogenizer.

[0026] The volume fraction of particles larger than 10 μm, as measured by laser diffraction scattering, in the dispersant of the present invention can be 0.1% or more, 0.3% or more, 0.5% or more, 1% or more, 1.5% or more, 3% or more, 4% or more, 5% or more, or 10% or more, and can be less than 50%, less than 30%, less than 20%, less than 15%, less than 10%, less than 5%, less than 3%, or less than 1.5%, preferably less than 30%, more preferably less than 15%. The method for achieving such a particle volume fraction within the above range is not limited; for example, the particles in the raw material and / or dispersion can be fined using a pulverizer or homogenizer.

[0027] The median volumetric particle size of the dispersant of the present invention, measured by laser diffraction scattering, can be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, and can be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less, and in one embodiment, 0.01 μm or more or 1 μm or less. In the present invention, the median volumetric particle size refers to the median particle size (D50) in the particle size distribution of the volumetric reference obtained by laser diffraction scattering.

[0028] [Liquid-repellent compounds] The liquid-repellent compound of the present invention has a portion from compound (a) and a portion from compound (b). Compound (a) has a structure in which a monovalent hydrocarbon group with 6 to 40 carbon atoms that may have substituents is bonded to the carbon or nitrogen atom of an amide or urea group, and has one or more reactive groups. Compound (b) does not have a monovalent hydrocarbon group with 6 to 40 carbon atoms that may have substituents, but has two or more reactive groups.

[0029] The liquid-repellent compound of the present invention is a compound obtained by reacting compound (a) with compound (b), having a portion from compound (a) and a portion from compound (b).

[0030] Specifically, the present invention’s liquid-repellent compound is formed by reacting the reactive groups of compound (a) with the reactive groups of compound (b).

[0031] An organic group is formed between the portion from compound (a) and the portion from compound (b) through the reaction of the reactive groups of compound (a) and compound (b). Such an organic group can be at least one selected from amide, urea, ester, and carbamate groups. These groups can improve the film-forming properties of the adhesive to the substrate.

[0032] The moiety from compound (a) and the moiety from compound (b) can be bonded together by groups or by direct bonding as shown in the following formula: -X 1 -CO-X 2 - [In the formula,] X 1 and X 2Each group is independently directly bonded and consists of one or more groups selected from -O- and -NH-. [X] 1 ] X 1 Each is independently directly bonded and consists of one or more groups selected from -O- and -NH-.

[0033] [X] 2 ] X 2 Each is independently directly bonded and consists of one or more groups selected from -O- and -NH-.

[0034] [-X] 1 -CO-X 2 -Example] As -X 1 -CO-X 2 Examples of this can be listed. -CO-O- -CO-NH- -O-CO- -O-CO-NH- -NH-CO- -NH-CO-O-, or -NH-CO-NH-.

[0035] In addition, in this invention, -CO- can refer to -C(=O)-.

[0036] X 1 and X 2 One of them can be -NH-.

[0037] The repellent of the present invention contains a liquid-repellent compound. The liquid-repellent compound of the present invention adheres to a substrate (particularly a fiber substrate and / or a pulp substrate) and imparts liquid-repellent properties, such as water resistance, oil resistance, water repellency, oil repellency and / or stain resistance, particularly oil resistance, to the substrate.

[0038] [Characteristics, etc.] The properties that liquid-repellent compounds can possess are described below.

[0039] The HD (n-hexadecane) contact angle of the liquid-repellent compound can be 10° or more, 20° or more, 25° or more, 30° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 60° or more, or 65° or more, preferably 25° or more, more preferably 30° or more, and can be 100° or less, 90° or less, or 75° or less. By giving the liquid-repellent compound an HD contact angle of the lower limit mentioned above, it is possible to impart good liquid-repellent properties (especially oil-repellent properties) to the substrate. The HD contact angle is the static contact angle relative to the spin-coated film of the liquid-repellent compound, which is the value obtained by dropping 2 μL of HD onto the spin-coated film at room temperature (25°C) and measuring the contact angle 1 second after dropping.

[0040] The water contact angle of a liquid-repellent compound can be 35° or higher, 40° or higher, 50° or higher, 55° or higher, 65° or higher, 75° or higher, 85° or higher, 90° or higher, or 100° or higher, and can be less than 160°, less than 140°, less than 130°, less than 120°, less than 110°, less than 100°, or less than 90°. By giving the liquid-repellent compound a water contact angle of the lower limit mentioned above, it is possible to impart good liquid-repellent properties (especially water-repellent properties) to the substrate. The water contact angle is the static contact angle relative to the spin-coated film of the liquid-repellent compound, which is the value obtained by adding 2 μL of water to the spin-coated film at room temperature (25°C) and measuring the contact angle after 1 second.

[0041] The repellent compound is preferably a bio-based compound with carbon of bio-based origin. The bio-based content is determined according to ASTM D6866. The bio-based content can be 20% or more, preferably 30% or more, more preferably 50% or more, further preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example, 100%. A high bio-based content means less use of fossil resources such as petroleum; from this perspective, a higher bio-based content of the repellent compound is preferable.

[0042] The biodegradability of the liquid-repellent compound at 180 days is preferably 5% or more. Higher biodegradability is preferred due to reduced environmental impact. The biodegradability of the liquid-repellent compound at 180 days can 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 30% or more, more preferably 50% or more, further preferably 70% or more, and most preferably 80% or more. The biodegradability of the liquid-repellent compound at 60 days is preferably 5% or more. Higher biodegradability is preferred due to reduced environmental impact. The biodegradability of the liquid-repellent compound at 60 days can 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 10% or more, more preferably 30% or more. Such biodegradability can be as specified in JIS K 6953-1 or ASTM D6400.

[0043] Liquid-repellent compounds can be low molecular weight (e.g., weight-average molecular weight less than 1500, less than 1000, less than 500) and / or high molecular weight. The weight-average molecular weight of the liquid-repellent compound can be above 100, above 200, above 300, above 400, above 500, above 1000, above 3000, above 5000, above 10000, above 30000, above 100000, above 300000, above 300000, or above 500000. It can also be below 1,000,000, below 750,000, below 500,000, below 300,000, below 100,000, below 75,000, below 50,000, below 30,000, below 10,000, below 9,000, below 8,000, below 7,000, below 6,000, below 5,000, below 3,000, below 2,000, below 1,000, or below 500.

[0044] [(a) compound] The liquid-repellent compound has a portion derived from compound (a), which has a structure in which a monovalent hydrocarbon group with 6 to 40 carbon atoms that may have substituents is bonded to the carbon or nitrogen atom of the amide or urea group, and one or more reactive groups.

[0045] [Structure, etc.] Compound (a) may not have any of the following: a compound having 8 or more carbon atoms, a compound having 8 or more carbon atoms, a compound having 4 ...

[0046] Compound (a) can be a compound other than a sugar alcohol. For example, compound (a) can be a compound that does not have a sugar alcohol skeleton. A sugar alcohol is a polyol formed by reducing the aldehyde and ketone groups of a sugar to alcohol groups. Examples of sugar alcohols include sorbitol, xylitol, maltitol, erythritol, and mannitol. The sugar alcohol skeleton refers to the molecular structure of a cyclic or acyclic sugar alcohol when one or more H atoms are removed from the hydroxyl group (-OH).

[0047] [Amide or urea group] Compound (a) has a structure in which a monovalent hydrocarbon group, having a number of carbon atoms of 6 to 40, may have substituents, is bonded to a carbon atom or nitrogen atom of an amide or urea group.

[0048] In compound (a), the carbon or nitrogen atom of the amide or urea group may be independently bonded to a monovalent hydrocarbon group with a number of carbon atoms of 6 to 40, which may have a substituent, or may be bonded to two or more.

[0049] A monovalent hydrocarbon group with 6 to 40 carbon atoms that can have a substituent can be attached to the nitrogen or carbon atom of the amide group.

[0050] A monovalent hydrocarbon group with 6 to 40 carbon atoms that can have a substituent can be attached to the nitrogen atom of an amide group.

[0051] A monovalent hydrocarbon group with 6 to 40 carbon atoms that can have a substituent can be attached to the carbon atom of an amide group.

[0052] A monovalent hydrocarbon group with 6 to 40 carbon atoms that can have a substituent can be attached to the nitrogen atom of the urea group.

[0053] Compound (a) may have one or more amide or urea groups that are monovalent hydrocarbon groups with a number of carbon atoms of 6 to 40 or more and may have substituents. For example, it may have two or more, three or more, or five or fewer, four or fewer, or three or fewer, typically one.

[0054] (Can be a monovalent hydrocarbon group with 6 to 40 carbon atoms that has a substituent) The hydrocarbon group can be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and aliphatic hydrocarbon groups, such as saturated or unsaturated aliphatic hydrocarbon groups (alkyl, alkenyl, etc.), are particularly examples. The hydrocarbon group can be branched, cyclic, or linear, and linear is more preferred.

[0055] The hydrocarbon group is typically monovalent and can be located at the end of the molecule. The end of the hydrocarbon group can have one or more methyl groups. In addition, in this specification, hydrocarbon compounds (e.g., hydrocarbon waxes) are understood to consist only of a monovalent hydrocarbon group and one hydrogen atom. For example, a 20-carbon n-alkane (eicosane) is understood to consist only of a 20-carbon alkyl group and one hydrogen atom.

[0056] The number of carbon atoms in the hydrocarbon group can be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 6 or more, 10 or more, 12 or more, or 16 or more, and can be 75 or less, 65 or less, 60 or less, 50 or less, 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 40 or less, 30 or less, 25 or less, or 20 or less. In one embodiment, it is 6 or more and 60 or less, 6 or more and 40 or less, 12 or more and 30 or less, or 12 or more and 20 or less. The number of carbon atoms in the hydrocarbon group can typically be 6 or more and 40 or less.

[0057] The hydrocarbon group may have substituents, but is preferably unsubstituented. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (where R' in each occurrence is independently a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms, respectively). The substituents may or may not have active hydrogen. 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 with substituents, the amount of carbon atoms 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 (e.g., 1) -OR' (especially -OH) (e.g., at positions other than the terminal) as substituents.

[0058] Compound (a) may contain at least one group selected from the groups shown in the following formulas: -NR 1 -CO-R 2 , -CO-NR 1 -R 2 , -NH-CO-NR 1 -R 2 ,and -NR 1 -CO-NH-R 2 [In the formula,] R 1 Each is independently a hydrogen atom or a monovalent hydrocarbon group with 1 to 20 carbon atoms that may have substituents. R 2 Each can be independently a monovalent hydrocarbon group with 6 to 40 carbon atoms, which may have substituents. In addition, the above R 2 It is a group attached to the carbon or nitrogen atom of an amide or urea group.

[0059] In the above formula, -NR 1 -CO-R 2 and -CO-NR 1 -R 2 It refers to a structure in which a monovalent hydrocarbon group with 6 to 40 carbon atoms that can have substituents is bonded to the nitrogen or carbon atom of the amide group.

[0060] In the above formula, -NH-CO-NR 1 -R 2 and -NR 1 -CO-NH-R 2 It refers to a structure in which a monovalent hydrocarbon group with 6 to 40 carbon atoms that can have substituents is bonded to the nitrogen atom of the urea group.

[0061] R 1 Each group is a monovalent hydrocarbon group consisting of 1 to 20 carbon atoms, which may be independently hydrogen atoms or may have substituents. The aliphatic hydrocarbon group, consisting of 1 to 20 carbon atoms, can be either straight-chain or branched.

[0062] Aliphatic hydrocarbons with 1 to 20 carbon atoms can have 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more carbon atoms, and can also have fewer than 20, 18, 16, 14, 12, 10, 8, 6, 4, or 3 carbon atoms.

[0063] Aliphatic hydrocarbons with 1 to 20 carbon atoms may have substituents, but are preferably unsubstituented. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (where R' in each occurrence is independently a hydrogen atom or a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms, respectively). Substituents may or may not have active hydrogen. 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 hydrocarbon groups with substituents, 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, a hydrocarbon group can be a substituent with 1 to 3 (e.g., 1) -OR' (especially -OH) (e.g., at a position other than the terminal).

[0064] R 2 Each can be a monovalent hydrocarbon group with 6 to 40 carbon atoms, which can independently have substituents. 2 Referring to the above description (which allows for a monovalent hydrocarbon group with 6 to 40 carbon atoms having substituents), it is preferable that the hydrocarbon group does not have substituents. Here, the hydrocarbon group is a monovalent group. The hydrocarbon group in compound (a) can be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, and particularly preferably a saturated aliphatic hydrocarbon group (alkyl). The hydrocarbon group can be branched or linear, more preferably linear. The hydrocarbon group can be saturated or unsaturated. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl). The number of carbon atoms in the hydrocarbon group can be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 10 or more, 12 or more, 14 or more, or 16 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, 25 or less, or 20 or less.

[0065] [Reactive groups] Compound (a) has more than one reactive group. The reactive group in compound (a) is a different reactive group from the reactive group in compound (b).

[0066] The reactive groups present in compound (a) may include hydroxyl, amino, carboxyl, isocyanate and their derivatives, but typically amino or carboxyl.

[0067] The reactive group of compound (a) can be a reactive group that reacts with the reactive group of compound (b) to form an amide group, a urea group, an ester group or a carbamate group, preferably a reactive group that forms an amide group or a urea group.

[0068] Compound (a) may have one or more reactive groups, or two or more, three or more, four or more or five or more, or less than ten, eight or less, six or less, five or less or three or less, and in one manner, one or more or five or more or three or less.

[0069] [Polyamine modified form] Compound (a) can be a polyamine modified. Specifically, compound (a) is a compound formed by modifying the amino group of a polyamine with a monovalent hydrocarbon group having 6 to 40 carbon atoms, and may have one or more amino groups or derivatives thereof.

[0070] The polyamine modifier can be a compound obtained by reacting a fatty acid with a monovalent hydrocarbon group having 6 to 40 carbon atoms that may have substituents with a polyamine, and can have one or more amino groups.

[0071] The polyamine modifier can be a polyamine modifier having one or more amide structures. For example, it can be a polyamide formed by modifying a p-amine (a starting amine compound, such as a polyamine) via an amide structure through one or more modifying groups. Here, the amide can be an amide structure contained in urethane groups, urea groups, imides, etc. The polyamine modifier can have a structure in which a monovalent hydrocarbon group with 6 to 40 carbon atoms, which may have substituents, is bonded to the carbon atom of the amide group.

[0072] The modifying group is preferably a hydrocarbon group with 6 to 40 monovalent carbon atoms that can have a substituent.

[0073] Compound (a) can be a compound formed by modifying the amino group of a polyamine with a monovalent hydrocarbon group having 6 to 40 carbon atoms as a substituent. Here, the monovalent hydrocarbon group having 6 to 40 carbon atoms as a substituent is explained above (the monovalent hydrocarbon group having 6 to 40 carbon atoms as a substituent).

[0074] Compound (a) may have one or more amino groups or derivatives thereof. Here, one or more amino groups or derivatives thereof are the reactive groups of the present invention.

[0075] Polyamine modifiers possess an amine skeleton. An amine skeleton refers to one or more amino groups with a specified number of bonding arms (valences), obtained by removing a specified number of atoms or groups of atoms (e.g., hydrogen) from an amine compound. The amino group in the amine skeleton is selected from -NH₂, -NH₻, and -N(-)₂, and also includes amino groups adjacent to carbonyl groups contained in amide groups, urethane groups, urea groups, imides, etc. Furthermore, the amine skeleton only needs to be an aliphatic or aromatic group having one or more amino groups; the presence of heteroatoms other than nitrogen is not excluded.

[0076] The weight-average molecular weight of the amine skeleton can be above 30, above 50, above 100, above 200, above 300, above 400, or above 500, and can be below 2800, below 2500, below 2000, below 1500, below 1000, below 750, below 600, below 450, below 300, or below 250.

[0077] 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 less than 100, less than 80, less than 60, less than 40, less than 30, less than 20, less than 10, or less than 5, preferably less than 50, and particularly less than 30.

[0078] The amine skeleton has one or more amino groups. The amino group is a 1- to 3-valent amino group, selected from one or more groups of -NH2, -NH- and -N(-)2. The number of amino groups in the amine skeleton can be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, preferably 2 or more, and can be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0079] The molar ratio (C / N ratio) of carbon atoms to nitrogen atoms in the amine skeleton can be 1 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, or 4 or more, and can be 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, or 2 or less, preferably 6 or less or 4 or less.

[0080] When compound (a) is a polyamine modifier, the portion from compound (a) may be a structure formed by removing at least one hydrogen atom bonded to a nitrogen atom of the polyamine modifier, or a structure formed by removing at least one nitrogen atom of the polyamine modifier and a hydrogen atom bonded to that nitrogen atom.

[0081] (Examples of polyamine modifiers) The polyamine modifier can be a compound as shown in the following formula: N(R 3 )l (-H) m -L 1 - [NR] 1 -L 1 -] t -N(-CO-R) 2 ) p (-H) q [In the formula,] L 1 Each can be an aliphatic or aromatic hydrocarbon group with 2 to 20 carbon atoms and may have substituents. R 1 Each is independently a hydrogen atom or a monovalent aliphatic hydrocarbon group with 1 to 20 carbon atoms that may have substituents. R 2 Each can be independently a monovalent hydrocarbon group with 6 to 40 carbon atoms that can have substituents. R 3 Each is independently a hydrogen atom, a monovalent aliphatic hydrocarbon group with 1 to 20 carbon atoms that may have substituents, or -CO-R. 2 , t is an integer greater than 0 and less than 10. p is an integer greater than 1 and less than 2. q is an integer greater than 0 and less than 2. p + q = 2 l is an integer greater than 0 and less than 2. m is an integer greater than 0 and less than 2. l + m equals 2. L 1 Each can be an aliphatic or aromatic hydrocarbon group with 2 to 20 carbon atoms and may have substituents. 1 It can be a cyclic, branched, or straight-chain hydrocarbon group, preferably a chain hydrocarbon group or an aromatic hydrocarbon.

[0082] L 1 The number of carbon atoms can be independently 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 less than 20, less than 18, less than 16, less than 14, less than 12, less than 10, less than 8, less than 6, less than 4, or less than 3.

[0083] The divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms may have substituents. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (where R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms, respectively). The substituents may or may not have active hydrogen. 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 divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms with substituents, the amount of carbon atoms 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, a hydrocarbon group can be a substituent having 1 to 3 (e.g., 1) -OR' (especially -OH) (e.g., at the end).

[0084] R 1 Each is an independent hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms that may have substituents. R 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 less than 20, less than 18, less than 16, less than 14, less than 12, less than 10, less than 8, less than 6, less than 4, or less than 3.

[0085] Monovalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms may have substituents. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (where R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms, respectively). Substituents may or may not have active hydrogen. 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 monovalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms with substituents, the amount of carbon atoms 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, a hydrocarbon group can be a substituent having 1 to 3 (e.g., 1) -OR' (especially -OH) (e.g., at the end).

[0086] R 2Each is independently a monovalent hydrocarbon group having 6 to 40 carbon atoms that can have substituents. The explanation above (monovalent hydrocarbon groups having 6 to 40 carbon atoms that can have substituents) is relevant.

[0087] t is an integer greater than or equal to 0 and less than or equal to 10. t can be greater than or equal to 0, greater than or equal to 1, greater than or equal to 2, greater than or equal to 4, greater than or equal to 4, greater than or equal to 4, greater than or equal to 4, less than or equal to 2, less than or equal to 1, for example, 0 or 1.

[0088] In each occurrence, p is an integer greater than or equal to 1 and less than or equal to 2, and q is an integer greater than or equal to 0 and less than or equal to 2, and p + q equals 2. Preferably, p can be greater than or equal to 1 in each occurrence, for example, 2.

[0089] R 3 Each is independently a hydrogen atom, a monovalent aliphatic hydrocarbon group with 1 to 20 carbon atoms that may have substituents, or -CO-R. 2 Here, regarding monovalent aliphatic hydrocarbon groups with 1 to 20 carbon atoms that can have substituents, refer to the above-mentioned R... 1 The content in the text is "a monovalent aliphatic hydrocarbon group that can have 1 to 20 carbon atoms as a substituent".

[0090] l is an integer greater than 0 and less than 2 in each occurrence, m is an integer greater than 0 and less than 2 in each occurrence, and l + m equals 2.

[0091] (Specific example) Specific examples of polyamine modifiers include the compounds shown below. R in the following formulas... 2Each of these refers independently to a monovalent hydrocarbon group having 6 to 40 carbon atoms that can have substituents. The definition of a monovalent hydrocarbon group having 6 to 40 carbon atoms that can have substituents is as described above. Furthermore, the compounds shown below have structures that modify one or two monovalent hydrocarbon groups having 6 to 40 carbon atoms that can have substituents to the amino groups of the polyamine, but the number of modifications is not limited to these. For example, in the polyamine modified forms shown below, other unmodified amino groups in the molecule may be further modified with monovalent hydrocarbon groups having 6 to 40 carbon atoms that can have substituents. In this case, the molecule must have one or more amino groups. The compounds shown below have a structure in which the amino group of a polyamine is modified by -C(=O)- with one or two monovalent hydrocarbon groups having a number of carbon atoms of 6 to 40 that may have substituents. However, the monovalent hydrocarbon groups having a number of carbon atoms of 6 to 40 that may have substituents may also have a structure in which the nitrogen atom of the amino group is directly bonded to the amino group without being modified by -C(=O)-. (Manufacturing method) There are no limitations on the method for manufacturing polyamine modifiers; various methods can be listed, such as reacting various polyamines with a modifying agent to synthesize them. The modifying agent can be a carboxylic acid, an acyl halide of a carboxylic acid, an anhydride, isocyanate, etc., having a monovalent hydrocarbon group with 6 to 40 carbon atoms that may have substituents. Depending on the need, the above reaction can also be carried out in the presence of a condensing agent. The condensing agent can be a known condensing agent, such as DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA, Py-Bop, etc.

[0092] The polyamine that reacts with the modifier is a compound having two or more amino groups. A polyamine is a compound having two or more amino groups within its molecule. The polyamine described in detail below can be used as the polyamine for manufacturing the polyamine-modified form of the present invention.

[0093] Examples of modifiers that react with polyamines are described below.

[0094] Acyl halide G(O=)C-R 2 Acid anhydride O(C(=O)-R 2 )2 Carboxylic acid HO(O=)C-R 2 Isocyanates O=C=N-R 2 [In the formula, R] 2 As mentioned above, G is a halogen atom (e.g., F, Cl, Br, or I). Polyamine modifiers can be synthesized by reacting a polyamine with the aforementioned modifiers. For example, by reacting a modifier that is an acyl halide, acid anhydride, or carboxylic acid with the amino group of a polyamine to form an amide bond, a polyamine modifier can be synthesized. Such a polyamine modifier has a structure in which a monovalent hydrocarbon group with 6 to 40 carbon atoms, which may have substituents, is modified onto the polyamine via an amide bond. Alternatively, by reacting an isocyanate modifier with the amino group of a polyamine to form a urea bond, a polyamine modifier can be generated. Such a polyamine modifier has a structure in which a monovalent hydrocarbon group with 6 to 40 carbon atoms, which may have substituents, is modified onto the polyamine via a urea bond.

[0095] The reaction conditions between polyamines and modifiers can be designed by those skilled in the art to utilize catalysts (e.g., acid catalysts, base catalysts) and condensing agents appropriately according to the target product.

[0096] The following describes a method for manufacturing the polyamine modified product of the present invention according to one embodiment.

[0097] In a Dean-Stark apparatus under a nitrogen atmosphere, diethylenetriamine and stearic acid were stirred overnight in an oil bath at 130°C–180°C. After the reaction was complete, the mixture was cooled to room temperature, and liquid-liquid extraction was performed with chloroform and pure water to recover the chloroform phase. After concentration under reduced pressure, a chloroform solution was added dropwise to hexane, and the mixture was stirred for 1 hour. By filtering the hexane, the polyamine-modified product was obtained.

[0098] [Polycarboxylic acid modified form] Compound (a) can be a polycarboxylic acid modified. Specifically, compound (a) is a compound formed by modifying the carboxyl group of a polycarboxylic acid with a monovalent hydrocarbon group having 6 to 40 carbon atoms, and may have one or more carboxyl groups or derivatives thereof.

[0099] The polycarboxylic acid modifier can be a compound obtained by reacting an alkylamine having a monovalent hydrocarbon group with 6 to 40 carbon atoms that can have substituents with a polycarboxylic acid, and can have one or more amino groups.

[0100] The polycarboxylic acid modifier can be a polycarboxylic acid modifier having one or more amide structures. For example, it can be a polycarboxylic acid (a raw carboxylic acid compound, such as a polycarboxylic acid) modified by one or more modifying groups via an amide structure. Here, the amide can be an amide structure contained in urethane groups, urea groups, imides, etc. The polycarboxylic acid modifier can have a structure in which a monovalent hydrocarbon group with 6 to 40 carbon atoms, which may have substituents, is bonded to the nitrogen atom of the amide group.

[0101] The modifying group is preferably a hydrocarbon group with 6 to 40 monovalent carbon atoms that can have a substituent.

[0102] Compound (a) can be a compound formed by modifying the carboxyl group of a polycarboxylic acid with a monovalent hydrocarbon group having 6 to 40 carbon atoms as a substituent. Here, the monovalent hydrocarbon group having 6 to 40 carbon atoms as a substituent is explained above (the monovalent hydrocarbon group having 6 to 40 carbon atoms as a substituent).

[0103] Compound (a) may have one or more carboxyl groups or their derivatives. Here, one or more carboxyl groups or their derivatives are the reactive groups of the present invention. The number of carboxyl groups or their derivatives in the polycarboxylic acid modifier may be independently one or more, or two or more, three or more, four or more, or five or more, or less than ten, nine or less, eight or less, seven or less, or five or less.

[0104] The average molecular weight of the polycarboxylic acid modifier can be above 100, above 200, above 300, above 400, above 500, above 1000, above 3000, above 5000, above 10000, above 30000, above 100000, above 300000, above 300000, or above 500000. It can also be below 1,000,000, below 750,000, below 500,000, below 300,000, below 100,000, below 75,000, below 50,000, below 30,000, below 10,000, below 9,000, below 8,000, below 7,000, below 6,000, below 5,000, below 3,000, below 2,000, below 1,000, or below 500.

[0105] When compound (a) is a polycarboxylic acid modifier, the portion derived from compound (a) may be a structure obtained by removing at least one hydroxyl group from a polycarboxylic acid modifier, or a structure obtained by removing at least one carboxyl group from a polycarboxylic acid modifier.

[0106] (Examples of polycarboxylic acid modifiers) Polycarboxylic acid modifiers can include compounds as shown in the following formula: A{-CONR 1 -R 2} n {-COOH} m [In the formula,] A is an aliphatic hydrocarbon group with 1 to 20 carbon atoms in the range of 2 to 4 valences, or an aromatic hydrocarbon group in the range of 2 to 4 valences. R 1 Each is an aliphatic hydrocarbon group, consisting independently of one or more hydrogen atoms or fewer than 20 carbon atoms, either straight-chain or branched. R 2 Each can be independently a monovalent hydrocarbon group with 6 to 40 carbon atoms that can have substituents. n is an integer greater than 1 and less than 4. m is an integer greater than 1 and less than 4. [n + m is an integer greater than 1 and less than 4.] A is an aliphatic hydrocarbon group with 1 to 20 carbon atoms in the range of 2 to 4 valences, or an aromatic hydrocarbon group in the range of 2 to 4 valences.

[0107] Aliphatic hydrocarbon groups with a valence of 1 to 20 carbon atoms (2 to 4) can be cyclic, branched, or straight-chain. These groups can be saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon groups. The number of carbon atoms in these groups can be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and can also be less than 20, less than 15, less than 10, or less than 5. The valence of the aliphatic hydrocarbon group can be 2 or more, 3 or more, or 4, or less than 4, less than 3, or 2.

[0108] Examples of 2- to 4-valent aromatic hydrocarbon groups include those formed by removing 2 to 4 hydrogen atoms from the aromatic rings of hydrocarbons such as benzene, naphthalene, anthracene, phenanthrene, benzo[a]nephthalene, penta[a]nephthalene, pyrene, and cardamom. The number of atoms in the ring of the aromatic hydrocarbon group is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the aromatic ring can be 2 or more, 3 or more, or 4, or it can be 4 or less, 3 or less, or 2.

[0109] R 1 Each is an aliphatic hydrocarbon group, either a straight-chain or branched, consisting of 1 to 20 carbon atoms, and is independently composed of either hydrogen atoms. R 1 It can be a hydrogen atom.

[0110] Aliphatic hydrocarbons with 1 to 20 carbon atoms can be either straight-chain or branched.

[0111] Aliphatic hydrocarbons with 1 to 20 carbon atoms can have 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more carbon atoms, and can also have fewer than 20, 18, 16, 14, 12, 10, 8, 6, 4, or 3 carbon atoms.

[0112] R 2 Each is independently a monovalent hydrocarbon group having 6 to 40 carbon atoms that can have substituents. The explanation above (monovalent hydrocarbon groups having 6 to 40 carbon atoms that can have substituents) is relevant.

[0113] n is the -CONR that binds to A. 1 -R 2 The number of elements. n is an integer between 1 and 4, and can be between 1 and 3, between 1 and 2, or 1.

[0114] m is the number of -COOH groups that combine with A. m is an integer between 1 and 4, and can be between 1 and 3, between 1 and 2, or 1.

[0115] n + m is an integer greater than 2 and less than 4.

[0116] (Specific example) Specific examples of polycarboxylic acid modifiers include compounds represented by the following formulas. R in the following formulas... 2 Each of these refers independently to a monovalent hydrocarbon group having 6 to 40 carbon atoms that can have substituents. The definition of a monovalent hydrocarbon group having 6 to 40 carbon atoms that can have substituents is as described above. Furthermore, the compounds shown below modify the carboxyl group of the polycarboxylic acid with one or two monovalent hydrocarbon groups having 6 to 40 carbon atoms that can have substituents, but the number of modifications is not limited to these. For example, in the polycarboxylic acid modified forms shown below, other unmodified carboxyl groups in the molecule may be further modified with monovalent hydrocarbon groups having 6 to 40 carbon atoms that can have substituents. In this case, the molecule must have more than one carboxyl group. The method for manufacturing polycarboxylic acid modifiers is not limited, and methods involving the reaction of various polycarboxylic acids with a modifying agent can be listed. The modifying agent can be an amine, epoxide, alcohol, etc., having a monovalent hydrocarbon group with 6 to 40 carbon atoms that can have substituents. Depending on the need, the above reaction can also be carried out in the presence of a condensing agent. The condensing agent can be a known condensing agent, such as DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA, Py-Bop, etc.

[0117] The polycarboxylic acid that reacts with the modifier is a compound having two or more carboxyl groups. A polycarboxylic acid is a compound having two or more carboxyl groups within its molecule. The polycarboxylic acid described in detail below can be used as the polycarboxylic acid used to manufacture the polycarboxylic acid modified body of the present invention.

[0118] Examples of modifiers that react with polycarboxylic acids are described below.

[0119] Epoxide (CH2OCH)CH2O-R 2 Amine H2N-R 2 Hydroxyl HO-R 2 [In the formula, R]2 As stated above. Polycarboxylic acid modifiers can be synthesized by reacting a polycarboxylic acid with the aforementioned modifiers. For example, by reacting an alcohol or epoxy compound modifier with the carboxyl group of a polycarboxylic acid to form an ester bond, a polycarboxylic acid modifier can be generated. Such a polycarboxylic acid modifier has a structure in which a monovalent hydrocarbon group with 6 to 40 carbon atoms, which may have substituents, is modified onto the polycarboxylic acid via an ester bond. Alternatively, by reacting an amine modifier with the carboxyl group of a polycarboxylic acid to form an amide bond, a polycarboxylic acid modifier can be generated. Such a polycarboxylic acid modifier has a structure in which a monovalent hydrocarbon group with 6 to 40 carbon atoms, which may have substituents, is modified onto the polycarboxylic acid via an amide bond.

[0120] The reaction conditions of polycarboxylic acids with modifiers can be designed by those skilled in the art to utilize catalysts (e.g., acid catalysts, base catalysts) and condensing agents appropriately according to the target product.

[0121] The following describes a method for manufacturing a polycarboxylic acid modified product of the present invention according to one embodiment.

[0122] In a Dean-Stark apparatus under a nitrogen atmosphere, pyromellitic acid and octadecylamine were stirred overnight in an oil bath at 130°C–180°C. After the reaction was complete, the mixture was cooled to room temperature and subjected to liquid-liquid extraction with chloroform and pure water to recover the chloroform phase. After concentration under reduced pressure, a chloroform solution was added dropwise to hexane, and the mixture was stirred for 1 hour. By filtering the hexane, a polycarboxylic acid modified product was obtained.

[0123] [(b) compound] The liquid-repellent compound has a portion derived from compound (b), which does not have a monovalent hydrocarbon group with 6 to 40 carbon atoms that can have substituents, but has two or more reactive groups.

[0124] [Structure, etc.] Compound (b) may not have any of the following: a compound having 8 or more carbon atoms, a compound having 8 or more carbon atoms, a compound having 4 ...

[0125] Compound (b) can be a compound other than a sugar alcohol. For example, compound (b) can be a compound that does not have a sugar alcohol skeleton. A sugar alcohol is a polyol formed by reducing the aldehyde and ketone groups of a sugar to alcohol groups. Examples of sugar alcohols include sorbitol, xylitol, maltitol, erythritol, and mannitol. The sugar alcohol skeleton refers to the molecular structure of a cyclic or acyclic sugar alcohol when one or more hydrogen atoms are removed from the hydroxyl group (-OH).

[0126] Compound (b) does not have a monovalent hydrocarbon group with 6 to 40 carbon atoms that can have substituents. For information on monovalent hydrocarbon groups with 6 to 40 carbon atoms that can have substituents, please refer to (monovalent hydrocarbon groups with 6 to 40 carbon atoms that can have substituents).

[0127] [Reactive groups] Compound (b) has two or more reactive groups. The reactive groups in compound (b) are different from the reactive groups in compound (a).

[0128] The reactive groups present in compound (b) can be hydroxyl, amino, carboxyl, isocyanate and their derivatives, but typically amino or carboxyl.

[0129] The reactive group of compound (b) can be a reactive group that reacts with the reactive group of compound (a) to form an amide group, urea group, ester group or urethane group, etc., preferably a reactive group that forms an amide group or urea group.

[0130] Compound (b) may have two or more reactive groups, or three or more, four or more, or five or more, or less than ten, eight or less, six or less, five or less, or three or less, and in one manner, two or more, five or less, or two or more, three or less.

[0131] Examples of compound (b) include polyamines, polycarboxylic acids, polyols, polyisocyanates, etc.

[0132] [Polyamines] Polyamines are compounds having two or more amino groups. Polyamines can be aliphatic or aromatic, but are preferably aliphatic.

[0133] Polyamines can be low molecular weight (e.g., weight average molecular weight less than 1000, less than 500) and / or high molecular weight. The weight average molecular weight of polyamines can be greater than 100, greater than 300, greater than 500, greater than 1000, greater than 3000, greater than 5000, greater than 10000, greater than 30000, greater than 100000, greater than 300000, or greater than 500000, and can be less than 1,00000, less than 7,500000, less than 500000, less than 3,00000, less than 100000, less than 75000, less than 50000, less than 30000, less than 10000, less than 5000, less than 3000, less than 2000, less than 1000, or less than 500.

[0134] The number of amino groups in a polyamine can be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more, and can be less than 3000, less than 1000, less than 750, less than 500, less than 300, less than 100, less than 50, less than 30, or less than 20.

[0135] The amine equivalent of a polyamine can be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, or 150 or more, and can be less than 1000, less than 800, less than 600, less than 400, less than 200, less than 100, or less than 75. The amine equivalent of a polyamine is the value obtained by dividing the weight-average molecular weight of the polyamine by the number of amino groups.

[0136] Examples of polyamines include: Ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine, cyclohexanediamine, methylenebiscyclohexylamine, and other alkylene diamines; Diethylenetriamine, triethylenetetramine, tris(2-aminoethyl)amine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tris(2-aminopropyl)amine, tetrapropylenepentamine, pentapropylenehexamine, iminodipropylamine, dibutyltriamine, bis(2-aminoethoxy)ethane, bis(2-aminoethyl) ether, bis[2-(2-aminoethoxy)ethyl] ether, bis[2-(3-aminopropoxy)ethyl] ether, spermine, spermidine, and other polyalkylene polyamines; Monocyclic aromatic polyamines such as ortho, meta or p-phenylenediamine, ortho, meta or p-phenylenediethylenediamine, diaminotoluene, 2,3-, 2,4- or 2,5-toluenediamine; Biphenyl diamine, bis(aminophenoxyphenyl)propane, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl sulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenylphenylethane, bis(aminophenoxybenzene), bis(aminobenzoylbenzene), bis(aminodimethylbenzylbenzene), aminophenoxybiphenyl, aminophenoxyphenyl ketone, bis(aminobis(trifluoromethylbenzylbenzene), aminophenoxyphenyl sulfone, aminophenoxyphenyl ether, aminophenoxyphenylpropane, bis(aminophenoxybenzoyl)benzene, bis(aminophenoxy-α,α-dimethylbenzyl)benzene, bis[(aminoaryloxy)benzoyl]diphenyl ether, bis(amino- α,α-dimethylbenzylphenoxy)benzophenone, aminophenoxyphenyl sulfide, bis[amino-α,α-dimethylbenzylphenoxy]diphenyl sulfone, 4,4'-bis[aminophenoxyphenoxy]diphenyl sulfone, diaminodiaryloxybenzophenone, diaminoaryloxybenzophenone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminotriphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenebisphenylamine, 4,4'-diphenylamine oxide, 1,3-bis(4-aminophenoxy)benzene, 4,4'-diaminodiphenyl ether, 4,4'-bis(aminophenyl)amine and other polycyclic aromatic polyamines; Polyamines containing hydroxyl groups include 2-hydroxyethyl ethylenediamine, 2-hydroxyethyl propanediamine, bis-2-hydroxyethyl ethylenediamine, bis-2-hydroxyethyl propanediamine, 2-hydroxypropyl ethylenediamine, and bis-2-hydroxypropyl ethylenediamine. Polyamines can also be substances obtained by polymerizing polymerizable compounds such as allylamine.

[0137] In one embodiment, alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine can be used instead of polyamines.

[0138] In the case that compound (b) is a polyamine, the portion derived from compound (b) may be a structure formed by removing at least one hydrogen atom bonded to a nitrogen atom of the polyamine, or a structure formed by removing at least one nitrogen atom of the polyamine and a hydrogen atom bonded to that nitrogen atom.

[0139] [Polycarboxylic acids] Polycarboxylic acids are compounds having two or more carboxyl groups. They can be aliphatic or aromatic, but are preferably aliphatic.

[0140] Polycarboxylic acids can be low molecular weight (e.g., weight average molecular weight less than 1000, less than 500) and / or high molecular weight. The weight average molecular weight of polycarboxylic acids can be greater than 100, greater than 300, greater than 500, greater than 1000, greater than 3000, greater than 5000, greater than 10000, greater than 30000, greater than 100000, greater than 300000, or greater than 500000, and can be less than 1,000,000, less than 7,500,000, less than 500,000, less than 3,000,000, less than 100,000, less than 75,000, less than 50,000, less than 30,000, less than 10,000, less than 5,000, less than 3,000, less than 2,000, less than 1,000, or less than 500.

[0141] The number of carboxyl groups in a polycarboxylic acid can be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more, and can be less than 3000, less than 1000, less than 750, less than 500, less than 300, less than 100, less than 50, less than 30, or less than 20.

[0142] The carboxyl equivalent of a polycarboxylic acid can be greater than 20, greater than 40, greater than 60, greater than 80, greater than 100, greater than 120, or greater than 150, and can be less than 1000, less than 800, less than 600, less than 400, less than 200, less than 100, or less than 75. The carboxyl equivalent of a polycarboxylic acid is the value obtained by dividing the weight-average molecular weight of the polycarboxylic acid by the number of hydroxyl groups.

[0143] Polycarboxylic acids can be natural products. These natural products can be high-molecular-weight natural products, low-molecular-weight natural products, or their derivatives. The aforementioned natural products also include compounds derived from microbial transformation.

[0144] Polycarboxylic acids can be at least one selected from dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, polymers containing carboxyl groups, and their salts.

[0145] Dicarboxylic acids are compounds having two carboxyl groups, such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid, terephthalic acid, malic acid, tartaric acid, aldonic acid, and their salts.

[0146] Tricarboxylic acids are compounds with three carboxyl groups, such as citric acid, procarboxylic acid, trans-aconitine, pyromellitic acid, trimellitic acid, tricarboxybenzene, and their salts.

[0147] Tetracarboxylic acids are compounds with four carboxyl groups, such as pyromellitic acid and its salts.

[0148] Polymers containing carboxyl groups are compounds with five or more carboxyl groups, such as alginate, tragacanth gum, gum arabic, polyacrylic acid, polymethacrylic acid, polymaleic acid, polyaspartic acid, polyglutamic acid, hyaluronic acid, heparin, xanthan gum, gellan gum, carboxymethyl cellulose, galacturonic acid, mannouronic acid and their salts.

[0149] In the case that compound (b) is a polycarboxylic acid, the portion derived from compound (b) may be a structure formed by removing at least one hydroxyl group of a polycarboxylic acid or a structure formed by removing at least one carboxyl group of a polycarboxylic acid.

[0150] [Polyols] Polyols are compounds having two or more hydroxyl groups. A polyol is a compound with two or more hydroxyl groups within its molecule. Polyols can be aliphatic or aromatic, but are preferably aliphatic.

[0151] Polyols may have ether bonds. Preferably, polyols may have two or more ether bonds. Specifically, polyols are preferably compounds having two or more hydroxyl groups and two or more ether bonds. In other words, polyols are preferably polyethers having two or more hydroxyl groups.

[0152] In the case of polyols as polymers, hydroxyl and ether bonds can be present in the repeating structure of monomer units.

[0153] Polyols can be low molecular weight (e.g., weight average molecular weight less than 1000, below 500) and / or high molecular weight. The weight average molecular weight of polyols can be above 50, above 100, above 300, above 500, above 1000, above 3000, above 5000, above 10000, above 30000, above 100000, above 300000, or above 500000, and can be below 1000000, below 750000, below 500000, below 300000, below 100000, below 75000, below 50000, below 30000, below 10000, below 5000, below 3000, below 2000, below 1000, or below 500.

[0154] The number of hydroxyl groups in a polyol can be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more, and can be less than 3000, less than 1000, less than 750, less than 500, less than 300, less than 100, less than 50, less than 30, or less than 20.

[0155] The hydroxyl equivalent of a polyol can be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, or 150 or more, and can be less than 1000, less than 800, less than 600, less than 400, less than 200, less than 100, or less than 75. The hydroxyl equivalent of a polyol is the value obtained by dividing the weight-average molecular weight of the polyol by the number of hydroxyl groups.

[0156] Examples of polyols include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerol, trimethylolpropane, trimethylolethane, polyglycerol, polyvinyl alcohol, hydroxyethyl methacrylate polymer, hydroxypropyl methacrylate polymer, and hydroxybutyl methacrylate polymer.

[0157] In the case that compound (b) is a polyol, the portion derived from compound (b) may be a structure formed by removing at least one hydroxyl group or a hydrogen atom bonded to the oxygen atom of the hydroxyl group of the polyol.

[0158] [Polyisocyanates] Examples of polyisocyanates include: Selected from toluene diisocyanate (2,4- or 2,6-toluene diisocyanate or mixtures thereof) (TDI), phenyl diisocyanate (m-, terephthalic diisocyanate or mixtures thereof), 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or mixtures thereof) (MDI), 4,4'-bitoluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, phenyl dimethyl ethylene diisocyanate (1,3- or 1,4-phenyl dimethyl ethylene diisocyanate or mixtures thereof) (XDI), tetramethylphenyl dimethyl ethylene diisocyanate (1,3- or 1,4-phenyl dimethyl ethylene diisocyanate or mixtures thereof), and tetramethylphenyl dimethyl ethylene diisocyanate (1,3- or 1,4-phenyl dimethyl ethylene diisocyanate). Aromatic polyisocyanates including 4-tetramethylphenyl dimethylene diisocyanate or mixtures thereof (TMXDI), ω,ω'-diisocyanate-1,4-diethylphenyl, naphthalene diisocyanate (1,5-, 1,4- or 1,8-naphthalene diisocyanate or mixtures thereof) (NDI), triphenylmethane triisocyanate, tri(isocyanate phenyl) thiophosphate, polymethylene polyphenyl polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate; Noncyclic aliphatic polyisocyanates selected from trimethylene diisocyanate, 1,2-propanediisocyanate, succinate (tetramethylene diisocyanate, 1,2-succinate, 2,3-succinate, 1,3-succinate), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate-methylhexanoate, lysine diisocyanate, lysine triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, and decamethylene diisocyanate; Selected from 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylene bis(cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylene bis(cyclohexyl isocyanate) or mixtures thereof) (hydrogenated MDI), methyl Cyclohexane diisocyanates (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane (1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or mixtures thereof) (hydrogenated XDI), dimer acid diisocyanates, trans-cyclohexane 1,4-diisocyanate, hydrogenated toluene diisocyanate (hydrogenated TDI), hydrogenated tetramethylphenyl dimethylene diisocyanate (hydrogenated TMXDI) and other cyclic alicyclic polyisocyanates; Bridged cyclic alicyclic polyisocyanates selected from norbornene diisocyanate, norbornane diisocyanate methyl, bicycloheptane triisocyanate, diisocyanate methyl bicycloheptane, and di(diisocyanate methyl)tricyclodecane. Compounds selected from the following compounds: ; And the biuret modified forms of the above-mentioned isocyanates, polymers of polyisocyanates (e.g., dimers, trimers (e.g., isocyanurate derivatives, iminooxadiazine dione derivatives), pentameres, heptameres, etc.), urethane derivatives (e.g., urethane derivatives generated by the reaction of the above-mentioned polyisocyanates with monovalent or divalent alcohols), polyol derivatives (e.g., polyol derivatives (alcohol adducts, preferably trimethylolpropane adducts) generated by the reaction of the above-mentioned polyisocyanates with trivalent alcohols (e.g., trimethylolpropane), etc.), biuret derivatives (e.g., biuret derivatives generated by the reaction of the above-mentioned polyisocyanates with water or amines), urea derivatives (e.g., urea derivatives generated by the reaction of the above-mentioned polyisocyanates with diamines), oxadiazine trione derivatives (e.g., oxadiazine triones generated by the reaction of the above-mentioned polyisocyanates with carbon dioxide), carbodiimide derivatives (carbodiimide derivatives generated by the decarboxylation condensation reaction of the above-mentioned polyisocyanates), urea dione derivatives, urea ketone imide derivatives, etc.

[0159] The average number of isocyanate groups in the polyisocyanate is 2 or more, preferably 2.5, more preferably 2.9, and for example 3.8 or less. The polyisocyanate can be a polyisocyanate having a plurality of isocyanate groups.

[0160] In the case that compound (b) is a polyisocyanate, the portion derived from compound (b) may be a structure in which one hydrogen atom is bonded to the nitrogen atom of the isocyanate group of the polyisocyanate, or a structure formed by removing at least one isocyanate group of the polyisocyanate.

[0161] [(c) compound] The liquid-repellent compound of the present invention may also have a portion derived from compound (c). Compound (c) may be: Monocarboxylic acids and their derivatives having a monovalent hydrocarbon group having 6 to 40 carbon atoms that can have substituents. Monoamines and their derivatives having a monovalent hydrocarbon group with 6 to 40 carbon atoms that can have substituents.

[0162] [Monocarboxylic acid] Monocarboxylic acids and their derivatives have a monovalent hydrocarbon group having 6 to 40 carbon atoms that can have substituents. Here, the monovalent hydrocarbon group having 6 to 40 carbon atoms that can have substituents is explained above (monovalent hydrocarbon group having 6 to 40 carbon atoms that can have substituents).

[0163] The derivative of a monocarboxylic acid can be a halide of a monocarboxylic acid, preferably a chloride of a monocarboxylic acid.

[0164] Monocarboxylic acids are compounds containing only one carboxyl group. A monocarboxylic acid is a compound that has one carboxyl group within its molecule. Monocarboxylic acids can be aliphatic or aromatic, but are preferably aliphatic.

[0165] Monocarboxylic acids can include, for example, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, icosanoic acid, benzyl acid, tridecanoic acid, ceramide, etc.

[0166] [Monoamine] Monoamines and their derivatives have a monovalent hydrocarbon group having 6 to 40 carbon atoms that can have substituents. Here, the monovalent hydrocarbon group having 6 to 40 carbon atoms that can have substituents is explained above (monovalent hydrocarbon group having 6 to 40 carbon atoms that can have substituents).

[0167] The derivative of the monoamine can be a salt of the monoamine, preferably a hydrochloride or phosphate of the monoamine.

[0168] A monoamine is a compound having one amino group. A monoamine is a compound that has one amino group within its molecule. Monoamines can be aliphatic or aromatic, but are preferably aliphatic.

[0169] Monoamines can be dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecanylamine, octadecylamine, nonadecanylamine, etc.

[0170] The dispensing agent of the present invention may also contain the following components.

[0171] 〔wax〕 The dissolving agent of the present invention may contain wax, particularly hydrocarbon wax. The wax may be an organic substance that is solid at room temperature and becomes liquid when heated. For example, the wax may be a hydrocarbon compound or a compound having a hydrocarbon group (e.g., an alkyl group) having 6 to 40 carbon atoms.

[0172] The wax of the present invention can adhere to a substrate (especially a pulp substrate) and impart liquid-repellent properties, such as water resistance, oil resistance, water repellency, oil repellency and / or stain resistance to the substrate.

[0173] [Properties of wax, etc.] The properties of wax are described below.

[0174] The wax can be in granular form (powder). The average particle size of the wax can be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, and can be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less. The above particle size refers to the primary particle size. By keeping it within the above range, the particle stability is excellent, and the liquid repellency is good. The average particle size can be measured using a microscope (scanning electron microscope). Specifically, the wax particle sample is observed under a microscope at any magnification. Next, if the particle shape is spherical, its diameter is taken; if it is non-spherical, the average of the longest and shortest diameters is taken as the particle size. The particle size of all particles present in the field of view is measured, the field of view is moved, the particle size is measured again, and this process is repeated to measure the particle size of more than 100 points, and the average of these measurements is taken as the average particle size.

[0175] The HD (n-hexadecane) contact angle of the wax can be 10° or more, 20° or more, 25° or more, 30° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 60° or more, or 65° or more, preferably 25° or more, more preferably 30° or more, and can be 100° or less, 90° or less, or 75° or less. By giving the wax an HD contact angle of at least the lower limit mentioned above, it is possible to impart good liquid repellency (especially oil repellency) to the substrate. The HD contact angle is the static contact angle relative to the spin-coated film of the wax, which is the value obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle after 1 second.

[0176] The water contact angle of a wax can be greater than 35°, greater than 40°, greater than 45°, greater than 50°, greater than 55°, greater than 65°, greater than 75°, greater than 85°, greater than 90°, or greater than 100°, and can be less than 160°, less than 140°, less than 130°, less than 120°, less than 110°, less than 100°, or less than 90°. By giving the wax a water contact angle greater than or equal to the lower limit mentioned above, it is possible to impart good liquid repellency (especially water repellency) to the substrate. The water contact angle is the static contact angle relative to the spin-coated film of the wax, which is the value obtained by adding 2 μL of water to the spin-coated film and measuring the contact angle after 1 second.

[0177] Waxes can be low molecular weight (e.g., molecular weight below 1000 or 500) or high molecular weight. When the wax is a high molecular weight, its weight-average molecular weight can be above 1000, above 3000, above 5000, above 7500, above 10000, above 30000, above 100000, above 300000, or above 500000. It can also be below 10000000, below 7500000, below 500000, below 300000, below 100000, below 750000, below 500000, below 300000, below 100000, below 75000, below 50000, below 30000, below 10000, below 7500, below 50000, below 30000, below 10000, below 7500, below 5000, or below 3000.

[0178] The melting point of the wax can be above 30°C, 40°C, 50°C, 60°C, 80°C, 100°C, or 120°C, preferably above 40°C, particularly preferably above 55°C, and can be below 250°C, 225°C, 200°C, 150°C, 130°C, 120°C, 110°C, 100°C, 80°C, or 50°C, preferably below 120°C. The melting point of the wax can be determined according to JIS K 2235-1991. The melting point is generally equivalent to the peak temperature of the endothermic peak at the maximum temperature before melting, as observed using DSC (differential scanning calorimetry).

[0179] [Types of wax, etc.] Examples of waxes include: mineral waxes (petroleum waxes) such as paraffin wax, microcrystalline wax, lignite wax, ozokerite wax, ceresin wax, and petrolatum wax; and synthetic waxes such as Fischer-Tropsch wax, polyethylene wax, and polypropylene wax, with paraffin wax or microcrystalline wax being preferred. The wax of this invention can be a hydrocarbon wax, preferably a chain-like aliphatic hydrocarbon, such as a straight-chain or branched hydrocarbon, especially a straight-chain hydrocarbon.

[0180] [Amount of wax] The amount of wax relative to 100 parts by weight of the repellent compound can be more than 0.1 parts by weight, more than 1 part by weight, more than 3 parts by weight, more than 5 parts by weight, more than 10 parts by weight, more than 15 parts by weight, or more than 20 parts by weight, and can be less than 50 parts by weight, less than 40 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight.

[0181] [Dispersant] The dispersant of the present invention may contain a dispersant. The dispersant may be at least one selected from organic and inorganic dispersants. The dispersant may be at least one selected from anionic, nonionic, cationic, amphoteric, and inorganic dispersants. In particular, the dispersant of the present invention may contain a nonionic dispersant.

[0182] Dispersants can be organic or inorganic dispersants, or a combination of organic and inorganic dispersants.

[0183] Organic dispersants can be used as dispersants. Organic dispersants can be classified into nonionic dispersants, anionic dispersants, cationic dispersants, and amphoteric dispersants. Organic dispersants can also refer to surfactants.

[0184] Dispersants may also be free of fluorine atoms.

[0185] [Nonionic dispersant] Dispersants may include nonionic dispersants. Nonionic dispersants may be nonionic surfactants.

[0186] Nonionic dispersants can be low molecular weight (e.g., molecular weight below 2000, especially below 10000) or high molecular weight (e.g., molecular weight above 2000). The molecular weight of nonionic dispersants can be above 100, above 500, above 1000, above 2000, above 4000, or above 6000, and can be below 1,000,000, below 750,000, below 500,000, below 250,000, below 100,000, below 50,000, below 10,000, below 7,500, below 5,000, below 25,000, below 750, or below 250.

[0187] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides.

[0188] Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0189] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are alcohols with 1 to 30 carbon atoms (especially 2 to 10 carbon atoms) and 1 to 50 carbon atoms (especially 10 to 30 carbon atoms), such as aliphatic alcohols. Examples of fatty acids are saturated or unsaturated fatty acids with 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0190] Examples of ester ethers are compounds obtained by adding an oxoalkylene group (especially an oxoethylene) to an ester of an alcohol and a fatty acid. Examples of alcohols are alcohols with 1 to 30 carbon atoms (especially 2 to 10 carbon atoms) and 1 to 50 carbon atoms (especially 3 to 30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0191] Examples of alkanolamides are formed from fatty acids and alkanolamines. Alkanolamides can be monoalkanolamides or dialkanolamides. Examples of fatty acids are saturated or unsaturated fatty acids with 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. Alkanolamines can be alkanols with 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0192] Polyols can be alcohols with 2 to 5 carbon atoms and 10 to 30 carbon atoms.

[0193] The amine oxide can be an oxide of an amine (secondary amine or preferably tertiary amine) (e.g., having 5 to 50 carbon atoms).

[0194] The nonionic dispersant is preferably a nonionic dispersant having an oxoalkylene group (preferably polyoxyethylene). The number of carbon atoms in the oxoalkylene group is preferably 2 to 10. The number of oxoalkylene groups in the nonionic dispersant molecule is usually preferably 2 to 100.

[0195] The nonionic dispersant is selected from ethers, esters, ester ethers, alkanolamides, polyols and amine oxides, and is preferably a nonionic dispersant with oxyalkylene groups.

[0196] Nonionic dispersants can be alkylene adducts of linear and / or branched aliphatic (saturated and / or unsaturated) groups, polyalkylene glycol esters of linear and / or branched fatty acids (saturated and / or unsaturated), dehydrated sorbitol esters of linear and / or branched fatty acids (saturated and / or unsaturated), glycerides of linear and / or branched fatty acids (saturated and / or unsaturated), polyglycerol esters of linear and / or branched fatty acids (saturated and / or unsaturated), sucrose esters of linear and / or branched fatty acids (saturated and / or unsaturated), polyoxyethylene (POE) / polyoxypropylene (POP) copolymers (random copolymers or block copolymers), alkylene glycol oxydiols, etc. Among these, compounds in which the oxyalkylene addition portion and the polyalkylene glycol portion are preferably polyoxyethylene (POE), polyoxypropylene (POP), or POE / POP copolymers (which can be random copolymers or block copolymers) are preferred.

[0197] In addition, nonionic dispersants may also be free of aromatic groups.

[0198] Nonionic dispersants can be compounds represented by the following formula: R 1 O-(CH2CH2O) p -(R) 2 O) q -R 3 [In the formula, R] 1 It is an alkyl group having 1 to 22 carbon atoms, or an alkenyl or acyl group having 2 to 22 carbon atoms. R 2 Each and every one of them is independently identical or different, and is an alkylene group having 3 or more carbon atoms (e.g., 3 to 10). R 3 It consists of hydrogen atoms, alkyl groups having 1 to 22 carbon atoms, or alkenyl groups having 2 to 22 carbon atoms. p is a number greater than or equal to 2. q is a number that is 0 or greater than 1. R 1 Preferably, the number of carbon atoms is 8–20, particularly 10–18. As R… 1 Preferred specific examples may include octyl, nonyl, trimethylnonyl, lauryl, tridecyl, oleyl, and stearyl.

[0199] R 2 Examples include propylidene and butylidene.

[0200] In nonionic dispersants, p can be a number greater than 3 (e.g., 5–200). q can be a number greater than 2 (e.g., 5–200). That is, -(R 2 O) q - It can form polyoxyalkylene chains.

[0201] The nonionic dispersant can be a polyoxyethylene alkylene ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (especially a polyoxyalkylene chain) at its center. Examples of hydrophobic oxyalkylene chains include oxypropylene chains, oxybutylene chains, and styrene chains, with oxypropylene chains being preferred.

[0202] Specific examples of nonionic dispersants include: ethylene oxide with hexylphenol, isooctylphenol, hexadecyl alcohol, oleic acid, and alkanes (C... 12 -C 16 Thiols, sorbitol monofatty acid esters (C7-C5) 19 ) or alkyl (C 12 -C 18Condensation products of amines, etc., dehydrated sorbitol fatty acid esters, fatty acid glycerides, polyglycerol fatty acid esters, fatty acid sucrose esters, fatty acid propylene glycol esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerol fatty acid esters, polyoxyethylene dehydrated sorbitol fatty acid esters, lecithin derivatives, etc. Examples of nonionic dispersants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycol, polyoxyethylene imine ethoxylates, etc.

[0203] The proportion of polyoxyethylene blocks relative to the molecular weight of the nonionic dispersant (copolymer) can be 5 to 80% by weight, for example 30 to 75% by weight, particularly 40 to 70% by weight.

[0204] The average molecular weight of nonionic dispersants is typically 300 to 5,000, for example, 500 to 3,000.

[0205] Nonionic dispersants can be a single type or a mixture of two or more. Nonionic dispersants can be mixtures of compounds with an HLB (hydrophilicity / hydrophobicity balance) of less than 15 (particularly less than 5) and compounds with an HLB of 15 or more. Specifically, they are preferably selected from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyethylene oxide, polyoxypropylene, or dehydrated sorbitol fatty acid esters, fatty acid glycerides, polyglycerol fatty acid esters, fatty acid sucrose esters, fatty acid propylene glycol esters, polyoxyethylene glycerol fatty acid esters, and polyoxyethylene dehydrated sorbitol fatty acid esters with an HLB value of less than 7.

[0206] [Catonic dispersant] Dispersants may include cationic dispersants. Cationic dispersants may be cationic surfactants. Cationic dispersants may also be compounds without amide groups.

[0207] Cationic dispersants can be low molecular weight (e.g., molecular weight below 2000, especially below 10000) or high molecular weight (e.g., molecular weight above 2000). The molecular weight of cationic dispersants can be above 100, above 500, above 1000, above 2000, above 4000, or above 6000, and can be below 1,000,000, below 750,000, below 500,000, below 250,000, below 100,000, below 50,000, below 10,000, below 7,500, below 5,000, below 25,000, below 750, or below 250.

[0208] Cationic dispersants can be aliphatic or aromatic, and examples include ammonium salts (such as quaternary ammonium salts). Cationic dispersants can also be addition-type ammonium salts of ethylene oxide. Specific examples include: amine salt dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazoline; quaternary ammonium salt dispersants such as alkyl trimethylammonium salts, dialkyl dimethylammonium salts, alkyl dimethyl benzylammonium salts, pyridinium salts, alkyl isoquinoline onion salts, benzalkonium chloride, and benzyl chloride; and high-molecular-weight cationic dispersants such as polyquaternium salts -1 to 47. Alkylamine salts and quaternary ammonium salts are examples of cationic dispersants.

[0209] Low-molecular-weight cationic dispersants can be compounds represented by the following formula: R 21 -N ＋ (-R 22 (-R) 23 (-R) 24 )X － [In the formula, R] 21 R 22 R 23 and R 24 It consists of hydrogen or a hydrocarbon group having 1 to 40 carbon atoms. X is an anionic group. R 21 R 22 R 23 and -R 24 Specific examples of X include alkyl groups (e.g., methyl, butyl, stearyl, palmityl), aromatic groups (e.g., benzyl, phenyl), etc. Specific examples of X include halogens (e.g., chlorine), acids (e.g., hydrochloric acid, acetic acid). Examples of cationic dispersants include monoalkyl trimethylammonium salts (alkyl groups with 4 to 40 carbon atoms), benzalkonium chloride, etc.

[0210] Specifically, low-molecular-weight cationic dispersants can be ammonium salts as shown in the following formula: R 1 p -N ＋ R 2 q X － [In the formula, R] 1 C 12 The above (e.g., C) 12 ~C 50 Straight-chain and / or branched aliphatic (saturated and / or unsaturated) groups, R 2It is an alkyl group, benzyl group, or polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (especially 2, especially 3) to 50) of H or C1 to 4 (particularly preferred CH3, C2H5). X is a halogen atom (e.g., chlorine), a C1-C4 fatty acid salt, or a C1-C4 sulfonate. p is 1 or 2, q is 2 or 3, and p + q = 4. R 1 The number of carbon atoms can be 12 to 50, for example 12 to 30.

[0211] Low molecular weight cationic dispersants may include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyl di(hydrogenated polyoxyethylene)ammonium chloride, benzyldodecyl di(hydrogenated polyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride, etc.

[0212] High-molecular-weight cationic dispersants can be various polymers (e.g., polyquaternium salts-1 to 47) containing cationic groups (e.g., ammonium groups, quaternary ammonium groups). Examples of high-molecular-weight cationic dispersants include: cationic starch, cationic cellulose (e.g., O-(2-hydroxy-3-(trimethylammonium)propylhydroxyethyl cellulose chloride)), cationic guar gum, cationic xanthan gum, chitosan, and other cationic natural products (especially cationic sugars); polymers of monomers containing cationic groups such as aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternized dimethylammonium ethyl methacrylate, diallyl dimethylammonium chloride, dimethylaminopropylamine, and quaternized vinylimidazole.

[0213] [Anionic dispersant] Dispersants may contain anionic dispersants. Anionic dispersants may be anionic surfactants. Dispersants may also not contain anionic dispersants.

[0214] Anionic dispersants can be low molecular weight (e.g., molecular weight below 2000, especially below 10000) or high molecular weight (e.g., molecular weight above 2000). The molecular weight of anionic dispersants can be above 100, above 500, above 1000, above 2000, above 4000, or above 6000, and can be below 1,000,000, below 750,000, below 500,000, below 250,000, below 100,000, below 50,000, below 10,000, below 7,500, below 5,000, below 25,000, below 750, or below 250.

[0215] Examples of anionic dispersants 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-sulfonyl fatty acid salts, N-acyl amino acid type dispersants, phosphate monoester or phosphate diester type dispersants, and sulfosuccinates. Examples of anionic dispersants include carboxylates (e.g., fatty acid salts), etc.

[0216] [Amphoteric Dispersant] Dispersants may include amphoteric dispersants. Amphoteric dispersants may be amphoteric surfactants.

[0217] Amphoteric dispersants can be low molecular weight (e.g., molecular weight below 2000, especially below 10000) or high molecular weight (e.g., molecular weight above 2000). The molecular weight of amphoteric dispersants can be above 100, above 500, above 1000, above 2000, above 4000, or above 6000, and can be below 1,000,000, below 750,000, below 500,000, below 250,000, below 100,000, below 50,000, below 10,000, below 7,500, below 5,000, below 25,000, below 750, or below 250.

[0218] Examples of amphoteric dispersants include alanine derivatives, imidazoline betaines, amide betaines, and acetate betaines, specifically lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazoline betaine, lauryl dimethyl aminoacetic acid betaine, and fatty amide propyl dimethyl aminoacetic acid betaine.

[0219] [Inorganic dispersant] Dispersants may include inorganic dispersants.

[0220] The average primary particle size of inorganic dispersants can be greater than 5 nm, greater than 30 nm, greater than 100 nm, greater than 1 μm, greater than 10 μm, or greater than 25 μm, and can also be less than 100 μm, less than 50 μm, less than 10 μm, less than 1 μm, less than 500 nm, or less than 300 nm. The average primary particle size can be determined, for example, by observation using a microscope (scanning electron microscope or transmission electron microscope). Inorganic dispersants can be hydrophilic particles.

[0221] Examples of inorganic dispersants include: tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, hydroxyapatite and other polyvalent metal salts of phosphate; carbonates of calcium carbonate, magnesium carbonate and other carbonates; silicates such as calcium metasilicate; sulfates such as calcium sulfate, barium sulfate and other sulfates; hydroxides such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide, etc.

[0222] [Amount of dispersant] The amount of dispersant relative to 100 parts by weight of the liquid-repellent compound can be more than 0.01 parts by weight, more than 0.1 parts by weight, more than 1 part by weight, more than 3 parts by weight, more than 5 parts by weight, more than 10 parts by weight, more than 15 parts by weight, more than 20 parts by weight, more than 50 parts by weight, more than 75 parts by weight, or more than 100 parts by weight, and can be less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, less than 5 parts by weight, less than 3 parts by weight, or less than 1 part by weight.

[0223] [Liquid medium] The dispersant 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 dispersant may be a dispersion or a solution. The dispersant of the present invention is suitable as an aqueous dispersion or an aqueous solution.

[0224] Examples of organic solvents include esters (e.g., esters with 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2 to 40 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols with 1 to 40 carbon atoms, specifically isopropanol), aromatic solvents (e.g., toluene and xylene), and petroleum-based solvents (e.g., alkanes with 5 to 10 carbon atoms, specifically naphtha and kerosene). Water-soluble organic solvents are preferred. Water-soluble organic solvents may contain compounds having at least one hydroxyl group (e.g., alcohols, diols, polyols, ethers of polyols (e.g., monoethers)). These compounds may be used alone or in combination of two or more.

[0225] The dispersant of the present invention can be an organic solvent solution or an organic solvent dispersion. An organic solvent solution refers to a liquid in which the solute is dissolved in a solvent to form a homogeneous phase. An organic solvent dispersion refers to a liquid in which the solute is suspended or floated in a solvent as particles and can be separated into solute (dispersed phase) and solvent (dispersed phase) by centrifugation or other methods.

[0226] [Amount of liquid medium] The amount of liquid medium relative to 1 part by weight of the repellent compound can be more than 1 part by weight, more than 3 parts by weight, more than 5 parts by weight, more than 10 parts by weight, more than 20 parts by weight, more than 30 parts by weight, more than 40 parts by weight, more than 50 parts by weight, more than 100 parts by weight, more than 200 parts by weight, more than 300 parts by weight, more than 500 parts by weight, or more than 1000 parts by weight, and can 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.

[0227] The amount of water relative to 1 part by weight of the liquid-repellent compound can be more than 1 part by weight, more than 3 parts by weight, more than 5 parts by weight, more than 10 parts by weight, more than 20 parts by weight, more than 30 parts by weight, more than 40 parts by weight, more than 50 parts by weight, more than 100 parts by weight, more than 200 parts by weight, more than 300 parts by weight, more than 500 parts by weight, or more than 1000 parts by weight, and can 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.

[0228] The amount of organic solvent relative to 1 part by weight of the liquid-repellent compound can be more than 1 part by weight, more than 3 parts by weight, more than 5 parts by weight, more than 10 parts by weight, more than 20 parts by weight, more than 30 parts by weight, more than 40 parts by weight, more than 50 parts by weight, more than 100 parts by weight, more than 200 parts by weight, more than 300 parts by weight, more than 500 parts by weight, or more than 1000 parts by weight, and can 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.

[0229] [Organic acids] The dissolving agent of the present invention may contain an organic acid. Known compounds can be used as the organic acid. Carboxylic acids, sulfonic acids, sulfinic acids, etc., are preferred examples of organic acids, with carboxylic acids being particularly preferred. Examples of such carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., with formic acid or acetic acid being particularly preferred. In the present invention, one organic acid may be used, or two or more may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0230] [Amount of organic acids] The amount of organic acid relative to 100 parts by weight of the repellent compound 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 less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 40 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight. The amount of organic acid can be adjusted so that the pH of the repellent is 3 to 10, for example 5 to 9, especially 6 to 8. The repellent can be acidic (pH 7 or below, for example 6 or below).

[0231] [Inorganic acids] The dispersant of the present invention may contain an inorganic acid. Known compounds can be used as the inorganic acid. Examples of inorganic acids include hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, boric acid, sulfuric acid, and phosphoric acid. In the present invention, one inorganic acid may be used, or two or more may be used in combination. By adding an inorganic acid, the stability of the aqueous dispersion can be improved.

[0232] [Amount of inorganic acid] The amount of inorganic acid relative to 100 parts by weight of the repellent compound 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 less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 40 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight. The amount of inorganic acid can be adjusted so that the pH of the repellent is 3 to 10, for example 5 to 9, especially 6 to 8. The repellent can be acidic (pH 7 or below, for example 6 or below).

[0233] [Curing agent] The release agent of the present invention may contain a curing agent (an active hydrogen reactive compound or a compound containing active hydrogen). When the release agent is used in paper (e.g., an oil-resistant agent for paper), it may not contain a curing agent.

[0234] The curing agent (crosslinking agent) in the release agent enables it to cure well. The curing agent can be an active hydrogen reactive compound or a compound containing active hydrogen, which reacts with active hydrogen or reactive groups of active hydrogen. Examples of active hydrogen reactive compounds include isocyanate compounds, epoxy compounds, compounds containing chloromethyl groups, compounds containing carboxyl groups, and acylhydrazine compounds. Examples of compounds containing active hydrogen include compounds containing hydroxyl groups, compounds containing amino groups, compounds containing carboxyl groups, compounds containing ketone groups, acylhydrazine compounds, melamine compounds, and urea-based compounds.

[0235] Curing agents can contain isocyanate compounds. Isocyanate compounds can be polyisocyanate compounds. Polyisocyanate compounds are compounds having two or more isocyanate groups in one molecule. Polyisocyanate compounds function as crosslinking agents. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. Isocyanate compounds can be end-capped isocyanate compounds (e.g., end-capped polyisocyanate compounds). End-capped isocyanate compounds are compounds in which the isocyanate groups are masked by a capping agent, thus inhibiting the reaction.

[0236] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propanediisocyanate, 1,2-butanediisocyanate, 2,3-butanediisocyanate, 1,3-butanediisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate-methylhexanoate, lysine triisocyanate, 1,4,8-triisocyanate-octane, 1,6,11-triisocyanate-undecane, 1,8-diisocyanate-4-isocyanate-methyloctane, 1,3,6-triisocyanate-hexane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate-methyloctane, and other aliphatic triisocyanates. These compounds can be used alone, or in combination of two or more.

[0237] 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), 1,3,5-triisocyanatocyclohexane, 4,4'-methylenebis(cyclohexyl isocyanate), and 1,3-bis(isocyanatomethyl)cyclohexane. These compounds can be used alone or in combination of two or more.

[0238] Examples of aromatic aliphatic polyisocyanates are aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of aromatic aliphatic polyisocyanates include 1,3- or 1,4-phenylene diisocyanate or mixtures thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylphenylene diisocyanate or mixtures thereof), and 1,3,5-triisocyanatomethylbenzene. These compounds can be used alone or in combination of two or more.

[0239] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include isophenylene diisocyanate, terephthalene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or mixtures thereof, 2,4- or 2,6-toluene diisocyanate or mixtures thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate, etc. These compounds can be used alone or in combination of two or more.

[0240] Derivatives of polyisocyanates include, for example, dimers, trimers, biurets, urethanes, carbodiimides, urea diketones, urea ketimides, isocyanurates, iminooxadiazine diketones, and other derivatives of the aforementioned polyisocyanate compounds. These compounds can be used alone or in combination of two or more.

[0241] These polyisocyanates can be used alone or in combination of two or more. As a polyisocyanate compound, a capped polyisocyanate compound (capped isocyanate) is preferred, formed by capping the isocyanate group of the polyisocyanate compound with a capping agent. Capped polyisocyanate compounds are preferred because they are more stable in solution and can be used even in solutions similar to the capping agent.

[0242] End-capping agents are used to end free isocyanate groups. End-capped polyisocyanate compounds, for example, can readily react with hydroxyl groups by regenerating the isocyanate groups through heating to above 100°C, such as above 130°C. Examples of end-capping agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, oxime compounds, and pyrazole compounds. Polyisocyanate compounds can be used alone or in combination of two or more.

[0243] Epoxy compounds are compounds containing epoxy groups. Examples of epoxy compounds include those containing polyoxyalkylene groups, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether, etc.

[0244] Compounds containing chloromethyl groups are compounds that have a chloromethyl group. Examples of compounds containing chloromethyl groups include chloromethyl polystyrene.

[0245] Compounds containing a carboxyl group are compounds that possess a carboxyl group. Examples of compounds containing a carboxyl group include (poly)acrylic acid and (poly)methacrylic acid.

[0246] Specific examples of compounds containing ketone groups include (poly)diacetone acrylamide and diacetone alcohol.

[0247] Specific examples of acylhydrazide compounds include hydrazine, carbonylhydrazide, and adipic acid dihydrazide.

[0248] Specific examples of melamine compounds include melamine resins and methyl etherified melamine resins.

[0249] Specific examples of urea compounds include dimethyloldihydroxyethyleneurea (DMDHEU) and dimethyldihydroxyethyleneurea.

[0250] [Amount of curing agent] The amount of curing agent relative to 100 parts by weight of the liquid-repellent compound can be more than 0.1 parts by weight, more than 1 part by weight, more than 3 parts by weight, more than 5 parts by weight, more than 10 parts by weight, more than 15 parts by weight, or more than 20 parts by weight, more than 50 parts by weight, more than 75 parts by weight, or more than 100 parts by weight, and can be less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 40 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight.

[0251] [Other ingredients] The repellent agent may contain other components besides those mentioned above. Other components may also be added after the manufacture of the hydrocarbon-based water-repellent resin. Examples of other components include water-repellent and / or oil-repellent agents, antislip agents, antistatic agents, preservatives, antibacterial agents, deodorizers, and penetrants. These compounds can be used alone or in combination of two or more. In addition to the components mentioned above, other components may include hand feel modifiers, softeners, antibacterial agents, flame retardants, anti-wrinkle agents, crosslinking agents, film-forming aids, compatibilizers, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, anti-shrinkage agents, detergent-resistant wrinkle-resistant agents, shape-retaining agents, drape-retaining agents, ironing agents, polymeric dispersants, scum dispersants, fluorescent whitening agents, dye fixatives, and defoaming agents. These can be used alone or in combination of two or more.

[0252] (Antistatic agent) Examples of antistatic agents include: cationic antistatic agents with cationic functional groups such as quaternary ammonium salts, pyridinium salts, and first, second, and third amino groups; anionic antistatic agents with anionic functional groups such as sulfonates, sulfates, phosphonates, and phosphates; amphoteric antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, and alanine and its derivatives; and nonionic antistatic agents such as amino alcohols and their derivatives, glycerol and its derivatives, and polyethylene glycol and its derivatives. Ionically conductive polymers can also be obtained by polymerizing or copolymerizing these cationic, anionic, and amphoteric monomers with ionically conductive groups. These can be used alone or in combination of two or more.

[0253] (preservative) Preservatives are mainly used to enhance preservative and bactericidal properties, maintaining preservation properties during long-term storage. Examples of preservatives include isothiazolinone-based organosulfur compounds, benzisothiazolinone-based organosulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol. The amount of preservative relative to the total weight of the extract is preferably 0.0001 to 1% by weight. When the amount of preservative is above the lower limit of the above range, the effect of adding preservative can be fully obtained, and when it is below the upper limit, the preservation stability of the extract is good.

[0254] (Antibacterial agent) Antimicrobial agents are ingredients that inhibit the proliferation of bacteria on fibers, thereby suppressing the production of unpleasant odors from microbial decomposition products. Examples of antimicrobial agents include cationic bactericides such as quaternary ammonium salts, zinc bis-(2-pyridinium-1-oxide), polyhexamethylene biguanide hydrochloride, 8-hydroxyquinoline, and polylysine.

[0255] (Deodorizer) Examples of deodorizing agents include clustered dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, amide-propyl dimethylamine oxide, and aminocarboxylic acid metal complexes (such as the zinc complex of sodium methylglycine diacetate described in International Publication No. 2012 / 090580).

[0256] (Anti-slip agent) Antislip agents are components that inhibit the misalignment of fiber loops and seams during sewing or wearing. Examples of antislip agents include polysiloxane compounds, colloidal silica, silicone resin derivatives, colloidal silicone systems, and amino-modified silicones.

[0257] (softener) Fabric softener is a component that imparts a soft and smooth feel to fabric. Examples of fabric softener components include cationic surfactants such as quaternary ammonium salts and amine salts, soaps, sulfurized oils, anionic surfactants such as higher alcohol sulfate salts and sulfonates, nonionic surfactants such as polyols and polyethylene glycols, amphoteric surfactants such as betaine-type and amino acid-type surfactants, and siloxane resins.

[0258] [Amount of other ingredients] Relative to 100 parts by weight of the liquid-repellent compound, the amount or total amount of each of the other components can be more than 0.1 parts by weight, more than 1 part by weight, more than 3 parts by weight, more than 5 parts by weight, more than 10 parts by weight, more than 15 parts by weight, more than 20 parts by weight, more than 50 parts by weight, more than 75 parts by weight, or more than 100 parts by weight, and can be less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 40 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight.

[0259] <Uses of the dispensing agent> Examples of uses of the release agent of the present invention include external treatment agents (surface treatment agents) or internal treatment agents, release agents (water repellent, oil repellent or water and oil repellent, etc., especially water repellent), antifouling agents, dirt removal agents, stripping agents, mold release agents (external mold release agents or internal mold release agents), etc.

[0260] <Method for manufacturing processed products> The manufacturing method of the treated article in this invention includes a step of treating the substrate with a stripping agent.

[0261] [Processed Products] Examples of substrates that can be treated with the release agent of the present invention include fiber substrates, stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, coatings, and gypsum. Various examples of fiber substrates can be cited. For instance, examples include natural plant and animal fibers such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and cellulose acetate; inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber; or blends thereof. As an example of a substrate treated with the release agent, an example of fabric will be described in detail.

[0262] (Fabric) Fabric manufacturing methods Fabrics can be obtained by weaving long and short fibers composed of the aforementioned fibers to produce greige fabric, followed by post-processing and water-repellent finishing. Weaving can be carried out using known looms and braiding machines, and the preparatory processes before weaving can also be performed using known equipment.

[0263] After weaving, the fabric can be further processed using known scouring, dyeing methods and equipment suitable for the fabric's fiber materials.

[0264] After post-processing, the fabric can undergo a water-repellent treatment. In this treatment, firstly, an aqueous solution containing a water-repellent agent (which can be the water-repellent agent used in this invention) is prepared. Then, based on methods such as padding, spraying, slit coating, or narrow-slit coating, the post-processed fabric is coated with this aqueous solution, dried, and then subjected to dry heat treatment. The aqueous solution may contain cross-linking agents, softeners, antistatic agents, etc., as needed. After the water-repellent treatment, the fabric can also be calendered.

[0265] The fabric is suitable for clothing applications requiring water repellency, especially for outdoor, skiing, snowboarding, golf and other sportswear, as well as uniforms.

[0266] Layered fabrics A laminated fabric with a breathable and waterproof layer on one side of the fabric of the present invention can also be provided. The breathable and waterproof layer can be directly laminated onto the fabric, or it can be laminated onto the fabric via an adhesive layer. In addition, when the laminated fabric of the present invention is used for clothing or other applications, the fabric side is positioned to repel rainwater.

[0267] • Breathable waterproof layer A breathable and waterproof layer refers to a single-sided layer of a fabric, which is a layer formed by a resin or membrane structure that has waterproof and breathable properties.

[0268] A breathable and waterproof layer can be formed by directly coating the fabric with resin (the resin that constitutes the breathable and waterproof layer), or by laminating it onto one side of the fabric via an adhesive layer described later.

[0269] There are no particular limitations on the resin used to form the breathable and waterproof layer; both non-porous and porous resins can be used. Non-porous resins include polyurethane resins and polyester elastomer resins, which have hydrophilic components to provide breathability. In addition, porous resins include polyurethane resins that form wet porous membranes and polyurethane resins that have been porousized by electrospinning, as well as porous membranes made of PTFE, PE, or PP.

[0270] As a polyurethane resin, conventionally known substances obtained by reacting a polyisocyanate component with a polyol component can be used.

[0271] A breathable and waterproof membrane with a microporous structure can be obtained by wet coagulation of a DMF solution of polyurethane resin containing inorganic micropowder.

[0272] Examples of inorganic micropowders include those composed of silicon dioxide, aluminum oxide, or titanium dioxide. Furthermore, the average primary particle size of the inorganic micropowder is preferably around 7 to 40 nm. The content of the inorganic micropowder relative to the total amount of the breathable and waterproof layer is preferably 3 to 50% by weight, more preferably 5 to 50% by weight.

[0273] The thickness of the breathable waterproof layer is preferably 5 μm or more, more preferably 10 to 30 μm. When the thickness is within the above range, the balance between waterproofness and breathability is excellent, and it is also advantageous in terms of feel, etc.

[0274] Adhesive layer The laminated fabric preferably contains an adhesive layer. That is, the fabric and the breathable waterproof layer are preferably laminated via an adhesive layer. In addition, from the viewpoint of breathability, the adhesive layer is preferably a discontinuous layer such as a dotted or grid pattern.

[0275] There are no particular restrictions on the type of adhesive used to form the adhesive layer, but a substance with excellent adhesion to the breathable and waterproof layer is preferred. For example, when a resin with polyurethane resin as the main component is selected as the resin for forming the breathable and waterproof layer, an adhesive layer composed of a polyurethane-based adhesive is preferred. Polyurethane-based adhesives can be substances with any structure, such as ether-based, ester-based, or polycarbonate-based adhesives.

[0276] The adhesive layer can be formed on the entire surface of one side of the fabric, or it can be patterned from the viewpoint of moisture permeability or hand feel. There are no particular limitations on the form of the pattern, and examples include dots, lines, grids, checkerboard patterns, tortoise shell patterns, etc., all of which are preferably evenly distributed throughout the fabric.

[0277] The thickness of the adhesive layer is preferably about 10 to 100 μm, and more preferably 20 to 80 μm.

[0278] Lining fabric made of fiber cloth In the layered fabric of the present invention, a lining fiber fabric may also be layered on the breathable and waterproof layer (the side of the breathable and waterproof layer opposite to the side of the fabric layer of the present invention). The lining fiber fabric can protect the breathable and waterproof layer, and can further enhance the waterproofness (water pressure resistance) and strength.

[0279] As lining fabrics, various types of woven fabrics and knitted fabrics can be listed. Among them, knitted fabrics are more suitable because, compared to woven fabrics, the yarns tend to protrude from the surface rather than forming a flat surface, making it easier to anchor and less likely to peel off from the breathable and waterproof layer.

[0280] In addition, Trico warp-knitted fabrics can produce long greige fabrics with fewer seams during the knitting process, and are also preferred from the point of being able to be evenly layered on a breathable and waterproof layer.

[0281] There are no particular limitations on the material of the fibers constituting the lining fabric, and appropriate selections can be made, but nylon fibers are preferred. This is because acid dyes are generally used in nylon fibers, thus reducing the likelihood of migration and sublimation of disperse dyes, which are problematic in polyester fibers and the like, that migrate to the breathable and waterproof layer. The morphology (long fibers, short fibers, or spun yarns) or fineness of the fibers constituting the lining fabric are not particularly limited, and can be appropriately selected within a range that does not impair the effects of the present invention.

[0282] Characteristics of layered fabrics The layered fabric has excellent water resistance. As a suitable example of the water resistance of the layered fabric of the present invention, the water level measured according to the water resistance test specified in JIS L 1092:2009 Method A (low water pressure method) can be cited, for example, 10,000 mm or more, preferably 15,000 mm or more, more preferably 16,000 mm or more, and particularly preferably 20,000 mm or more.

[0283] The layered fabric exhibits excellent moisture permeability. As a suitable example of the moisture permeability of the layered fabric of this invention, a moisture permeability measured according to the JIS L 1099:2021 B-1 method (potassium acetate method) can be cited, for example, as 10000 g / m². 2 • More than 24 hours, preferably 15000g / m 2 • More than 24 hours, preferably 20000 g / m 2 • More than 24 hours. There is no specific upper limit to this permeability; for example, 40,000 g / m² could be cited. 2 ·24h or 35000g / m2 • 24h • mm. Additionally, the permeability measured according to JIS L1099:2021 A-1 method (calcium chloride method) is, for example, 4000 g / m³. 2 • More than 24 hours, preferably 8000g / m 2 • 24 hours or more, preferably 10000 g / m 2 • More than 24 hours. Regarding the upper limit of this permeability, as the limit of the measurement method, it is 13000~15000g / m³. 2 Approximately 24 hours.

[0284] In the layered fabric of the present invention, as the peel strength between the fabric and the breathable and waterproof layer, a peel strength of 2.55 N / 2.54 cm or more, as measured according to the method of JIS K 6404-2, is preferred for the purpose of clothing application, and sometimes 5 N / 2.54 cm or more is preferred depending on the application.

[0285] Manufacturing method of layered fabrics There are no particular limitations on the manufacturing method of the layered fabric. For example, the first manufacturing method and the second manufacturing method shown below can be listed.

[0286] First manufacturing method: including a process of forming the above-mentioned breathable and waterproof layer by coating the surface of a fabric with a resin constituting the above-mentioned breathable and waterproof layer.

[0287] The second manufacturing method includes a process of forming an adhesive layer on a fabric or a breathable waterproof layer, and a process of bonding the fabric to the breathable waterproof layer via the adhesive layer.

[0288] In the first manufacturing method, a method for applying a resin constituting a breathable and waterproof layer to the surface of the fabric can be, for example, a coating method. In the coating method, a doctor blade coater or a comma coater can be used. Furthermore, from the viewpoint of achieving excellent breathability, a wet method is preferred for obtaining the breathable and waterproof layer.

[0289] In the second manufacturing method, lamination is an example of a method for forming an adhesive layer on a fabric or a breathable waterproof layer. In lamination, the adhesive layer can be formed using a resin solution or a hot-melt method. First, a breathable waterproof layer is formed by adjusting the thickness of a resin composition (e.g., a resin composition containing resin and organic solvent) on the surface of a release material (release paper, release cloth, or release film, etc.) with gaps, and then dried and heat-treated to obtain a film. The release material can be appropriately removed after lamination or curing. Alternatively, in the case of hot-melt lamination, the release material can be peeled off, and the film monomer can be used for lamination.

[0290] In addition, as a breathable and waterproof membrane, it can be laminated with membranes produced by solvent-free T-die extrusion, blown film extrusion, porous membranes produced by electrospinning, porous membranes of PTFE, PE, PP, etc.

[0291] Then, an adhesive layer is formed on the fabric or the breathable waterproof layer. For example, in the case of using a resin solution, a polyurethane resin solution that is a two-component curing type and whose viscosity is adjusted to the range of 500 to 5000 mPa·s can be prepared by coating the entire surface or in a pattern. After drying, an adhesive layer is formed, and the fabric and the breathable waterproof layer are bonded together via the adhesive layer. The second manufacturing method can be implemented by pressing or heat-pressing the two together.

[0292] On the other hand, in the case of heat fusion, a moisture-curing resin that reacts with moisture in the air is suitable, and practically, a substance that melts in a temperature range of approximately 80–150°C is more preferred. In this case, firstly, the heat-melting resin is melted while taking into account the resin's melting point and viscosity during melting. Then, the molten resin is coated onto the fabric or the breathable waterproof layer to form an adhesive layer, and the fabric is bonded and pressed against the breathable waterproof layer, thereby enabling the second manufacturing method. Alternatively, if a good feel is desired, the breathable waterproof membrane can be coated in a pattern and bonded to the fabric.

[0293] Subsequently, a suitable, known technique can be used to layer a lining fabric on top of the breathable and waterproof layer.

[0294] Uses of layered fabrics Layered fabrics offer excellent water repellency and breathability, and the breathable and waterproof layers do not peel off even in harsh environments, making them suitable for use in outdoor uniforms, sportswear, and outdoor products.

[0295] [Handling Method] The repellent of the present invention can be used as a treatment agent (especially a surface treatment agent) and applied to a substrate using conventionally known methods. This can be achieved by dispersing the repellent in an organic solvent or water as needed, diluting it with known methods such as dip coating, spraying, or foam coating, and then drying it. After drying, a fiber substrate with the solid components of the repellent attached is obtained. Alternatively, it can be applied together with a suitable crosslinking agent for curing, as needed. Furthermore, the repellent of the present invention can be used in combination with various additives such as water-repellent and / or oil-repellent agents, antislip agents, antistatic agents, hand feel modifiers, softeners, antibacterial agents, flame retardants, coating fixatives, anti-wrinkle agents, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, and defoamers. Examples of various additives include substances identical to those described in the "Other Components" section of the repellent described above. The concentration of the hydrocarbon-based water-repellent resin in the treatment agent that contacts the substrate can be appropriately varied depending on the application, and can be 0.01 to 10% by weight, for example 0.05 to 5% by weight.

[0296] [Fiber-based substrate] Various examples can be cited of fiber substrates, such as fabric products and paper products.

[0297] Examples of textile products include natural plant and animal fibers such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester (especially polyethylene terephthalate, preferred), polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and cellulose acetate; and inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber, or blends thereof. Textile products include woven fabrics, knitted fabrics, nonwoven fabrics, and clothing and blankets, but can also be made from fibers, yarns, and intermediate fiber products (such as cotton slivers or rovings) in their state before being made into fabric.

[0298] Examples of paper products include paper made from bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp, high-yield bleached or unbleached pulps such as wood pulp, mechanical pulp or thermomechanical pulp, recycled newsprint, recycled magazine paper, corrugated paper or deinked paper, etc.; containers made of paper; and molded objects made of paper. Specific examples of paper products include food packaging paper, gypsum board base paper, coated base paper, medium-quality paper, ordinary liner paper and core, neutral pure white toilet paper, neutral liner paper, rust-proof liner paper and metal composite paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral heat-sensitive paper, neutral compression base paper, neutral inkjet paper and neutral information paper, and molding paper (molded containers).

[0299] The repellent agent can be applied to the fiber substrate (e.g., fabric) by any method known as liquid treatment of the fiber substrate. The fiber substrate can be immersed in the repellent agent, or the solution can be applied to or sprayed onto the fiber substrate. For the treated fiber substrate, to exhibit water-repellent and oil-repellent properties, it is preferable to dry and cure by heating. Heating temperatures can be, for example, 100°C–200°C, 100°C–170°C, or 100°C–120°C. In this invention, good performance can be obtained even with low-temperature heating (e.g., 100°C–140°C). In this invention, the heating time can be from 5 seconds to 60 minutes, for example, from 30 seconds to 3 minutes.

[0300] Alternatively, the liquid-repellent compound can be applied to the fiber substrate by a dry cleaning method, for example, by a washing application or a dry cleaning process.

[0301] The treated fiber substrate can be fabric, including woven fabrics, knitted fabrics, nonwoven fabrics, clothing items, blankets, etc., but can also be fibers, yarns, or intermediate fiber products (e.g., slivers or rovings). The repellent agent of the present invention is particularly effective in imparting water-repellent properties to fiber substrates (e.g., synthetic fibers).

[0302] The fibers constituting the fiber substrate can be natural fibers, synthetic fibers, semi-synthetic fibers, regenerated fibers, or inorganic fibers. A single type of fiber can be used, or two or more can be used in combination.

[0303] Examples of natural fibers include cellulose fibers such as cotton, flax, and pulp, as well as chitin, chitosan, wool, and silk. Specific examples of wood pulp include mechanical pulps such as groundwood pulp (GP), press-groundwood pulp (PGW), and thermomechanical pulp (TMP); chemical pulps such as high-yield unbleached coniferous kraft pulp (HNKP; N-grade), bleached coniferous kraft pulp (NBKP; N-grade, NB-grade), unbleached hardwood kraft pulp (LUKP; L-grade), bleached hardwood kraft pulp (LBKP, L-grade); deinking pulp (DIP); waste paper pulp (WP); and semi-chemical pulp (CP).

[0304] Examples of synthetic fibers include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, and copolyester; polyolefins such as linear low-density polyethylene, low-density polyethylene, high-density polyethylene, and polypropylene; polyamides such as nylon 6, nylon 66, nylon 610, and nylon 46; acrylic fibers such as polyacrylonitrile; and polyvinyl alcohol, polyurethane, and polyvinyl chloride.

[0305] Examples of semi-synthetic fibers include cellulose acetate and cellulose triacetate. Examples of regenerated fibers include rayon, cupro, polynix, lyocell, and Tencel. Examples of inorganic fibers include glass fiber and carbon fiber.

[0306] Alternatively, the fiber substrate can be leather. To make the leather hydrophobic and oleophobic, a repellent compound can be applied to the leather from an aqueous solution or aqueous emulsion at various stages of leather processing, such as during the wet processing of the leather or during the finishing of the leather.

[0307] Alternatively, the fiber substrate can be paper. The liquid-repellent compound can be applied to pre-formed paper or at various stages of papermaking, such as during paper drying.

[0308] "Treatment" refers to the application of a repellent agent to a substrate through methods such as impregnation, spraying, or coating. Through treatment, the repellent compound, as the active ingredient of the repellent agent, penetrates into the interior of the substrate and / or adheres to the surface of the substrate.

[0309] [Pretreatment of fiber substrate] The fiber substrate can also undergo pretreatment before being treated with the release agent of the present invention. By pretreating the fiber substrate, excellent fastness can be imparted to the fiber substrate after treatment with the release agent.

[0310] Examples of pretreatment for fiber substrates include cationization, sulfonation, carboxylation, phosphorylation and other anionization treatments such as reaction with reactive quaternary ammonium salts, acetylation after anionization treatment, benzoylation, carboxymethylation, grafting, tannic acid treatment, and polymer coating treatment.

[0311] There are no limitations on the method for pretreating the fiber substrate; it can be performed using methods already known. One possible method is to disperse the pretreatment solution in an organic solvent or water for dilution, then apply it to the surface of the fiber substrate using known methods such as dip coating, spraying, or foam coating, followed by drying. The pH and temperature of the pretreatment solution can be adjusted according to the desired level of treatment. As an example of a method for pretreating the fiber substrate, a method using a hydrocarbon-based water-repellent agent will be described in detail.

[0312] The pretreatment method for fiber substrates can also be equipped with a substance selected from SO3M 1 (where M) 1 (representing a monovalent cation) The monovalent group, -COOM 2 (where M) 2 The monovalent radicals (representing monovalent cations) and -O-P(O)(OX) are shown. 1 (OX) 2 (where X) 1 and X 2A process comprising at least one functional group (hereinafter sometimes referred to as "specific functional group") of a monovalent group consisting of a group of hydrogen atoms or an alkyl group having 1 to 22 carbon atoms, each independently representing a hydrogen atom or a carbon atom, respectively.

[0313] As M 1 Examples include H, K, Na, or ammonium ions that may have substituents. As M... 2 Examples include H, K, Na, or ammonium ions that may have substituents. In X 1 or X 2 When the alkyl group is used, it is preferably an alkyl group with 1 to 22 carbon atoms, and more preferably an alkyl group with 4 to 12 carbon atoms.

[0314] Fibers containing the aforementioned specific functional groups (hereinafter sometimes referred to as "fibers containing functional groups") can be prepared, for example, by the following methods.

[0315] (i) To attach a compound having the aforementioned specific functional groups to a fibrous material. Furthermore, the attachment of the compound can be a state in which a portion of the compound is chemically bonded to a portion of the fiber, within a range where a sufficient amount of the aforementioned specific functional groups are retained.

[0316] (ii) A fiber in which the aforementioned specific functional groups are directly introduced into the material constituting the fiber.

[0317] In case (i), for example, by treating the fiber material with a pretreatment solution containing one or more compounds having the aforementioned specific functional groups in the functional group introduction process, it is possible to obtain fibers containing functional groups.

[0318] There are no particular restrictions on the raw materials used for fiber materials. Examples include natural fibers such as cotton, linen, silk, and wool; semi-synthetic fibers such as rayon and cellulose acetate; and synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene, as well as composite fibers and blended fibers of these. Fiber materials can take any form, including fibers (tows, slivers, etc.), yarns, knitted fabrics (including blends), woven fabrics (including blends), nonwoven fabrics, and paper.

[0319] In this embodiment, from the viewpoint that the obtained fiber substrate has good water repellency, it is preferable to use fiber materials made from polyamide and polyester, and particularly preferable to use nylon 6, nylon 6,6 and other nylons, polyethylene terephthalate (PET), polyethylene terephthalate, polylactic acid and other polyesters, and mixed fibers containing these.

[0320] As having the above-mentioned -SO3M 1 For compounds, phenolic polymers can be used. Examples of such phenolic polymers include substances containing at least one compound represented by the following general formula. [In formula (2), X] 2 Indicates - SO3M 3 (where M) 3 [A cation with a monovalent charge (or a group represented by the following general formula), where n is an integer from 20 to 3000.] [In the formula, M] 4 This represents a cation with a monovalent charge. As for the above M 3 Examples of possible ions include H, K, Na, or ammonium ions that may have substituents.

[0321] Examples of M4 include H, K, Na, or ammonium ions that may have substituents.

[0322] The compounds represented by the above general formula can be, for example, formaldehyde condensates of phenol sulfonic acid or formaldehyde condensates of sulfonated bisphenol S.

[0323] As having the above-mentioned -COOM 2 Compounds that can be listed include polycarboxylic acid polymers.

[0324] As a polycarboxylic acid polymer, polymers synthesized by conventional free radical polymerization using monomers such as acrylic acid, methacrylic acid, and maleic acid, or commercially available substances can be used.

[0325] One method for manufacturing polycarboxylic acid polymers is to add a free radical polymerization initiator to an aqueous solution of the monomers and / or their salts, and then heat the solution at 30–150°C for 2–5 hours. Alternatively, an alcohol such as methanol, ethanol, or isopropanol, or an aqueous solvent such as acetone, can be added to the aqueous solution of the monomers and / or their salts. Examples of free radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; redox polymerization initiators consisting of combinations of persulfates and sodium bisulfite; hydrogen peroxide; and water-soluble azo polymerization initiators. These free radical polymerization initiators can be used alone or in combination of two or more. Furthermore, during free radical polymerization, a chain transfer agent (e.g., octyl mercaptoacetate) can be added to adjust the degree of polymerization.

[0326] In free radical polymerization, in addition to the monomers mentioned above, copolymerizable monomers can also be used. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate; acrylamide; acrylates; and methacrylates. Acrylates and methacrylates are preferably substances with a hydrocarbon group having 1 to 3 carbon atoms and substituents such as hydroxyl groups. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, and propyl methacrylate. These copolymerizable monomers can be used alone or in combination of two or more.

[0327] In polycarboxylic acid polymers, the carboxyl groups can be free or neutralized by alkali metals or amine compounds. Examples of alkali metals include sodium, potassium, and lithium, while examples of amine compounds include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0328] From the viewpoint that the obtained fiber substrate has good water repellency, the weight-average molecular weight of the polycarboxylic acid polymer is preferably 1,000 to 20,000, more preferably 3,000 to 15,000.

[0329] As a polycarboxylic acid polymer, commercially available products such as "Neocrystal 770" (manufactured by Nichika Chemical Co., Ltd., trade name) and "Celopol PC-300" (manufactured by Sanyo Chemical Co., Ltd., trade name) can be used.

[0330] As having the above-mentioned -O-P(O)(OX) 1 (OX) 2 Compounds of which, for example, can be listed as phosphate ester compounds represented by the following general formula. [In the formula, X] 1 or X 2 Synonymous with the above, X 3 [Represents alkyl groups with 1 to 22 carbon atoms.] As the aforementioned phosphate ester compounds, phosphate monoesters, diesters, and triesters, as well as mixtures thereof, can be used, wherein the alkyl ester portion is an alkyl group having 1 to 22 carbon atoms.

[0331] From the viewpoint that the resulting fiber products have good water repellency, lauryl phosphate and decyl phosphate are preferred.

[0332] Phosphate compounds, for example, can be commercially available products such as "Phosphanol ML-200" (manufactured by Toho Chemical Industry Co., Ltd., trade name).

[0333] The pretreatment solution containing one or more compounds having the specific functional groups described above can be, for example, an aqueous solution of the aforementioned compounds. Additionally, the pretreatment solution may also contain acids, bases, surfactants, chelating agents, etc.

[0334] Methods for treating fibrous materials with the aforementioned pretreatment solution include, for example, padding, impregnation, spraying, and coating. For padding, methods using the padding apparatus described in pages 396-397 of the *Dictionary of Fiber Dyeing Processing* (Published by Nikkan Kogyo Shimbun, 1949) and pages 256-260 of *Dyeing Chemistry III* (Published by Jitsukyo Publishing Co., Ltd., 1975) can be cited. For coating, methods using the coating machine described in pages 473-477 of the *Overview of Dyeing and Finishing Equipment* (Published by Kogyo Publishing Co., Ltd., 1956) can be cited. For impregnation, methods using the intermittent dyeing machine described in pages 196-247 of the *Overview of Dyeing and Finishing Equipment* (Published by Kogyo Publishing Co., Ltd., 1956) can be cited, including liquid flow dyeing machines, airflow dyeing machines, drum dyeing machines, winch dyeing machines, washing dyeing machines, and yarn package dyeing machines. As a spray treatment, examples include air spraying that uses compressed air to atomize the treatment liquid and blow it out, or air spraying using hydraulic atomization. The concentration of the treatment liquid and subsequent heat treatment conditions can be adjusted appropriately, considering the purpose and performance. Furthermore, if the pretreatment liquid contains water, it is preferable to dry it after it adheres to the fibrous material to remove the water. There are no particular limitations on the drying method; both dry heat and wet heat methods are acceptable. There are also no particular limitations on the drying temperature; for example, drying at room temperature to 200°C for 10 seconds to several days is sufficient. If necessary, after drying, it can also be heat-treated at 100–180°C for approximately 10 seconds to 5 minutes.

[0335] In addition, when the fiber material is dyed, the pretreatment with the pretreatment solution can be carried out before dyeing or in the same bath as dyeing. However, when performing reduction soaping, since the compounds with the above-mentioned specific functional groups (such as phenolic polymers) adsorbed during the process may be shed, it is preferable to perform the treatment after reduction soaping after dyeing.

[0336] The treatment temperature during impregnation can be 60–130℃. The treatment time can be 5–60 minutes.

[0337] In the pretreatment process, when introducing functional groups into the pretreatment solution, it is preferable to treat the material with an amount of the compound having the aforementioned specific functional groups in a quantity of 1.0 to 7.0 parts by weight relative to 100 parts by weight of the fiber material. Within this range, a high level of both durable water repellency and hand feel can be achieved.

[0338] The pH of the pretreatment solution is preferably adjusted to 3-5. pH adjustment agents such as acetic acid and malic acid can be used.

[0339] In the pretreatment solution, in order to effectively adsorb compounds with the aforementioned specific functional groups onto the fiber material using the salting-out effect, salts may also be used. Examples of salts that can be used include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate.

[0340] In the process of introducing functional groups into the pretreatment solution, it is preferable to remove over-treated compounds containing the aforementioned specific functional groups. Washing with water is an example of such removal methods. Sufficient removal prevents the expression of water-repellent properties from being hindered in the subsequent water-repellent processing, and the resulting fiber product has a good hand feel. Furthermore, the resulting fibers containing functional groups are preferably thoroughly dried before contacting with the hydrocarbon-based water-repellent agent.

[0341] (ii) As a fiber in which the above-mentioned specific functional groups are directly introduced into the material constituting the fiber, cationic dyeable polyester (CD-PET) can be listed as an example.

[0342] From the viewpoint of improving the water repellency of the resulting fiber product, the zeta potential of the fiber surface containing functional groups 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 the zeta potential and particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0343] Example The present invention will be described in detail below with reference to specific embodiments, but the present invention is not limited to these embodiments.

[0344] <Experimental Methods> The experimental procedure is as follows.

[0345] [Water contact angle] A 1.0% solid component solution (or dispersion) of the stripping agent was spin-coated onto a silicon wafer at 2000 rpm for 30 seconds to obtain a spin-coated film. The stripped silicon wafer was then heated at 150°C for 5 minutes to prepare the stripped silicon wafer. Chloroform was used as the solvent or dispersion medium. 2 μL of water was dropped onto the stripped silicon wafer, and the contact angle 1 second after the drop was taken as the water contact angle.

[0346] [HD Contact Angle] A 1.0% solid component solution (or dispersion) of the stripping agent was spin-coated onto a silicon wafer at 2000 rpm for 30 seconds to obtain a spin-coated film. The stripped silicon wafer was then prepared by heating it at 150°C for 5 minutes. Chloroform was used as the solvent or dispersion medium. 2 μL of n-hexadecane was dropped onto the stripped silicon wafer, and the contact angle 1 second after the drop was taken as the water contact angle.

[0347] Example 1 In a Dean-Stark apparatus under a nitrogen atmosphere, 18.1 g of diethylenetriamine and 10.0 g of stearic acid were stirred overnight in an oil bath at 155 °C. After the reaction was complete, the mixture was cooled to room temperature and subjected to liquid-liquid extraction with chloroform and pure water to recover the chloroform phase. After concentration under reduced pressure, a chloroform solution was added dropwise to 500 mL of hexane, and the mixture was stirred for 1 hour. Filtering the hexane yielded 9.49 g of the polyamine-modified product.

[0348] 1.56 g of the polyamine modifier was weighed into a 30 mL side-ended reaction tube and placed under a nitrogen atmosphere. 2.67 g of triethylamine and 7 mL of dehydrated chloroform were added, and the mixture was heated and stirred (80 °C, 700 rpm) until dissolved. 0.70 g of trimellitic acid chloride was dissolved in 7 mL of dehydrated chloroform and added dropwise to the polyamine modifier solution. The mixture was heated and stirred overnight (80 °C, 700 rpm). After cooling to room temperature, 30 mL of pure water was added to the reaction solution, and the mixture was stirred for 1 hour. The chloroform phase was then added dropwise to 300 mL of methanol, and the mixture was stirred for 1 hour. The methanol was filtered to obtain 1.55 g of the polymer.

[0349] The polymer was used to evaluate the water contact angle and HD contact angle. The results are shown in Table 1.

[0350] Example 2 Weigh 1.45 g of the solid obtained in Example 1 into a 30 mL reaction tube with a side arm, and set the atmosphere to nitrogen. Add 3.14 g of triethylamine and 7 mL of dehydrated chloroform, and heat and stir (90 °C, 700 rpm) to dissolve it. Dissolve 0.94 g of stearoyl chloride in 7 mL of dehydrated chloroform, and add it dropwise to the above reaction solution, and heat and stir overnight (90 °C, 700 rpm). After cooling to room temperature, add 30 mL of pure water to the reaction solution and stir for 1 hour. Add the chloroform phase dropwise to 300 mL of methanol and stir for 1 hour. Filter the methanol to obtain 1.30 g of polymer.

[0351] The polymer was used to evaluate the water contact angle and HD contact angle. The results are shown in Table 1.

[0352] Example 3 In a Dean-Stark apparatus under a nitrogen atmosphere, 5.0 g of triethylenetetramine and 17.5 g of stearic acid were stirred overnight in an oil bath at 155 °C. After the reaction was complete, the mixture was cooled to room temperature and subjected to liquid-liquid extraction with chloroform and pure water to recover the chloroform phase. After concentration under reduced pressure, a chloroform solution was added dropwise to 500 mL of hexane, and the mixture was stirred for 1 hour. Filtering the hexane yielded 10.5 g of the polyamine-modified product.

[0353] 1.94 g of the polyamine modifier was weighed into a 30 mL side-ended reaction tube and placed under a nitrogen atmosphere. 1.93 g of triethylamine and 7 mL of dehydrated chloroform were added, and the mixture was heated and stirred (80°C, 700 rpm) until dissolved. 0.51 g of trimellitic acid chloride was dissolved in 7 mL of dehydrated chloroform and added dropwise to the polyamine modifier solution. The mixture was heated and stirred overnight (80°C, 700 rpm). After cooling to room temperature, 30 mL of pure water was added to the reaction solution, and the mixture was stirred for 1 hour. The chloroform phase was then added dropwise to 300 mL of methanol, and the mixture was stirred for 1 hour. The methanol was filtered to obtain 1.87 g of the polymer.

[0354] The polymer was used to evaluate the water contact angle and HD contact angle. The results are shown in Table 1.

[0355] Example 4 0.34 g of the polyamine modifier from Example 3 was weighed into an 18 mL side-ended reaction tube and placed under a nitrogen atmosphere. 0.50 g of triethylamine and 2 mL of dehydrated chloroform were added, and the mixture was heated and stirred (90°C, 700 rpm) until dissolved. 0.10 g of terephthaloyl chloride was dissolved in 2 mL of dehydrated chloroform and added dropwise to the polyamine modifier solution. The mixture was heated and stirred overnight (90°C, 700 rpm). After cooling to room temperature, 10 mL of pure water was added to the reaction solution, and the mixture was stirred for 1 hour. The chloroform phase was then added dropwise to 200 mL of methanol, and the mixture was stirred for 1 hour. The methanol was filtered to obtain 0.18 g of the polymer.

[0356] The polymer was used to evaluate the water contact angle and HD contact angle. The results are shown in Table 1.

[0357] Comparative Example 1 The untreated silicon wafers were cleaned with ethanol and acetone, and then dried by heating at 150°C for 5 minutes to obtain untreated silicon wafers.

[0358] The water contact and HD contact angle were evaluated using this substrate. The results are shown in Table 1.

[0359] [Table 1]

Claims

1. A dispensing agent, characterized in that: It contains a liquid-repellent compound having a portion from compound (a) and a portion from compound (b). The compound (a) has a structure in which a monovalent hydrocarbon group with 6 to 40 carbon atoms that may have substituents is bonded to the carbon or nitrogen atom of the amide or urea group, and has one or more reactive groups. The compound (b) does not have a monovalent hydrocarbon group with 6 to 40 carbon atoms that can have substituents, but has two or more reactive groups.

2. The dispensing agent as described in claim 1, characterized in that: The portion from compound (a) and the portion from compound (b) are linked by groups or direct bonds as shown in the following formula. -X 1 -CO-X 2 - In the formula, X 1 and X 2 Each is independently directly bonded and consists of one or more groups selected from -O- and -NH-.

3. The dispensing agent as described in claim 2, characterized in that: X 1 and X 2 One of them is -NH-.

4. The dispensing agent according to any one of claims 1 to 3, characterized in that: The compound (a) comprises at least one group selected from the groups shown in the following formulas, -NR 1 -CO-R 2 、 -CO-NR 1 -R 2 、 -NH-CO-NR 1 -R 2 ,and -NR 1 -CO-NH-R 2 In the formula, R 1 Each is independently a hydrogen atom or a monovalent hydrocarbon group with 1 to 20 carbon atoms that may have substituents. R 2 Each can be a monovalent hydrocarbon group with 6 to 40 carbon atoms that can have substituents.

5. The dispensing agent according to any one of claims 1 to 4, characterized in that: The compound (a) is a polyamine modifier, which is formed by modifying the amino group of a polyamine with a monovalent hydrocarbon group having a substituent of 6 to 40 carbon atoms, and the polyamine modifier has one or more amino groups or derivatives thereof.

6. The dispensing agent as described in claim 5, characterized in that: The polyamine modifier is a compound represented by the following formula. N(R 3 ) l (-H) m -L 1 -[NR 1 -L 1 -] t -N(-CO-R 2 ) p (-H) q In the formula, L 1 Each can be independently a divalent aliphatic or aromatic hydrocarbon group with 2 to 20 carbon atoms and may have substituents. R 1 Each is independently a hydrogen atom or a monovalent aliphatic hydrocarbon group with 1 to 20 carbon atoms that may have substituents. R 2 Each can be independently a monovalent hydrocarbon group with 6 to 40 carbon atoms that can have substituents. R 3 Each is independently a hydrogen atom, a monovalent aliphatic hydrocarbon group with 1 to 20 carbon atoms that may have substituents, or -CO-R. 2 , t is an integer greater than 0 and less than 10. p is an integer greater than 1 and less than 2. q is an integer greater than 0 and less than 2. p + q = 2 l is an integer greater than 0 and less than 2. m is an integer greater than 0 and less than 2. l + m = 2.

7. The dispensing agent according to any one of claims 1 to 4, characterized in that: The compound (a) is a polycarboxylic acid modified body, which is formed by modifying the carboxyl group of a polycarboxylic acid with a monovalent hydrocarbon group having a substituent of 6 to 40 carbon atoms, and the polycarboxylic acid modified body has one or more carboxyl groups or derivatives thereof.

8. The dispensing agent as described in claim 7, characterized in that: The polycarboxylic acid modified body comprises compounds shown in the following formula. A{-CONR 1 -R 2 } n {-COOH} m In the formula, A is an aliphatic hydrocarbon group with 1 to 20 carbon atoms in the range of 2 to 4 valences, or an aromatic hydrocarbon group in the range of 2 to 4 valences. R 1 Each is an aliphatic hydrocarbon group, consisting independently of one or more hydrogen atoms or fewer than 20 carbon atoms, either straight-chain or branched. R 2 Each can be independently a monovalent hydrocarbon group with 6 to 40 carbon atoms that can have substituents. n is an integer greater than 1 and less than 4. m is an integer greater than 1 and less than 4. n + m is an integer greater than 2 and less than 4.

9. The dispensing agent according to any one of claims 1 to 8, characterized in that: The liquid-repellent compound also includes a portion from compound (c). The compound (c) is Monocarboxylic acids and their derivatives having a monovalent hydrocarbon group having 6 to 40 carbon atoms that may have substituents, and / or Monoamines and their derivatives having a monovalent hydrocarbon group with 6 to 40 carbon atoms that can have substituents.

10. The dispensing agent as described in claim 1, characterized in that: Compound (a) is a polyamine modified by modifying the amino group of a polyamine with a monovalent hydrocarbon group having 6 to 40 carbon atoms that can be substituted. Compound (b) is a polycarboxylic acid without a monovalent hydrocarbon group having 6 to 40 carbon atoms that can be substituted. The portion from compound (a) and the portion from compound (b) are linked by groups represented by the following formula: -X 1 -CO-X 2 - In the formula, X 1 and X 2 Each is independently directly bonded and consists of one or more groups selected from -O- and -NH-.

11. The dispensing agent according to any one of claims 1 to 10, characterized in that: Compound (a) and compound (b) are compounds other than sugar alcohols.

12. The dispensing agent according to any one of claims 1 to 11, characterized in that: The liquid-repellent compound does not contain fluorine atoms.

13. The dispensing agent according to any one of claims 1 to 12, characterized in that: It is an organic solvent solution, an organic solvent dispersion, or an aqueous dispersion.

14. A method for manufacturing a fiber product, characterized in that: The step includes applying the dissolving agent according to any one of claims 1 to 13 to the fiber substrate.

15. A fiber product, characterized in that: The repellent compound of any one of claims 1 to 13 is attached to the fiber substrate.

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