Composition

Abstract

To provide a novel composition that can impart liquid repellency to a base material.SOLUTION: Provided is a composition comprising a hydrophobic compound (A) formed from a hydrophobic compound (A1) and a hydrophobic compound (A2) different from the hydrophobic compound (A1), wherein the Shore A hardness [PEAK] of the hydrophobic compound (A) is smaller than the Shore A hardness [PEAK] of the hydrophobic compound (A1) by 10 or more and 100 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to compositions, particularly compositions that can impart liquid repellency to a substrate. [Background technology]

[0002] Patent Document 1 discloses a powdery papermaking composition that can improve paper quality such as bulkiness and sizing properties, and also improve workability. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-60921 Summary of the Invention [Problem to be solved by the invention]

[0004] Patent Document 1 neither describes nor suggests the use of a combination of multiple hydrophobic compounds, nor does Patent Document 1 consider imparting liquid repellency to a substrate.

[0005] An object of the present disclosure is to provide a novel composition that can impart liquid repellency to a substrate. [Means for solving the problem]

[0006] The present disclosure includes the following aspects: [Section 1] A composition comprising a hydrophobic compound (A) consisting of a hydrophobic compound (A1) and a hydrophobic compound (A2) different from the hydrophobic compound (A1), A composition, wherein the Shore A hardness [PEAK] of the hydrophobic compound (A) is smaller than the Shore A hardness [PEAK] of the hydrophobic compound (A1) by 10 or more and 100 or less. [Section 2] Item 1. The composition according to item 1, which is a water-dispersed composition. [Section 3] Item 3. The composition according to item 1 or 2, which is a repellent. [Section 4] Item 4. The composition according to any one of Items 1 to 3, wherein the hydrophobic compound (A1) has a contact angle with hexadecane of 30° or more. [Section 5] Item 5. The composition according to any one of Items 1 to 4, wherein the hydrophobic compound (A) has a Shore A hardness [PEAK] of 4.0 or more and 70 or less. [Section 6] Item 6. The composition according to any one of Items 1 to 5, wherein the hydrophobic compound (A1) and the hydrophobic compound (A2) are each independently a compound having a hydrocarbon group having 6 to 40 carbon atoms. [Section 7] Item 7. The composition according to any one of Items 1 to 6, wherein the hydrophobic compound (A1) and the hydrophobic compound (A2) are each independently a compound selected from the group consisting of an amine-modified compound, a polyol-modified compound, a polycarboxylic acid-modified compound, and other liquid or solid oils. [Section 8] the hydrophobic compound (A1) has an amide structure, 8. The composition according to any one of items 1 to 7, wherein the hydrophobic compound (A2) does not have an amide structure. [Section 9] the hydrophobic compound (A1) is a compound selected from the group consisting of an amine-modified compound, a polyol-modified compound, a polycarboxylic acid-modified compound, a paraffin wax, and a microcrystalline wax; The amine-modified compound is an amine skeleton, and The following formula: -Y N -Z N n [In the formula, Y N is Y N1 and Y N2 is a (1+n) valent group consisting of one or more members selected from the group consisting of Y N1is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -C(=S)-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), Y N2 is a group consisting of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles, Z N represents a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, n is an integer between 1 and 3. and having one or more groups represented by At least one -Y N -Z N n is bonded to a nitrogen atom of the amine skeleton; The polyol modification may be achieved by modifying one or more hydroxy groups of the polyol to the formula: -Y O -Z O n [In the formula, Y O is Y O1 and Y O2 is a (1+n) valent group consisting of one or more members selected from the group consisting of Y O1 is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -C(=S)-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), Y O2is a group consisting of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles, Z O represents a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, n is an integer between 1 and 3. A compound substituted with a group represented by the formula: The polycarboxylic acid modification product is a polycarboxylic acid modified by converting a hydroxy group of one or more carboxyl groups of the polycarboxylic acid to the following formula: -Y C -Z C n [In the formula, Y C is Y C1 and Y C2 is a (1+n) valent group consisting of one or more members selected from the group consisting of Y C1 is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -C(=S)-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), Y C2 is a group consisting of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles, Z C represents a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, n is an integer between 1 and 3. A compound substituted with a group represented by the formula: The composition according to any one of items 1 to 8. [Section 10] the hydrophobic compound (A2) has a hydrocarbon group having 3 or more carbon atoms, Item 10. The composition according to any one of items 1 to 9, wherein the hydrophobic compound (A2) has a melting point of 40° C. or lower. [Section 11] Item 11. The composition according to any one of items 1 to 10, wherein the amount of the hydrophobic compound (A1) is 15% by weight or more and 95% by weight or less based on the amount of the hydrophobic compound (A). [Section 12] Item 12. The composition according to any one of items 1 to 11, wherein the amount of the hydrophobic compound (A2) is 5 parts by weight or more and 500 parts by weight or less per 100 parts by weight of the hydrophobic compound (A1). [Section 13] The melting point of the hydrophobic compound (A1) is 50°C or higher, Item 13. The composition according to any one of items 1 to 12, wherein the hydrophobic compound (A2) has a melting point of 40° C. or lower. [Section 14] Item 14. The composition according to any one of items 1 to 13, wherein the melting point of the hydrophobic compound (A1) is higher than the melting point of the hydrophobic compound (A2) by 30° C. or more. [Section 15] the composition comprises a dispersant; Item 15. The composition according to any one of items 1 to 14, wherein the amount of the dispersant is 0.1 parts by weight or more and 100 parts by weight or less, based on 100 parts by weight of the hydrophobic compound (A). [Section 16] A papermaking additive kit comprising a first agent and a second agent, the first agent contains a hydrophobic compound (A1), the second agent contains a hydrophobic compound (A2) which is a compound different from the hydrophobic compound (A1), the Shore A hardness [PEAK] of the hydrophobic compound (A) is smaller than the Shore A hardness [PEAK] of the hydrophobic compound (A1) by 10 or more and 100 or less; The papermaking additive kit is used by adding and mixing the first agent and the second agent separately to a pulp base material. [Section 17] A substrate, and a hydrophobic compound (A) consisting of a hydrophobic compound (A1) and a hydrophobic compound (A2) different from the hydrophobic compound (A1); A product comprising: A product in which the Shore A hardness [PEAK] of the hydrophobic compound (A) is smaller by 10 or more and 100 or less than the Shore A hardness [PEAK] of the hydrophobic compound (A1). [Section 18] The substrate is a pulp substrate, Item 18. The product according to item 17, wherein the product is a pulp product. [Section 19] Item 17. A method for producing a product, comprising treating a substrate with the composition according to any one of items 1 to 15 or the papermaking additive kit according to item 16. [Effects of the Invention]

[0007] According to the present disclosure, it is possible to impart liquid repellency to a substrate in an excellent manner. DETAILED DESCRIPTION OF THE INVENTION

[0008] <Terminology> As used herein, an "n-valent group" refers to a group having n bonds, i.e., a group that forms n bonds. An "n-valent organic group" refers to an n-valent group containing carbon. Such organic groups are not particularly limited, but may be hydrocarbon groups or derivatives thereof. A hydrocarbon group derivative refers to a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc. at the end or molecular chain of the hydrocarbon group.

[0009] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, which is obtained by removing a hydrogen atom from a hydrocarbon. Such hydrocarbon groups include, but are not limited to, C 1-20Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may contain one or more ring structures. The hydrocarbon group may be substituted with one or more substituents, if explicitly stated.

[0010] In this specification, when a term (symbol) that may appear multiple times in a chemical structure is defined, that definition applies independently at each occurrence, unless otherwise stated, regardless of whether "independently at each occurrence," "independently of each other," "independently of each other," or similar expressions are explicitly stated.

[0011] The chemical structures illustrated herein should be understood not to encompass chemical structures that would be recognized by those skilled in the art as being chemically impossible or extremely unstable.

[0012] <Composition> The composition of the present disclosure includes a hydrophobic compound (A) consisting of a hydrophobic compound (A1) and a hydrophobic compound (A2) different from the hydrophobic compound (A1). The composition of the present disclosure can be used as a treatment agent (e.g., a barrier coating agent, a surface treatment agent, a repellent (liquid repellent), particularly a repellent), and can adhere to a substrate (particularly a pulp substrate) to impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the substrate. It can also function as a water resistance agent, oil resistance agent, water repellent agent, oil repellent agent, and / or stain resistance agent. For example, the repellent agent of the present disclosure has excellent oil resistance (e.g., room temperature oil resistance, high temperature oil resistance, stain resistance), etc., making it possible to reduce the required amount of additive.

[0013] The composition of the present disclosure may be the hydrophobic compound (A) itself, or the hydrophobic compound (A) may be used by itself as a treatment agent (particularly a repellent agent), or may be combined with other components as described below.

[0014] The composition of the present disclosure may not contain any compound selected from the group consisting of a compound having a fluoroalkyl group having 8 or more carbon atoms, a compound having a perfluoroalkyl group having 8 or more carbon atoms, a compound having a fluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The composition of the present disclosure can impart liquid repellency to a substrate even if it does not contain these fluorine compounds.

[0015] The volumetric abundance ratio of particles of 100 μm or larger in the composition of the present disclosure, as measured by laser diffraction scattering, may be 0.1% or larger, 0.3% or larger, 0.5% or larger, 1% or larger, 1.5% or larger, 3% or larger, 4% or larger, 5% or larger, or 10% or larger, or may be 50% or smaller, 30% or smaller, 20% or smaller, 15% or smaller, 10% or smaller, 5% or smaller, 3% or smaller, or 1.5% or smaller. The method for achieving the volumetric abundance ratio of particles of 100 μm or larger, as measured by laser diffraction scattering, within the above range is not limited, and may be, for example, by using a grinder, homogenizer, or the like to micronize the particles in the raw material and / or dispersion.

[0016] The volume median diameter of the composition of the present disclosure, as measured by a laser diffraction scattering method, may be 0.1 μm or more, 0.3 μm or more, 0.5 μm or more, 0.7 μm or more, 1 μm or more, 3 μm or more, 5 μm or more, 10 μm or more, 15 μm or more, 30 μm or more, or 50 μm or more, or may be 300 μm or less, 200 μm or less, 100 μm or less, 50 μm or less, 30 μm or less, 20 μm or less, 10 μm or less, 5 μm or less, or 1 μm or less. In the present disclosure, the volume median diameter refers to the median diameter (D50) in a volume-based particle size distribution measured by a laser diffraction scattering method.

[0017] When the composition contains a liquid medium (for example, the composition is an aqueous dispersion), the 25°C penetration of the residue obtained by removing the liquid medium from the composition may be 5 or more, 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, and may be 200 or less, 150 or less, 125 or less, or 100 or less. The conditions for measuring the penetration may be as described in JIS K 2235 6.4.

[0018] When the composition contains a liquid medium (for example, the composition is an aqueous dispersion), the hardness of the residue obtained by removing the liquid medium from the composition may be as follows. The Shore A hardness [PEAK] of the peak strength during testing may be 0.5 or more, 1.0 or more, 1.5 or more, 2.0 or more, 2.5 or more, 3.0 or more, 4.0 or more, 5.0 or more, 7.5 or more, or 10.0 or more, and may be 80 or less, 75 or less, 70 or less, 65 or less, or 60 or less. The Shore A hardness [1s], which is the Shore A hardness one second after the start of the test, may be 0.5 or more, 1.0 or more, 1.5 or more, 2.0 or more, 2.5 or more, 3.0 or more, 4.0 or more, 5.0 or more, 7.5 or more, or 10.0 or more, and may be 80 or less, 75 or less, 70 or less, 65 or less, or 60 or less. The Shore A hardness [3s], which is the Shore A hardness 3 seconds after the start of the test, may be 0.5 or more, 1.0 or more, 1.5 or more, 2.0 or more, 2.5 or more, 3.0 or more, 4.0 or more, 5.0 or more, 7.5 or more, or 10.0 or more, and may be 80 or less, 75 or less, 70 or less, 65 or less, or 60 or less.

[0019] [Hydrophobic compound (A)] The hydrophobic compound (A) in the present disclosure is a mixture of a hydrophobic compound (A1) and a hydrophobic compound (A2) different from the hydrophobic compound (A1). The hydrophobic compound (A) in the present disclosure is an active ingredient when the composition in the present disclosure is used as a repellent, and can adhere to a substrate (particularly a pulp substrate) to impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the substrate.

[0020] [Characteristics, etc.] The properties that the hydrophobic compound (A), the hydrophobic compound (A1), and the hydrophobic compound (A2) may have are shown below. Note that, when the properties of the hydrophobic compound (A) itself are mentioned below, the hydrophobic compound (A) is intended to be a mixture obtained by melt-mixing the hydrophobic compound (A1) and the hydrophobic compound (A2) at a temperature above their melting points and allowing the mixture to cool at room temperature.

[0021] (solubility characteristics) The hydrophobic compound (A1) and the hydrophobic compound (A2) are hydrophobic and have low water solubility. The hydrophobic compound (A1) and the hydrophobic compound (A2) may each independently have a water solubility at 25°C of 3.0 g / L or less, 1.0 g / L or less, 0.5 g / L or less, 0.1 g / L or less, or 0.01 g / L or less, for example, 1.0 g / L or less. The water solubility can be calculated by adding the compound in small amounts to a predetermined amount of water (25°C) and calculating the amount of the compound dissolved at the point where the compound no longer dissolves (e.g., floating, precipitation, deposition, or cloudiness is observed). A compound that is highly water-soluble (e.g., a compound that is a water-miscible liquid) cannot be considered a hydrophobic compound.

[0022] The solubility parameters (SP values) of the hydrophobic compounds (A1) and (A2) may each independently be 3.0 or more, 4.0 or more, 5.0 or more, 6.0 or more, 7.0 or more, 8.0 or more, 9.0 or more, 10.0 or more, or 11.0 or more; and each independently may be 15.0 or less, 14.0 or less, 13.0 or less, 12.0 or less, 10.0 or less, 9.0 or less, or 8.0 or less, preferably 10.5 or less, particularly 10.0 or less. The SP value can be calculated using Fedors' formula (Polym. Eng. Sci., 14[2], 147 (1974)). Only the hydrophobic compound (A1), only the hydrophobic compound (A2), or both may satisfy the above range, preferably both.

[0023] The difference in SP value between the hydrophobic compound (A1) and the hydrophobic compound (A2) may be greater than 0, 0.1 or greater, 0.2 or greater, 0.3 or greater, 0.4 or greater, 0.5 or greater, 0.6 or greater, 0.7 or greater, 0.8 or greater, 0.9 or greater, 1.0 or greater, 2.0 or greater, 3.0 or greater, 4.0 or greater, or 5.0 or greater; or may be 6.0 or less, 5.0 or less, 4.0 or less, 3.0 or less, 2.0 or less, 1.5 or less, 1.0 or less, 0.8 or less, 0.6 or less, or 0.5 or less, preferably 5.0 or less, more preferably 3.0 or less. The hydrophobic compound (A1) may have a larger value, or the hydrophobic compound (A2) may have a larger value. When multiple compounds are present in each of the hydrophobic compounds (A1) and (A2), a weighted average based on the weight ratio may be used to calculate each value. Unless otherwise specified, the difference in this specification is an absolute difference.

[0024] The octanol / water partition coefficients (logPow) of the hydrophobic compounds (A1) and (A2) may each independently be 0 or more, 0.1 or more, 0.3 or more, 0.5 or more, 1 or more, 1.5 or more, 2.0 or more, 2.5 or more, 3.0 or more, 3.5 or more, 4.0 or more, 4.5 or more, 5.0 or more, 5.5 or more, or 6.0 or more, preferably 0.5 or more, 1.5 or more, 2.5 or more, or 3.5 or more, and may be 10.0 or less, 9.0 or less, 8.0 or less, 7.0 or less, 6.0 or less, 5.0 or less, 4.0 or less, 3.0 or less, 2.0 or less, or 1.0 or less. Only the hydrophobic compound (A1), only the hydrophobic compound (A2), or both may satisfy the above range, preferably both satisfy the above range.

[0025] The difference in octanol / water partition coefficient (logPow) between the hydrophobic compound (A1) and the hydrophobic compound (A2) may be greater than 0, 0.1 or greater, 0.3 or greater, 0.5 or greater, 1.0 or greater, 1.5 or greater, or 2.0 or greater; or may be 5.0 or less, 4.5 or less, 4.0 or less, 3.0 or less, 2.5 or less, 2.0 or less, 1.5 or less, 1.0 or less, 0.5 or less, 0.3 or less, or 0.1 or less, preferably 2.5 or less, more preferably 1.0 or less. The hydrophobic compound (A1) may have a larger value, or the hydrophobic compound (A2) may have a larger value. When multiple compounds are present in each of the hydrophobic compounds (A1) and (A2), a weighted average based on the weight ratio may be used to calculate each value.

[0026] The HLB (hydrophile-lipophile balance) value of the hydrophobic compound (A2) may be 0.5 or more, or 1.0 or more, and may be 11.5 or less, 11.0 or less, 10.5 or less, 10.0 or less, 9.5 or less, 9.0 or less, 8.5 or less, 8.0 or less, 7.5 or less, or 7.0 or less. By being equal to or less than the upper limit, the effects of the present disclosure can be favorably achieved. The HLB (hydrophile-lipophile balance) value is a numerical value devised by W. Griffin and assigned to nonionic surfactants, and it represents the balance between the strength of the lipophilic group (e.g., alkyl group) and the hydrophilic group (e.g., polyoxyalkylene chain) of the nonionic surfactant. In the present invention, the HLB value is the value calculated by the Griffin method (references: W. Griffin, J. Soc. Cosmetic Chemists, 1, 311 (1949) and W. Griffin, J. Soc. Cosmetic Chemists, 5, 249 (1954)). If a catalog value is available, the catalog value may be used as a simple method of judgment, but if the catalog value and the calculated value differ, the calculated value shall be used. The HLB value of the hydrophobic compound (A1) may be larger than that of the hydrophobic compound (A2), or the hydrophobic compound (A2) may have a larger value. When a plurality of compounds are present in each of the hydrophobic compounds (A1) and (A2), a weighted average based on the weight ratio may be used to calculate each value.

[0027] (Thermal properties) The endothermic peak of the hydrophobic compound (A1) (single compound) may be low-temperature shifted when mixed with the hydrophobic compound (A2) to form the hydrophobic compound (A) (mixture) in DSC. The endothermic peak temperature of the hydrophobic compound (A1) in differential scanning calorimetry may be low-temperature shifted by 2°C or more and 80°C or less in differential scanning calorimetry of the hydrophobic compound (A). The low-temperature shifted endothermic peak may be any peak of the hydrophobic compound (A1) (e.g., the maximum peak, any endothermic peak in the top 30% of peak intensity, etc.), and at least one (e.g., 50% or more, 70% or more, 100%) of all peaks in the range of -50°C to 300°C (e.g., -30°C to 240°C, particularly -20°C to 180°C, particularly 0°C to 180°C) may be low-temperature shifted. The low-temperature shift may be 0.5°C or more, 1°C or more, 1.5°C or more, 2°C or more, 2.5°C or more, 3°C or more, 4°C or more, 6°C or more, 8°C or more, 10°C or more, 12°C or more, 15°C or more, 20°C or more, or 30°C or more, and may be 80°C or less, 75°C or less, 65°C or less, 55°C or less, 45°C or less, 35°C or less, 25°C or less, 20°C or less, 15°C or less, 12°C or less, 11°C or less, or 10°C or less, for example, 20°C or less, and in one embodiment, it may be 0.5°C or more and 80°C or less, particularly 0.5°C or more and 20°C or less, 3°C or more and 12°C or less, or 3°C or more and 11°C or less. It is believed that the combination of two hydrophobic compounds changes the thermal properties, causing a low-temperature shift of the endothermic peak in DSC. The hydrophobic compound (A1) may have one or more endothermic peaks at 45°C or higher, and the endothermic peaks may be shifted to a lower temperature. Preferably, the endothermic peak of the hydrophobic compound (A1) that is shifted to a lower temperature is the endothermic peak at the highest temperature in the measurement range, and may be, for example, a peak associated with melting (melting point peak). Note that the endothermic peak does not include an endothermic peak due to decomposition of the compound, but is an endothermic peak in a range in which the compound does not decompose. In the case of a compound that decomposes without melting, the melting point of the compound is understood to be at least equal to or higher than the decomposition temperature.

[0028] The DSC measurement conditions may be as follows: In a nitrogen atmosphere, DSC is performed by cooling to below -20°C, and then measuring the endothermic peak observed during the subsequent heating process at 10°C / min to above 180°C. The endothermic heat is calculated by calculating the heat quantity within a range of ±10°C from the endothermic peak temperature.

[0029] The melting points of the hydrophobic compounds (A1) and (A2) may each independently be -100°C or higher, -75°C or higher, -50°C or higher, -25°C or higher, 0°C or higher, 30°C or higher, 40°C or higher, 50°C or higher, 60°C or higher, 80°C or higher, 100°C or higher, or 120°C or higher, preferably 40°C or higher, and each independently be 250°C or lower, 225°C or lower, 200°C or lower, 150°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, 80°C or lower, 50°C or lower, 40°C or lower, 30°C or lower, 20°C or lower, 10°C or lower, 0°C or lower, or -10°C or lower. Only the hydrophobic compound (A1), only the hydrophobic compound (A2), or both may satisfy the above range, and preferably both satisfy the above range. The hydrophobic compound (A1) may be solid at room temperature (melting point 30°C or higher), for example 50°C or higher, and the hydrophobic compound (A2) may have a melting point of 40°C or lower, for example 30°C or lower (less than 30°C), particularly a liquid at room temperature (melting point 20°C or lower). In particular, the melting point of the hydrophobic compound (A1) may be 50°C or higher, and the melting point of the hydrophobic compound (A2) may be 40°C or lower.

[0030] The difference in melting point between the hydrophobic compound (A1) and the hydrophobic compound (A2) may be greater than 0°C, 5°C or higher, 10°C or higher, 15°C or higher, 20°C or higher, 25°C or higher, 30°C or higher, 50°C or higher, 70°C or higher, 90°C or higher, 110°C or higher, 130°C or higher, 150°C or higher, 175°C or higher, or 200°C or higher, for example, 30°C or higher, 50°C or higher, 70°C or higher, or 90°C or higher, preferably 30°C or higher, more preferably 70°C or higher, and even more preferably 90°C or higher, and may be 300°C or lower, 250°C or lower, 200°C or lower, 150°C or lower, 100°C or lower, 80°C or lower, 60°C or lower, 50°C or lower, 40°C or lower, 30°C or lower, 20°C or lower, or 10°C or lower. The hydrophobic compound (A1) may have a larger value, or the hydrophobic compound (A2) may have a larger value, and it is particularly preferable that the hydrophobic compound (A1) has a larger value. When a plurality of compounds are present in each of the hydrophobic compounds (A1) and (A2), a weighted average based on the weight ratio may be used to calculate each value. For example, the hydrophobic compound (A1) may have a larger melting point than the hydrophobic compound (A2), and for example, the melting point of the hydrophobic compound (A1) may be 30°C or more higher than the melting point of the hydrophobic compound (A2).

[0031] (mechanical properties) The penetration at 25°C of the hydrophobic compound (A) may be 5 or more, 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, and may be 200 or less, 150 or less, 125 or less, or 100 or less. The conditions for measuring the penetration may be as described in JIS K 2235 6.4.

[0032] The 25°C penetration of the hydrophobic compound (A) may be smaller than the larger of the 25°C penetrations of the hydrophobic compounds (A1) and (A2), and the difference therebetween ([(the larger of the 25°C penetrations of the hydrophobic compounds (A1) and (A2)] - [the 25°C penetration of the hydrophobic compound (A)]) may be greater than 0, 2 or more, 5 or more, 10 or more, 15 or more, 20 or more, 30 or more, 40 or more, or 50 or more, or may be 100 or less, 80 or less, 70 or less, 60 or less, 50 or less, 40 or less, 30 or less, 20 or less, or 10 or less.

[0033] The Shore A hardness of the hydrophobic compound (A) may be as follows: The peak Shore A hardness [PEAK] during testing may be 0.5 or more, 1.0 or more, 1.5 or more, 2.0 or more, 2.5 or more, 3.0 or more, 4.0 or more, 5.0 or more, 7.5 or more, or 10.0 or more, for example 5.0 or more, and may be 80 or less, 75 or less, 70 or less, 65 or less, or 60 or less, for example 60 or less. The Shore A hardness [1s], which is the Shore A hardness 1 second after the start of the test, may be 0.5 or more, 1.0 or more, 1.5 or more, 2.0 or more, 2.5 or more, 3.0 or more, 4.0 or more, 5.0 or more, 7.5 or more, or 10.0 or more, for example, 10 or more, and may be 80 or less, 75 or less, 70 or less, 65 or less, or 60 or less, for example, 60 or less. The Shore A hardness [3s], which is the Shore A hardness 3 seconds after the start of the test, may be 0.5 or more, 1.0 or more, 1.5 or more, 2.0 or more, 2.5 or more, 3.0 or more, 4.0 or more, 5.0 or more, 7.5 or more, or 10.0 or more, for example, 10 or more, and may be 80 or less, 75 or less, 70 or less, 65 or less, or 60 or less, for example, 60 or less.

[0034] The Shore A hardness of the hydrophobic compound (A) is preferably smaller than the larger of the Shore A hardnesses of the hydrophobic compounds (A1) and (A2), and the difference therebetween may be as follows: [(the larger value of the Shore A hardness [PEAK] of the hydrophobic compound (A1) or (A2))] - [the Shore A hardness [PEAK] of the hydrophobic compound (A)] may be greater than 0, 2 or more, 5 or more, 10 or more, 15 or more, 20 or more, 25 or more, 30 or more, 35 or more, 40 or more, 45 or more, or 50 or more, for example, 10 or more, particularly 20 or more, 25 or more, 30 or more, 35 or more, 40 or more, 50 or more, 55 or more, 60 or more, It may be 65 or more, or 70 or more, for example 56 or more, and may be 100 or less, 90 or less, 80 or less, 70 or less, 60 or less, 50 or less, 40 or less, 30 or less, 20 or less, or 10 or less, preferably 90 or less, particularly 80 or less, and in one embodiment 10 or more and 100 or less, 30 or more and 90 or less, 35 or more and 90 or less, 40 or more and 90 or less, 56 or more and 90 or less, particularly 56 or more and 80 or less. [(the larger value [1s] of the Shore A hardness of the hydrophobic compound (A1) or (A2)] minus [the Shore A hardness [1s] of the hydrophobic compound (A)] may be greater than 0, 2 or more, 5 or more, 10 or more, 15 or more, 20 or more, 25 or more, 30 or more, 35 or more, 40 or more, 45 or more, or 50 or more, for example, 10 or more, particularly 20 or more, 25 or more, 30 or more, 35 or more, 40 or more, 50 or more, 55 or more, 60 or more, 65 It may be 100 or less, 90 or less, 80 or less, 70 or less, 60 or less, 50 or less, 40 or less, 30 or less, 20 or less, or 10 or less, preferably 90 or less, particularly 80 or less, and in one embodiment, 10 or more and 100 or less, 30 or more and 90 or less, 35 or more and 90 or less, 40 or more and 90 or less, 56 or more and 90 or less, particularly 56 or more and 80 or less. [(the larger value of Shore A hardness [3s] of hydrophobic compound (A1) or (A2)] - [Shore A hardness [3s] of hydrophobic compound (A)] It may be greater than 0, 2 or more, 5 or more, 10 or more, 15 or more, 20 or more, 25 or more, 30 or more, 35 or more, 40 or more, 45 or more, or 50 or more, for example 10 or more, particularly 20 or more, 25 or more, 30 or more, 35 or more, 40 or more, 50 or more, 55 or more, 60 or more, 65 or more, or 70 or more, for example 56 or more, and may be 100 or less, 90 or less, 80 or less, 70 or less, 60 or less, 50 or less, 40 or less, 30 or less, 20 or less, or 10 or less, preferably 90 or less, particularly 80 or less, and in one embodiment 10 or more to 100, 30 or more to 90, 35 or more to 90, 40 or more to 90, 56 or more to 90, particularly 56 or more to 80. The Shore A hardness of the hydrophobic compound (A1) may be greater than the Shore A hardness of the hydrophobic compound (A2).

[0035] (liquid repellency) The HD (n-hexadecane) contact angles of the hydrophobic compounds (A1) and (A2) may each independently be 10° or greater, 20° or greater, 25° or greater, 30° or greater, 35° or greater, 40° or greater, 45° or greater, 50° or greater, 55° or greater, 60° or greater, or 65° or greater, preferably 25° or greater, more preferably 30° or greater, and each independently be 100° or less, 90° or less, or 75° or less. When the hydrophobic compounds (A1) and (A2) each independently have an HD contact angle equal to or greater than the lower limit described above, the substrate can be imparted with excellent liquid repellency (particularly oil repellency). The HD contact angle is the static contact angle of the hydrophobic compound (A) with respect to a spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle 1 second after the drop has landed. Only the hydrophobic compound (A1), only the hydrophobic compound (A2), or both may satisfy the above range, and preferably both satisfy the above range.

[0036] The difference in HD contact angle between the hydrophobic compound (A1) and the hydrophobic compound (A2) may be greater than 0°, 5° or more, 10° or more, 15° or more, 20° or more, 25° or more, or 30° or more, or may be 60° or less, 50° or less, 40° or less, 30° or less, 20° or less, or 10° or less. The hydrophobic compound (A1) may have a larger value, or the hydrophobic compound (A2) may have a larger value. When a plurality of compounds are present in each of the hydrophobic compounds (A1) and (A2), a weighted average based on the weight ratio may be used to calculate each value.

[0037] The water contact angles of the hydrophobic compounds (A1) and (A2) may each independently be 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more, and may each independently be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When the hydrophobic compounds (A1) and (A2) each independently have a water contact angle equal to or greater than the above lower limit, the substrate can be imparted with good liquid repellency (particularly water repellency). The water contact angle is the static contact angle of the hydrophobic compound (A) with respect to a spin-coated film, and is obtained by dropping 2 μL of water onto the spin-coated film and measuring the contact angle 1 second after the drop has landed. Only the hydrophobic compound (A1), only the hydrophobic compound (A2), or both may satisfy the above range, and preferably both satisfy the above range.

[0038] The difference in water contact angle between the hydrophobic compound (A1) and the hydrophobic compound (A2) may be greater than 0°, 5° or more, 10° or more, 15° or more, 20° or more, 25° or more, or 30° or more, or may be 60° or less, 50° or less, 40° or less, 30° or less, 20° or less, or 10° or less. The hydrophobic compound (A1) may have a larger value, or the hydrophobic compound (A2) may have a larger value. When a plurality of compounds are present in each of the hydrophobic compounds (A1) and (A2), a weighted average based on the weight ratio may be used to calculate each value.

[0039] (Other characteristics) The hydrophobic compounds (A1) and (A2) are preferably biobased compounds containing carbon of biobased origin. The biobased content is measured in accordance with ASTM D6866. The biobased content of the hydrophobic compounds (A1) and (A2) may each independently be 20% or more, preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example, 100%. A high biobased content means that the amount of fossil resource-based materials, such as petroleum, used is reduced. From this perspective, the higher the biobased content of the hydrophobic compound (A), the more preferable it is. Only the hydrophobic compound (A1), only the hydrophobic compound (A2), or both may satisfy the above range, and preferably both satisfy the above range.

[0040] The biodegradability of the hydrophobic compounds (A1) and (A2) after 180 days is preferably 5% or more, independently. Since the environmental impact is reduced, the higher the biodegradability, the better. The biodegradability of the hydrophobic compounds (A1) and (A2) after 180 days is preferably 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, and is preferably 30% or more, more preferably 50% or more, even more preferably 70% or more, and most preferably 80% or more. The biodegradability of the hydrophobic compounds (A1) and (A2) after 60 days is preferably 5% or more, independently. Since the environmental impact is reduced, the higher the biodegradability, the better. The biodegradability of hydrophobic compounds (A1) and (A2) after 60 days may be, for example, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, or 45% or more, preferably 10% or more, and more preferably 30% or more. Such biodegradability may be the biodegradability specified in JIS K 6953-1 or ASTM D6400. Only hydrophobic compound (A1), only hydrophobic compound (A2), or both may satisfy the above range, and preferably both satisfy the above range.

[0041] The biodegradability of the hydrophobic compound (A) after 180 days is preferably 5% or more. Higher biodegradability is preferable because it reduces the environmental load. The biodegradability of the hydrophobic compound (A) after 180 days may be, for example, 10% or more, 20% or more, 30% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, and is preferably 30% or more, more preferably 50% or more, even more preferably 70% or more, and most preferably 80% or more. The biodegradability of the hydrophobic compound (A) after 60 days is preferably 5% or more. Higher biodegradability is preferable because it reduces the environmental load. The biodegradability of the hydrophobic compound (A) after 60 days may be, for example, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, or 45% or more, preferably 10% or more, and more preferably 30% or more. In particular, it is preferable that the biodegradability of the hydrophobic compound (A) is higher than that of the less biodegradable compound, hydrophobic compound (A1) or hydrophobic compound (A2), and the difference therebetween may be more than 0%, 5% or more, 10% or more, 15% or more, 20% or more, 25% or more, or 30% or more, or may be 60% or less, 50% or less, 40% or less, 30% or less, 20% or less, or 10% or less.

[0042] The biodegradability of hydrophobic compound (A) after 180 days may be higher than the biodegradability of hydrophobic compound (A1) after 180 days, and may also be higher than the biodegradability of hydrophobic compound (A2) after 180 days. The difference between the biodegradability of hydrophobic compound (A) after 180 days and the biodegradability of hydrophobic compound (A1) after 180 days may be 1% or more, 2.5% or more, 5% or more, 7.5% or more, 10% or more, 15% or more, 25% or more, 30% or more, or 40% or more, or may be 90% or less, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, or 20% or more. The difference between the biodegradability of hydrophobic compound (A) after 180 days and the biodegradability of hydrophobic compound (A2) after 180 days may be 1% or more, 2.5% or more, 5% or more, 7.5% or more, 10% or more, 15% or more, 25% or more, 30% or more, or 40% or more, and may be 90% or less, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, or 20% or more.

[0043] [Structure etc.] The structure and the like of the hydrophobic compound (A) are explained below. In each explanation, either one of the hydrophobic compounds (A) (only the hydrophobic compound (A1) or only the hydrophobic compound (A2)) or both may satisfy the explanation of the structure and the like, and preferably both satisfy the characteristics.

[0044] The hydrophobic compounds (A1) and (A2) in the present disclosure may each independently not contain any one selected from the group consisting of a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, and a fluorine atom. Even if the hydrophobic compounds (A1) and (A2) each independently do not contain these fluorine-containing groups, they can still impart liquid repellency to a substrate.

[0045] The hydrophobic compounds (A1) and (A2) may each independently be a compound having a monovalent hydrocarbon group having from 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group. From the viewpoint of improving liquid repellency, the hydrophobic compounds (A1) and (A2) may each independently have a hydrocarbon group having from 3 to 40 carbon atoms (for example, an aliphatic hydrocarbon group), and the hydrophobic compound (A1) may have a hydrocarbon group having from 6 to 40 carbon atoms, and the hydrophobic compound (A2) may have a hydrocarbon group having from 3 to 40 carbon atoms.

[0046] (Optionally substituted monovalent hydrocarbon group) The hydrophobic compounds (A1) and (A2) may each independently have a monovalent hydrocarbon group which may have a substituent.

[0047] The hydrocarbon group may be a monovalent hydrocarbon group having from 1 to 40 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, for example, a saturated or unsaturated aliphatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include alkyl groups and groups having 1 to 4 (for example, 1 to 2) unsaturated carbon bonds. The hydrocarbon group may be branched, cyclic, or linear, and is more preferably linear. It is preferred that either one or both of the hydrophobic compounds (A1) and (A2) have an unsaturated hydrocarbon group.

[0048] The number of carbon atoms in the hydrocarbon group may be 1 or more, 3 or more, 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 3 or more, 6 or more, 10 or more, 12 or more, or 16 or more, for example, 10 or more, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, 25 or less, or 20 or less.

[0049] The hydrocarbon group may have a substituent, preferably four or fewer substituents, and more preferably one or no substituents. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (wherein R' is, independently in each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an active hydrogen. The number of substituents may be six or fewer, five or fewer, four or fewer, three or fewer, two or fewer, one or fewer, or zero. In the substituted hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, the hydrocarbon group may have 1 to 3 (for example, 1) -OR' (particularly -OH) as a substituent (for example, other than at the terminal).

[0050] (monovalent polysiloxane group) The hydrophobic compounds (A1) and (A2) may each independently contain a monovalent polysiloxane group. The monovalent polysiloxane group, like the monovalent hydrocarbon group, can impart liquid repellency to the substrate.

[0051] The polysiloxane group has the formula: -[-Si(R s )2-O-] a - [In the formula, R s is independently in each occurrence a hydrocarbon group or a reactive group having 1 to 40 carbon atoms; a is an integer between 5 and 10,000. It may be expressed as:

[0052] R s is a hydrocarbon group having 1 to 40 carbon atoms or a reactive group.

[0053] Examples of hydrocarbon groups having 1 to 40 carbon atoms include hydrocarbon groups having 1 to 5 carbon atoms and hydrocarbon groups having 6 to 40 carbon atoms.

[0054] Examples of hydrocarbon groups having 1 to 5 carbon atoms include hydrocarbon groups having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group (particularly aliphatic hydrocarbon groups, particularly alkyl groups such as a methyl group or an ethyl group, particularly a methyl group).

[0055] The hydrocarbon group having 6 to 40 carbon atoms may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, and particularly preferably a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be cyclic, linear, or branched, preferably linear. The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, preferably 10 or more, more preferably 12 or more, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, more preferably 25 or less.

[0056] Examples of reactive groups include groups having functional groups (e.g., hydroxyl, amino, mercapto, epoxy, carboxyl, halogen-substituted alkyl, vinyl, (meth)acrylic, (meth)acryloyloxy, and (meth)acrylamide groups, and hydrogen atoms directly bonded to silicon atoms). These functional groups may be directly bonded to the silicon atom or to an organic group directly bonded to the silicon atom. The organic group may be a hydrocarbon group, such as an alkylene group or a divalent aromatic group. The hydrocarbon group may have from 2 to 12 carbon atoms, and alkylene groups preferably have from 2 to 10 carbon atoms. Divalent aromatic groups preferably have from 6 to 12 carbon atoms. The reactive group may be a group selected from the group consisting of a hydroxyl group, an epoxy ring, a carboxyl group, a (meth)acrylic group, and an amino group, and may be, for example, at least one selected from the group consisting of an epoxy ring, a hydroxyl group, a (meth)acrylic group, and a carboxyl group.

[0057] a may be 3 or more, 5 or more, 10 or more, 30 or more, 50 or more, 100 or more, 500 or more, 1000 or more, 2000 or more, or 3000 or more, and is preferably 10 or more, and may be 10,000 or less, 7,500 or less, 5,000 or less, 3,000 or less, 1,500 or less, 1,000 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less, and is preferably 500 or less.

[0058] In the polysiloxane group, R is a hydrocarbon group having 1 to 5 carbon atoms. s The quantity of R s It may be 20 mol% or more, 40 mol% or more, 60 mol% or more, or 80 mol% or more, preferably 50 mol% or more, and may be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less, based on the total of R s Based on the total number of groups, 50 mol % or more may be methyl groups or ethyl groups (particularly methyl groups).

[0059] In the polysiloxane group, R is a hydrocarbon group having 6 to 40 carbon atoms. s The quantity of R s and may be 100 mol % or less, 90 mol % or less, 80 mol % or less, or 70 mol % or less, based on the total of

[0060] In the polysiloxane group, the reactive group R s The quantity of R s and may be 5 mol % or more, 10 mol % or more, 20 mol % or more, or 30 mol % or more, and may be 50 mol % or less, 40 mol % or less, 30 mol % or less, or 20 mol % or less, based on the total of

[0061] R s The groups may be introduced randomly or in blocks, but are preferably introduced randomly.

[0062] The terminal structure of the polysiloxane group is not limited, but may be, for example, -ORs , -Si(R s )3, etc. The R s Examples of the reactive group are as described above, and may be, for example, at least one selected from the group consisting of an epoxy ring, a hydroxy group, a (meth)acrylic group, and a carboxyl group.

[0063] The polysiloxane group may have a linker, and the raw material compound and the polysiloxane group may be bonded via a linker. Such a linker may be, but is not limited to, a hydrocarbon group having 1 to 40 (e.g., 1 to 20) carbon atoms which may be interrupted by an oxygen atom, for example, a (poly)oxyalkylene group having 1 to 40 (e.g., 1 to 20) carbon atoms.

[0064] Examples of polysiloxane groups include: -[-Si(R s )2-O-] a -Si(R s )3 -L s1 -[-Si(R s )2-O-] a -Si(R s )3 -L s1 -OL s1 -[-Si(R s )2-O-] a -R s -L s1 -[-Si(R s )2-O-] a -Si(R s )3 -L s1 -OL s1 -[-Si(R s )2-O-] a -R s -L s1 -[-Si(R s )2-O-] a -Si(R s ) 3、 -L s1 -[-Si(R s )2-O-]a -R s [In the formula, R s is independently in each occurrence a hydrocarbon group or a reactive group having 1 to 40 carbon atoms, and the terminal R s has one or more reactive groups, R s 50 mol % or more of the total groups are methyl groups, L s1 is a hydrocarbon group having 1 to 20 carbon atoms, a is between 5 and 10,000. TIFF0007787456000001.tif2069 [In the formula, a represents an integer of 0 to 150, b represents an integer of 1 to 150, (a+b) is 5 to 200, and n is an integer of 0 to 36.] etc.

[0065] [Examples of hydrophobic compounds (A)] Examples of the hydrophobic compound (A) include hydrocarbon compounds and compounds having a hydrocarbon group. Examples and preferred ranges of the hydrocarbon group are as described above.

[0066] An example of the hydrophobic compound (A) is a compound selected from the group consisting of amine-modified compounds, polyol-modified compounds, polycarboxylic acid-modified compounds, and other liquid or solid oils (described in detail below). For example, the hydrophobic compound (A1) may be a compound selected from the group consisting of amine-modified compounds, polyol-modified compounds, polycarboxylic acid-modified compounds, paraffin wax, and microcrystalline wax (e.g., a compound selected from the group consisting of amine-modified compounds, polycarboxylic acid-modified compounds, paraffin wax, and microcrystalline wax; particularly an amine-modified compound), and the hydrophobic compound (A2) may be a liquid or solid oil that does not fall under the category of the compound (A1) (e.g., a liquid or solid oil other than an amine-modified compound; particularly, a liquid or solid oil that is not a compound selected from the group consisting of amine-modified compounds, polycarboxylic acid-modified compounds, paraffin wax, and microcrystalline wax; in one embodiment, a liquid or solid oil that is not a compound selected from the group consisting of amine-modified compounds, polyol-modified compounds, polycarboxylic acid-modified compounds, paraffin wax, and microcrystalline wax).

[0067] The hydrophobic compound (A) may be a hydrocarbon, but may also be a non-hydrocarbon compound having a functional group such as an ester group, an ether group, or an amide group (amide structure). For example, the hydrophobic compound (A) may include a compound having an amide structure. Here, the amide structure may be a broad amide structure and may be selected from amides (carboxylic acid amides), ureas, urethanes, imides, thioamides, thioureas, thiourethanes, thioimides, sulfonamides, sulfoneureas, sulfoneurethanes, sulfonimides, etc. The amide structure may be an amide structure selected from the group consisting of -(C=O)N(-)2, -(C=S)N(-)2, and -S(=O)2N(-)2 (each group may be inverted). Here, at least one of the bonds of the N in the amide structure may be bonded to a hydrogen atom. The amide structure is preferably -(C=O)N(-)2, and may be an amide structure in a group selected from the group consisting of an amide group, a urea group, a urethane group, and an imide group.

[0068] For example, the hydrophobic compound (A1) may have an amide structure, and the hydrophobic compound (A2) may not have an amide structure.

[0069] [Composition of Hydrophobic Compound (A)] The amount of the hydrophobic compound (A1) may be 15% by weight or more, 25% by weight or more, 35% by weight or more, 45% by weight or more, 55% by weight or more, 65% by weight or more, 75% by weight or more, 85% by weight or more, or 95% by weight or more, and may be 97.5% by weight or less, 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 10% by weight or less, based on the hydrophobic compound (A).

[0070] The amount of the hydrophobic compound (A1) may be 5 parts by weight or more, 10 parts by weight or more, 25 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, or 300 parts by weight or more, relative to 100 parts by weight of the hydrophobic compound (A2), and may be 2000 parts by weight or less, 1750 parts by weight or less, 1500 parts by weight or less, 1250 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 250 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, or 10 parts by weight or less.

[0071] The amount of the hydrophobic compound (A2) may be 15% by weight or more, 25% by weight or more, 35% by weight or more, 45% by weight or more, 55% by weight or more, 65% by weight or more, 75% by weight or more, 85% by weight or more, or 95% by weight or more, and may be 97.5% by weight or less, 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 10% by weight or less, based on the amount of the hydrophobic compound (A).

[0072] The amount of the hydrophobic compound (A2) may be 5 parts by weight or more, 10 parts by weight or more, 25 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, or 300 parts by weight or more, relative to 100 parts by weight of the hydrophobic compound (A1), and may be 2000 parts by weight or less, 1750 parts by weight or less, 1500 parts by weight or less, 1250 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 250 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, or 10 parts by weight or less.

[0073] [Amount of hydrophobic compound (A)] The amount of the hydrophobic compound (A) in the composition may be 0.01% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, or 30% by weight or more, and may be 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight or less. The hydrophobic compound (A) alone may be used as the composition.

[0074] [Amine-modified compounds] As an example of each of the hydrophobic compounds (A1) and (A2), an amine-modified compound will be described. The amine-modified compound is a compound obtained by chemically modifying an amine compound so as to exhibit liquid repellency.

[0075] Due to their structure, the amine-modified compounds disclosed herein have excellent dispersibility in liquid media, and the compositions disclosed herein can have stable performance. Compositions that use polymeric compounds as active ingredients tend to have broad molecular weight distributions and contain relatively large amounts of impurities. On the other hand, amine-modified compounds can be made into low-molecular-weight compounds, narrowing (uniformizing) the molecular weight distribution, and can therefore have good performance.

[0076] The melting point of the amine-modified product may be 30° C. or higher, 40° C. or higher, 60° C. or higher, 80° C. or higher, 100° C. or higher, or 120° C. or higher, preferably 40° C. or higher, 50° C. or higher, 60° C. or higher, 70° C. or higher, or 80° C. or higher, and may be 250° C. or lower, 225° C. or lower, 200° C. or lower, 150° C. or lower, 130° C. or lower, 120° C. or lower, 110° C. or lower, 100° C. or lower, 80° C. or lower, or 50° C. or lower, for example, 150° C. or lower, or 100° C. or lower. The melting point of the amine-modified product may be measured in accordance with JIS K 2235-1991.

[0077] [Structure etc.] The molecular weight of the amine-modified product may be 200 or more, 300 or more, 350 or more, 400 or more, 500 or more, 550 or more, or 750 or more; and may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 900 or less, 800 or less, 750 or less, or 500 or less.

[0078] The amine-modified product of the present disclosure may not have an active hydrogen-containing group. Examples of the active hydrogen-containing group include an amino group (an amino group that is not adjacent to a carbonyl group, e.g., a primary or secondary amino group), a hydroxyl group, and a carboxyl group. In particular, the amine-modified product of the present disclosure may not have a primary or secondary amino group that is not adjacent to a carbonyl group.

[0079] The amine-modified compound in the present disclosure may be a polyamide having a plurality of amide groups, for example, a compound in which a plurality of modifying groups (for example, Z N ) may be a polyamide modified via an amide group. Here, the amide may include an amide moiety contained in a urethane group, a urea group, an imide, or the like.

[0080] The amine-modified product may be a compound obtained by modifying an amine (raw amine compound) with a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group.

[0081] In the amine-modified product, one or more amino groups of the amine are substituted with a modifying group. The modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent. From the viewpoint of improving liquid repellency, the amine-modified product may have a structure in which an amine is modified with an aliphatic hydrocarbon group having 3 to 40 carbon atoms (for example, 6 to 40 carbon atoms).

[0082] For details of the monovalent hydrocarbon group which may have a substituent and the monovalent polysiloxane group, the embodiments in the above description of the (monovalent hydrocarbon group which may have a substituent) and (monovalent polysiloxane group) are incorporated herein by reference.

[0083] (amine skeleton) The amine-modified product of the present disclosure has an amine skeleton. The amine skeleton has one or more amino groups with a predetermined number of bonds (valence) obtained by removing a predetermined number of atoms or atomic groups (e.g., hydrogen) from an amine compound. The amino group in the amine skeleton refers to a group selected from the group consisting of -NH, -NH-, and -N(-) and includes amino groups adjacent to carbonyl groups contained in amide groups, urethane groups, urea groups, imides, etc. Note that the amine skeleton may be any aliphatic or aromatic group having one or more amino groups, and does not exclude the presence of heteroatoms other than nitrogen.

[0084] The molecular weight of the amine skeleton may be 30 or more, 50 or more, 100 or more, 200 or more, 300 or more, 400 or more, or 500 or more, and may be 2800 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 600 or less, 450 or less, 300 or less, or 250 or less.

[0085] The number of carbon atoms in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and may be 100 or less, 80 or less, 60 or less, 40 or less, 30 or less, 20 or less, 10 or less, or 5 or less, preferably 50 or less, particularly 30 or less.

[0086] The amine skeleton has one or more amino groups. The amino groups are monovalent to trivalent amino groups, and are one or more groups selected from the group consisting of -NH2, -NH-, and -N(-)2. The number of amino groups in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, preferably 2 or more, and may be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0087] The amine skeleton has a hydrocarbon group (an aliphatic hydrocarbon group or an aromatic hydrocarbon group). The hydrocarbon group may be cyclic, branched, or linear. The hydrocarbon group may be saturated or unsaturated (e.g., saturated). Here, the hydrocarbon group may be interrupted by oxygen atoms and / or sulfur atoms, or may consist of only carbon atoms, nitrogen atoms, and hydrogen atoms. The hydrocarbon group may be a hydrocarbon group (e.g., a chain-like saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having one to two hydrocarbon aromatic rings) that may be interrupted by oxygen atoms and / or sulfur atoms, or may be a general hydrocarbon group (e.g., a chain-like saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having one to two hydrocarbon aromatic rings). When the hydrocarbon group is interrupted by oxygen atoms and / or sulfur atoms, it has an ether, thioether, polyether, or polythioether structure. The number of hydrocarbon groups in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and may be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0088] The amine skeleton may be composed of a monovalent to trivalent amino group and a chain saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group which may be interrupted by an oxygen atom and / or a sulfur atom.

[0089] The molar ratio of carbon atoms to nitrogen atoms (C / N ratio) in the amine skeleton may be 1 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, or 4 or more, and may be 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, or 2 or less, and is preferably 6 or less or 4 or less.

[0090] (-Y N -Z N n ) The amine modification in the present disclosure has the following formula: -Y N -Z N n [In the formula, Y N is a direct bond or a group with a valence of 1+n, Z N represents a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, n is an integer between 1 and 3. and having one or more groups represented by At least one -Y N -Z N n is bonded to the nitrogen atom of the amine skeleton.

[0091] Amine modification has -Y N -Z N n The number may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, preferably 2 or more, and may be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0092] At least one -Y in the amine modification N -Z N n is bonded to the nitrogen atom of the amine skeleton. N -Z N n Among the number of -Y bonded to the nitrogen atom of the amine skeleton, N -Z N n The proportion of the number of -Y groups not bonded to a nitrogen atom of the amine skeleton may be 10% or more, 30% or more, 60% or more, 80% or more, or 100%, and may be 75% or less, 50% or less, or 25% or less. N -Z Nn is bonded to another group (for example, a hydrocarbon group) on the amine skeleton.

[0093] (Y N ) Y N is a direct bond or a 1+n valent group, preferably a 1+n valent group. N is an amine skeleton and n Z N It acts as a linker connecting the

[0094] n is Y N Z combines with N and may be an integer of 1 or more and 3 or less. n may be 1 or more, 2 or more, or 3 or more, or 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0095] Y N may be an aliphatic group (unsaturated or saturated) or an aromatic group.

[0096] Y N The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 300 or less.

[0097] Y N may have a carbonyl group. N may have one or more selected from the group consisting of an amide group, a urea group, a urethane group, and an imide group, or Y N may form, together with the amino group in the amine skeleton, one or more selected from the group consisting of an amide group, a urea group, a urethane group, and an imide group. Examples of such an amide group, a urea group, a urethane group, and an imide group include: -OC(=O)-NR'-, -NR'-C(=O)-, —NR′—C(═O)—O—, -NR'-C(=O)-NR'- -C(=O)-NR'- -C(=O)-NR'-C(=O)- [In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)] Examples include: Y N is preferably attached to the nitrogen atom in the amine skeleton via a -(C=O)- group.

[0098] Y N represents a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2, a divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent to tetravalent hydrocarbon aromatic ring, and a divalent to tetravalent heterocycle. [In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)] It may be a (1+n) valent group consisting of one or more groups selected from the group consisting of:

[0099] Y N is Y N1 and Y N2 is a (1+n) valent group consisting of one or more members selected from the group consisting of Y N1 is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)), Y N2 is a group consisting of one or more members selected from the group consisting of di- to tetravalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, di- to tetravalent hydrocarbon aromatic rings, and di- to tetravalent heterocycles, In this specification, Y N The group shown as follows has an amine skeleton on the left and Z on the right. NCombine with.

[0100] 〇 Y N1 Y N1 is a non-hydrocarbon linker.

[0101] Y N1 is a direct bond or a divalent or higher valent group. N1 The valence of Y may be 2 to 4, 2 to 3, or 2. N1 is preferably not only a direct bond.

[0102] Y N1 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0103] Y N1 may be one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms). Y N1 Examples include: direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, —NR′—C(═O)—O—, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, —C(═O)—NR′—, —C(═O)—NR′—C(═O)—, -C(=NR')-, -S-, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2 etc. [In the formula, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).] In addition, Y N1 is bonded to a nitrogen atom of the amine skeleton, the nitrogen atom is considered to be part of the amine skeleton (amino group).

[0104] 〇 Y N2 Y N2 is a linker composed of one or more members selected from the group consisting of a hydrocarbon group which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, and a heterocycle which may have a substituent.

[0105] Y N2 Y may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). N2 Y may be aliphatic or aromatic. N2 may be linear, branched or cyclic.

[0106] Y N2 is a divalent or higher valent group. N2 The valence of may be, for example, 2 to 4, 2 to 3, or 2.

[0107] Y N2 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more carbon atoms, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0108] Y N2 is composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles.

[0109] The di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight-chain hydrocarbon group. The di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may be 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less. The valence of the aliphatic hydrocarbon group may be 2 or more, 3 or more, or 4 or less, 3 or less, or 2.

[0110] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (wherein, 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). The substituent may or may not have an 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 substituted aliphatic hydrocarbon group, 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.

[0111] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0112] The hydrocarbon aromatic ring may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and a halogen atom (wherein 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). The substituent may or may not have an 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 substituted hydrocarbon aromatic ring, the ratio of carbon atoms to the total 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.

[0113] The divalent to tetravalent heterocycle may be an aliphatic group or an aromatic group. Examples of divalent to tetravalent heterocycles include groups obtained by removing 2 to 4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring-constituting atoms of the heterocycle is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the heterocycle may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0114] The heterocycle may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and a halogen atom (wherein 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). The substituent may or may not have an 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 substituted heterocycle, the ratio of carbon atoms to the total carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more, and 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0115] Y N2 Examples include: -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali(-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or heterocycle.] etc.

[0116] Y N2 Specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond; a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms; -(CH2) q -Cy-(CH2) r -(q and r each independently represent a number from 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0117] Y N Examples Y N In the following, R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[0118] Y N An example of this is Y N If is bivalent, -Y N1 -, -Y N1 -Y N2 -, -Y N1 -Y N2 -Y N1 -, -Y N1 -Y N2 -Y N1 -Y N2 -, -Y N2 -, -Y N2 -Y N1 -, -Y N2 -Y N1 -Y N2 -, -Y N2 -Y N1 -Y N2 -Y N1 -, etc.

[0119] Y N An example of this is Y N If is trivalent, -Y N1 (-)2, -Y N1 -Y N2 (-)2, -Y N1 -(Y N2 -)2, -Y N1 -Y N2 -Y N1 (-)2, -Y N1 -Y N2 (-Y N1 -)2, -Y N1 -(Y N2 -YN1 -), 2, -Y N1 -Y N2 -Y N1 -Y N2 (-), 2, -Y N1 -Y N2 -Y N1 -(Y N2 -) 2、 -Y N1 -Y N2 -(Y N1 -Y N2 -) 2、 -Y N1 -(Y N2 -Y N1 -Y N2 -), 2; -Y N2 (-), 2, -Y N2 -Y N1 (-), 2, -Y N2 -(Y N1 (-), 2, -Y N2 -Y N1 -Y N2 (-), 2, -Y N2 -Y N1 (-Y N2 (-), 2, -Y N2 -(Y N1 -Y N2 (-), 2, -Y N2 -Y N1 -Y N2 -Y N1 (-), 2, -Y N2 -Y N1 -Y N2 -(Y N1 -) 2、 -Y N2 -Y N1 -(Y N2 -Y N1 -) 2、 -Y N2 -(Y N1 -Y N2 -Y N1 Examples include -), 2, etc.

[0120] Y N As an example of Y N when it is tetravalent, -Y N1 (-), 3, -Y N1 -Y N2 (-), 3, -Y N1 -(YN2 -), 3, -Y N1 -Y N2 -Y N1 (-), 3, -Y N1 -Y<O000252>(-Y N1 -), 3, -Y N1 -(Y N2 -Y N1 -), 3, -Y N1 -Y N2 -Y N1 -Y N2 (-), 3, -Y N1 -Y N2 -Y N1 -(Y N2 -), 3、 -Y N1 -Y N2 -(Y<0OOG268>-Y N2 '-), 3、 -Y N1 -(Y N2 -Y N1 -Y N2 -), 3; -Y N2 (-), 3, -Y N2 -Y N1 (-), 3, -Y N2 -(Y N1 -), 3, -Y N2 -Y N1 -Y N2 (-), 3, -Y N2 -Y N1 (-Y N2 -), 3, -Y N2 -(Y N1 -Y N2 -), 3, -Y[[ID=B6]] N2 -Y N1 '-Y N2 -Y N1 (-), 3, -Y N2 -Y N1 -Y [[ID=S8]] N2 [ -(Y N1 -), 3、 -Y N2 [[ID=IOS]]-Y N1 [[ID=1G7]]-(Y N2 -Y N1 -), 3、 -Y N2 -(Y N1 -Y N2 -Y N1 -), 3; etc. can be mentioned.

[0121] Y N Preferred examples of -Y N1 -, -Y N1 -Y N2 -, -Y N1 -Y N2 -Y N1 -, -Y N1 -Y N2 (-)2, -Y N2 -, -Y N2 -Y N1 -, -Y N2 -Y N1 -Y N2 -, -Y N2 -Y N1 (-)2, In the amine-modified compound, one or more Y N However, it is preferred that the terminal on the amine skeleton side is -(C=O)- and that it is bonded to a nitrogen atom in the amine skeleton.

[0122] Y N is preferably -Y N1 -, -Y N1 -Y N2 -, -Y N1 -Y N2 -Y N1 -, -Y N1 -Y N2 (-)2, -Y N2 -, -Y N2 -Y N1 -, -Y N2 -Y N1 -Y N2 -, -Y N2 -Y N1 (-)2, [In the formula, Y N1 but independently in each occurrence, direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, —NR′—C(═O)—O—, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, or -C(=O)-NR'- -C(=O)-NR'-C(=O)- (In the formula, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) and Y N2 is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a divalent aromatic group (for example, a divalent phenyl group or a divalent triazole group). This makes it possible to impart good liquid repellency to the substrate.

[0123] Y N Further specific examples of *-(C=O)- —O—(C═O)—NR′— [wherein * means bonding to a nitrogen atom of an amine skeleton, R' is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). etc.

[0124] (Z N ) Z N represents a monovalent hydrocarbon group or monovalent polysiloxane group having from 1 to 40 carbon atoms which may have a substituent, and the embodiments described above for (the monovalent hydrocarbon group which may have a substituent) and (the monovalent polysiloxane group) are applicable.

[0125] [Examples of amine-modified compounds] (Amine Modification Example 1) Examples of amine-modified compounds include those of the following formula: N(-Y N -Z N n ) p (-H) q-L 1 -[N(-Y N -Z N n ) r (-H) s -L 1 -] t -N(-Y N -Z N n ) p (-H) q [In the formula, Y N is independently in each occurrence a direct bond or a group with a valence of 1+n; Z N is independently in each occurrence an optionally substituted linear or branched monovalent hydrocarbon group having from 3 to 40 carbon atoms, L 1 is independently in each occurrence a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be interrupted by an oxygen atom and / or a sulfur atom; n, in each occurrence, is independently an integer between 1 and 3, inclusive; p, in each occurrence, is independently an integer between 0 and 2, inclusive; q, independently in each occurrence, is an integer between 0 and 2, inclusive; p+q is the sum of each N(-Y N -Z N n ) p (-H) q In, 2, r is independently in each occurrence 0 or 1; s is independently in each occurrence 0 or 1; r+s is the sum of each N(-Y N -Z N n ) r (-H) s In, 1, the sum of all p's and all r's is greater than or equal to 1, t is an integer between 0 and 10. Examples of the compound include a compound represented by the following formula (amine modified example 1):

[0126] In the amine modification example 1, Y N , Z N For details of n, the embodiments in the above description are used.

[0127] In the amine modification example 1, L 1 L is a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be interrupted by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched, or straight-chain hydrocarbon group, and is preferably a straight-chain hydrocarbon group or an aromatic hydrocarbon. 1 The hydrocarbon group in the above description of the [amine skeleton] may be used as L, and the hydrocarbon group may be separated by oxygen atoms and / or sulfur atoms, or may consist of only carbon atoms, nitrogen atoms, and hydrogen atoms. 1 L may be, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings. 1 is preferably a cyclic group having both a ring (e.g., an aromatic ring) and a chain structure (e.g., a linear structure, ether oxygen, or thioether sulfur), and specific examples thereof include a 1,3-phenylenebisalkylene group, a 1,4-phenylenebisalkylene group, a diphenyletherdiyl group, and a diphenylthioetherdiyl group. 1 may have 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more carbon atoms, and may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less carbon atoms.

[0128] In Amine Modification Example 1, p, in each occurrence, is independently an integer of 0 to 2, inclusive; q, in each occurrence, is independently an integer of 0 to 2, inclusive; and p+q is the sum of the values ​​of each N(-Y N -Z N n ) p (-H) q In the formula, p is 2. Preferably, p may be independently in each occurrence 1 or more, for example 2.

[0129] In Amine Modification Example 1, r is independently in each occurrence 0 or 1, s is independently in each occurrence 0 or 1, and r+s is independently in each occurrence 0 or 1. N -Z N n ) r (-H) s In the formula, p is 1. Preferably, p may be independently in each occurrence 1 or more, for example 2.

[0130] The sum of all p's and all r's is 1 or greater, i.e., Amine Modification Example 1 contains one or more -Y N -Z N n The sum of all p's and all r's may be 1 or more, 3 or more, 5 or more, 7 or more, 9 or more, or 12 or more (the sum of all q's and all s's may be 0), and may be 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, or 4 or less.

[0131] In Amine Modification Example 1, t is an integer of 0 or more and 10 or less. t may be 0 or more, 1 or more, 2 or more, 4 or more, or 6 or more, preferably 0 or more or 2 or more, and may be 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1 or less, for example, 0 or 1.

[0132] (Amine Modification Example 2) Other examples of amine modifications include those of the formula: N(-Y N -Z N n ) p (-H) q -L 2 (-Y N -Z N n ) u [In the formula, Y N is independently in each occurrence a direct bond or a group with a valence of 1+n; Z N is independently in each occurrence an optionally substituted linear or branched monovalent hydrocarbon group having from 3 to 40 carbon atoms, L2 represents a 1+u-valent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be interrupted by an oxygen atom and / or a sulfur atom, n, in each occurrence, is independently an integer between 1 and 3, inclusive; p is an integer between 0 and 2, q is an integer between 0 and 2, p+q is 2, u is an integer between 1 and 3, The sum of p and u is greater than or equal to 1.] An example of the compound represented by the formula (amine modified compound example 2) is:

[0133] In the amine modification example 2, Y N , Z N For details of n, the embodiments in the above description are referred to.

[0134] In the amine modification example 2, L 2 is a 1+u valent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be interrupted by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched, or straight-chain hydrocarbon group, preferably a straight-chain hydrocarbon group or an aromatic hydrocarbon. 2 The hydrocarbon group in the above description of the [amine skeleton] may be used as L, and the hydrocarbon group may be separated by oxygen atoms and / or sulfur atoms, or may consist of only carbon atoms, nitrogen atoms, and hydrogen atoms. 2 L may be, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings. 2 is preferably a cyclic group having both a ring (e.g., an aromatic ring) and a chain structure (e.g., a linear structure, ether oxygen, or thioether sulfur), and specific examples thereof include a 1,3-phenylenebisalkylene group, a 1,4-phenylenebisalkylene group, a diphenyletherdiyl group, and a diphenylthioetherdiyl group. 2may have 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more carbon atoms, and may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less carbon atoms.

[0135] In the amine modification example 2, p is an integer of 0 or more and 2 or less, q is an integer of 0 or more and 2 or less, and p+q is 2. Preferably, p may be 1 or more, for example, 2.

[0136] In the amine modification example 2, u is an integer of 1 or more and 3 or less. u is 1, 2, or 3, for example, 2 or 3.

[0137] In the amine modified example 2, the sum of p and u is 1 or more, that is, the amine modified example 2 has one or more -Y N -Z N n The sum of all p's and u's may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more (the sum of all q's may be 0), and may be 5 or less, 4 or less, 3 or less, or 2 or less.

[0138] (Example) Specific examples of the amine-modified compound include compounds represented by the following formula: In the following formula, the details of Z are as described above for Z N The embodiments in the description of the above are incorporated by reference.

[0139] TIFF0007787456000002.tif3340

[0140] TIFF0007787456000003.tif2757

[0141] TIFF0007787456000004.tif3042

[0142] TIFF0007787456000005.tif1843

[0143] TIFF0007787456000006.tif1755

[0144] TIFF0007787456000007.tif1851

[0145] TIFF0007787456000008.tif1660

[0146] The amine-modified wax may be a synthetic wax derived from animal or vegetable oils. The synthetic wax may be obtained by condensing a fatty acid derived from animal or vegetable oils with an aliphatic amine or an aromatic amine. Examples of synthetic waxes include fatty acid amide compounds such as hydroxy fatty acid amide compounds, palmitic acid amide compounds, octadecanoic acid amide compounds, stearic acid amide compounds, arachidic acid amide compounds, behenic acid amide compounds, lignoceric acid amide compounds, oleic acid amide compounds, linoleic acid amide compounds, α-linolenic acid amide compounds, γ-linolenic acid amide compounds, arachidonic acid amide compounds, eicosapentaenoic acid amide compounds, and docosahexaenoic acid amide compounds.

[0147] [Manufacturing method] The method for producing the amine-modified product is not limited, but may be carried out by reacting various amines (raw material amines) with Z in the presence of a condensing agent as needed. N A method for synthesizing by reacting a carboxylic acid containing a Z group with various amines. N Examples of the synthesis method include a method of reacting a group-containing carboxylic acid with an acid chloride, acid anhydride, isocyanate, etc. The condensing agent may be a known condensing agent, such as DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA, or Py-Bop.

[0148] (Amine (raw material amine)) Examples of amines (raw material amines) that are precursors of the amine skeleton are those that can constitute the amine skeleton, and include alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine; alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine, cyclohexanediamine, and methylenebiscyclohexylamine; diethylenetriamine, triethylenetetramine, tris(2-aminoethyl)amine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tris(2-aminopropyl)amine, tetrapropylenepentamine, pentapropylenehexamine, iminobispropylamine, dibutylenetriamine, bis(2-aminoethoxy)ethane, bis(2-aminoethyl)ether, bis[2-(2-aminoethoxy)ethyl]ether, and bis[2-(3-aminoprotoxy)ethyl]ether. polyalkylenepolyamines such as ether, spermine, and spermidine; oxygen- or sulfur-containing aliphatic amines such as 1-aminopropanediol, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, polyoxypropylenediamine, and polyoxyethylenediamine; aromatic monoamines such as aniline, 1- or 2-naphthylamine, 1-, 2-, or 9-aminoanthracene, 9-aminophenanthracene, and 2-, 3-, or 4-aminobiphenyl; monocyclic aromatic polyamines such as o-, m-, or p-phenylenediamine, o-, m-, or p-xylylenediamine, diaminotoluene, and 2,3-, 2,4-, or 2,5-tolylenediamine;Diaminobiphenyl, bisaminophenoxyphenylpropane, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl sulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenyl phenylethane, bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, aminophenoxybiphenyl, aminophenoxyphenylketone, bisaminoditrifluoromethylbenzylbenzene, aminophenoxyphenyl sulfone, aminophenoxyphenyl ether, aminophenoxyphenylpropane, bis(aminophenoxybenzoyl)benzene, bis(aminophenoxy-α,α-dimethylbenzyl)benzene, bis[(aminoaryloxy)benzoyl]diphenyl ether, bis(amino-α,α-dimethylbenzylphenoxy)benzophenone, aminophenoxyphenyl sulfide, bis[amino-α, α-dimethylbenzylphenoxy]diphenyl sulfone, 4,4'-bis[aminophenoxyphenoxy]diphenyl sulfone, diaminodiaryloxybenzophenone, Polycyclic aromatic polyamines such as diaminoaryloxybenzophenone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminotriphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenebisaniline, 4,4'-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 4,4'-diaminodiphenyl ether, and 4,4'-bis(aminophenyl)amine; oxygen- or sulfur-containing polycyclic aromatic polyamines such as 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 3,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl sulfide;Examples of the polyamine include hydroxyl group-containing polyamines such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine. The polyamine may be a polymerized product of a polymerizable compound such as allylamine.

[0149] [Polyol Modification] As an example of each of the hydrophobic compounds (A1) and (A2), a modified polyol will be described. The modified polyol is a compound obtained by chemically modifying a polyol so as to exhibit liquid repellency.

[0150] The melting point of the polyol-modified product may be 30° C. or higher, 40° C. or higher, 60° C. or higher, 80° C. or higher, 100° C. or higher, or 120° C. or higher, preferably 40° C. or higher, 50° C. or higher, 60° C. or higher, 70° C. or higher, or 80° C. or higher, and may be 250° C. or lower, 225° C. or lower, 200° C. or lower, 150° C. or lower, 130° C. or lower, 120° C. or lower, 110° C. or lower, 100° C. or lower, 80° C. or lower, or 50° C. or lower, for example, 150° C. or lower, or 100° C. or lower. The melting point of the polyol-modified product may be measured in accordance with JIS K 2235-1991.

[0151] [Structure etc.] The polyol-modified product may be a polymer having a degree of polymerization of at least 1. From the viewpoint of improving liquid repellency, the degree of polymerization of the polyol-modified product may be at least 2, at least 3, at least 5, at least 6, preferably at least 7, more preferably at least 8, and even more preferably at least 9; from the viewpoint of improving the handleability of the composition, it may be at most 100, preferably at most 50, more preferably at most 30, and even more preferably at most 15. The degree of polymerization refers to the number of repeating monomer units constituting the polymer.

[0152] The degree of polymerization in the present disclosure refers to an average degree of polymerization. The average degree of polymerization in the present disclosure refers to polymerization obtained by measurement under the following conditions. When the polyol-modified product in the present disclosure is a polyglycerol-modified product obtained by modifying polyglycerol, the degree of polymerization of the polyol-modified product refers to the average degree of polymerization of the polyglycerol. The average degree of polymerization of the polyglycerol is the average degree of polymerization (n) calculated from the hydroxyl value by end group analysis. Specifically, the average degree of polymerization and the average molecular weight are calculated from the following formulas (Formula 1) and (Formula 2). (Formula 1) Average molecular weight = 74n+18 (Equation 2) Hydroxyl value = 56110(n+2) / average molecular weight The hydroxyl value in the above formula (2) is a numerical value that indicates the number of hydroxyl groups contained in polyglycerol. The hydroxyl value is calculated from the amount of potassium hydroxide required to neutralize the acetic acid required to acetylate the free hydroxy groups contained in 1 g of polyglycerol, and is calculated in accordance with the "Standard Test Methods for the Analysis of Fats, Oils, and Related Compounds (I) 2003 Edition" compiled by the Japan Oil Chemists' Society. The hydroxyl value of the raw material polyglycerol is measured according to the above Standard Test Methods for the Analysis of Fats, Oils, and Related Compounds, and the average degree of polymerization and average molecular weight of the polyglycerol can be calculated from the above formula.

[0153] When the polyol-modified product in the present disclosure is a polyvinyl alcohol-modified product obtained by modifying polyvinyl alcohol, the degree of polymerization of the polyol-modified product refers to the average degree of polymerization of the polyvinyl alcohol, which can be measured in accordance with JIS K 6726, Testing Method for Polyvinyl Alcohol.

[0154] When the polyol-modified polysaccharide in the present disclosure is a polysaccharide obtained by modifying a polysaccharide, the degree of polymerization of the polyol-modified polysaccharide refers to the average degree of polymerization of the polysaccharide. The average degree of polymerization of a polysaccharide can be analyzed as follows. The degree of polymerization refers to the number of monosaccharide units (fructose and glucose units) in the polysaccharide. The average degree of polymerization is determined, for example, by the top of the peaks in the analysis results obtained by a conventional analytical method such as HPLC, GC, or HPAEC. The average degree of polymerization can be measured using, for example, an ULTRON PS-80N (8 × 300 mm) column manufactured by Shinwa Chemical Industry Co., Ltd. (solvent: water, flow rate: 0.5 ml / min, temperature: 50°C) or a TSK-GEL G30000 PWXL (7.8 × 300 mm) column manufactured by Tosoh Corporation (solvent: water, flow rate: 0.5 ml / min, temperature: 50°C) and a differential refractometer as a detector.

[0155] The modified polyol may be low molecular weight (eg, weight average molecular weight less than 1500, less than 1000, 500 or less) and / or high molecular weight. The weight average molecular weight of the polyol-modified product may be 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more; or may be 10,000,000 or less, 3,000,000 or less, 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 9,000 or less, 8,000 or less, 7,000 or less, 6,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,000 or less, or 500 or less.

[0156] The substitution rate of hydroxy groups in the polyol-modified product may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%, preferably 10% or more, for example 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, particularly 80% or more, and may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, for example 95% or less. Here, the "substitution rate" refers to the proportion (mol%) of hydroxy groups derived from the polyol that are modified, and may refer to the proportion (mol%) that are modified with optionally substituted monovalent hydrocarbon groups having from 1 to 40 carbon atoms or monovalent polysiloxane groups.

[0157] The residual hydroxyl group ratio in the polyol-modified product may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, for example, 5% or more, and may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, or 5% or less, for example, 50% or less, 30% or less, or 10% or less. Here, the "residual ratio" refers to the proportion (mol%) of unmodified hydroxyl groups derived from the polyol.

[0158] The number of modifying groups in the polyol modified product may be 2 or more, 5 or more, 7 or more, 8 or more, 9 or more, 10 or more, 12 or more, 15 or more, 30 or more, or 50 or more, and may be 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent.

[0159] The modifying group equivalent of the polyol modified product may be 150 or more, 250 or more, 350 or more, 450 or more, 550 or more, 650 or more, 750 or more, or 1000 or more, and may be 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 400 or less. This is the value obtained by dividing the weight-average molecular weight of the polyol modified product by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent.

[0160] In the polyol-modified product, one or more hydroxy groups of the polyol are substituted with a modifying group. The modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent. From the viewpoint of improving liquid repellency, the polyol-modified product may have a structure in which a polyol is modified with an aliphatic hydrocarbon group having 3 to 40 carbon atoms (for example, 6 to 40 carbon atoms).

[0161] For details of the monovalent hydrocarbon group which may have a substituent and the monovalent polysiloxane group, the embodiments in the above description of the (monovalent hydrocarbon group which may have a substituent) and (monovalent polysiloxane group) are incorporated herein by reference.

[0162] (-Y O -Z O n ) In the present disclosure, modified polyols are those in which one or more hydroxy groups of the polyol have the formula: -Y O -Z O n [In the formula, Y O is Y O1 and Y O2 is a (1+n) valent group consisting of one or more members selected from the group consisting of Y O1is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)), Y O2 is a group consisting of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles, Z O represents a monovalent hydrocarbon group having from 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group, n is an integer between 1 and 3. It may be substituted with a group represented by the following formula:

[0163] (Y O ) Y O is Y O1 and Y O2 is a (1+n) valent group consisting of one or more members selected from the group consisting of Y O1 is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)), Y O2 is a group composed of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles.

[0164] n is Y O Z combines withO and may be an integer of 1 or more and 3 or less. n may be 1 or more, 2 or more, or 3 or more, or 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0165] Y O The molecular weight of may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more, and may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[0166] Y O may have an amide structure. Here, the amide structure may be a broad amide structure and may be selected from amide (acid amide), urea, urethane, imide, thioamide, thiourea, thiourethane, thioimide, sulfonamide, sulfoneurea, sulfoneurethane, sulfonimide, etc. The amide structure may be an amide structure selected from the group consisting of -(C=O)N(-)2, -(C=S)N(-)2, and -S(=O)2N(-)2 (each group may be inverted). Here, at least one of the bonds possessed by N in the amide structure may be bonded to a hydrogen atom. The amide structure is preferably -(C=O)N(-)2, and may be an amide structure in a group selected from the group consisting of an amide group, a urea group, a urethane group, and an imide group. The presence of an amide structure can improve liquid repellency.

[0167] ○ Y O1 Y O1 is a non-hydrocarbon linker.

[0168] Y O1 is a direct bond or a divalent or higher valent group. O1 The valence of Y may be 2 to 4, 2 to 3, or 2. O1 is preferably not only a direct bond.

[0169] Y O1The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0170] Y O1 may be one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2 (wherein R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)). Y O1 Examples include: direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, —NR′—C(═O)—O—, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, —C(═O)—NR′—, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2 etc. (In the formula, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) Examples include:

[0171] Y O2may have at least an amide structure. Here, the amide structure may be a broad amide structure and may be selected from amide (acid amide), urea, urethane, imide, thioamide, thiourea, thiourethane, thioimide, sulfonamide, sulfoneurea, sulfoneurethane, sulfonimide, etc. The amide structure may be an amide structure selected from the group consisting of -(C=O)N(-)2, -(C=S)N(-)2, and -S(=O)2N(-)2 (each group may be inverted). Here, at least one of the bonds possessed by N in the amide structure may be bonded to a hydrogen atom. The amide structure is preferably -(C=O)N(-)2, and may be an amide structure in a group selected from the group consisting of an amide group, a urea group, a urethane group, and an imide group. The presence of an amide structure can improve liquid repellency.

[0172] ○ Y O2 Y O2 is a linker composed of one or more members selected from the group consisting of a hydrocarbon group which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, and a heterocycle which may have a substituent.

[0173] Y O2 Y may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). O2 Y may be aliphatic or aromatic. O2 may be linear, branched or cyclic.

[0174] Y O2 is a divalent or higher valent group. O2 The valence of may be, for example, 2 to 4, 2 to 3, or 2.

[0175] Y O2 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more carbon atoms, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0176] Y O2 is composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles.

[0177] The di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight-chain hydrocarbon group. The di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may be 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less. The valence of the aliphatic hydrocarbon group may be 2 or more, 3 or more, or 4 or less, 4 or less, 3 or less, or 2.

[0178] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (wherein, 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). The substituent may or may not have an 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 substituted aliphatic hydrocarbon group, 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.

[0179] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0180] The hydrocarbon aromatic ring may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and a halogen atom (wherein 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). The substituent may or may not have an 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 substituted hydrocarbon aromatic ring, 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.

[0181] The divalent to tetravalent heterocycle may be an aliphatic group or an aromatic group. Examples of divalent to tetravalent heterocycles include groups obtained by removing 2 to 4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring-constituting atoms of the heterocycle is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the heterocycle may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0182] The heterocycle may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and a halogen atom (wherein 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). The substituent may or may not have an 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 substituted heterocycle, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more, and 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0183] Y O2 Examples include: -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali(-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or heterocycle.] etc.

[0184] Y O2 Specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond; a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms; -(CH2) q -Cy-(CH2) r -(q and r each independently represent a number from 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0185] (Y O (Example) Y O In the following, R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[0186] Y O An example of this is Y O If is bivalent, -Y O1 -, -Y O1 -Y O2 -, -Y O1 -Y O2 -Y O1 -, -Y O1 -Y O2 -Y O1 -Y O2 -, -Y O2 -, -Y O2 -Y O1 -, -Y O2 -YO1 -Y O2 - and -Y O2 -Y O1 -Y O2 -Y O1 - etc. can be mentioned.

[0187] Y O As an example of Y O when Y is trivalent, -Y O1 (-)2, -Y O1 -Y O2 (-)2, -Y O1 -(Y O2 -)2, -Y O1 -Y O2 -Y O1 (-)2, -Y O1 -Y O2 (-Y O1 -)2, -Y O1 -(Y O2 -Y O1 -)2, -Y O1 -Y O2 -Y O1 -Y O2 (-)2, -Y O1 -Y O2 -Y O1 -(Y O2 -) 2、 -Y<​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​O1 (-)2, -Y O2 -Y O1 -Y O2 -(Y O1 -) 2、 -Y O2 -Y O1 -(Y O2 -Y O1 -) 2、 -Y O2 -(Y O1 -Y O2 -Y O1 -)2, etc. can be mentioned.

[0188] Y O Examples of Y O When Y is tetravalent, -Y O1 (-)3, -Y O1 -Y O2 (-)3, -Y O1 -(Y O2 -)3, -Y O1 -Y O2 -Y​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​O2 -Y O1 (-Y O2 -)3, -Y O2 -(Y O1 -Y O2 -)3, -Y O2 -Y O1 -Y O2 -Y O1 (-)3, -Y O2 -Y O1 -Y O2 -(Y O1 -) 3、 -Y O2 -Y O1 -(Y O2 -Y O1 -) 3、 -Y O2 -(Y O1 -Y O2 -Y O1 -)3; etc.

[0189] Y O Preferred examples of -Y O1 -, -Y O1 -Y O2 -, -Y O1 -Y O2 -Y O1 -, -Y O1 -Y O2 (-)2, -Y O2 -, -Y O2 -Y O1 -, -Y O2 -Y O1 -Y O2 -, -Y O2 -Y O1 (-)2, etc.

[0190] (Preferred Y O (Example) Preferably, Y O but -OY O11 -or -OY O11 -Y O21 -Y O12 - wherein each symbol represents independently at each occurrence: YO11 is a direct bond, —C(═O)—, —C(═O)—NR′—, or —C(═S)—NR′—; Y O21 is a hydrocarbon group having 1 to 40 carbon atoms, Y O12 is -O-, -OC(=O)-, -OC(=O)-O-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SON2NR'-, -C(OR')R'-, or -C(OR')(-)2; It may be.

[0191] Y O11 is a non-hydrocarbon linker, which is a direct bond or a divalent or higher valent group.

[0192] Y O11 The molecular weight of may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0193] Y O11 may be a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-.

[0194] Y O21 is a divalent hydrocarbon linker, which may be a hydrocarbon group having 1 to 40 carbon atoms.

[0195] Y O21 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more carbon atoms, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0196] Here, the hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched chain, or straight chain hydrocarbon group, and may be a saturated or unsaturated (for example, saturated) aliphatic hydrocarbon group.

[0197] Y O21 Specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond; a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms; -(CH2) q -Cy-(CH2) r -(q and r each independently represent a number from 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0198] Y O12 may be —O—, —OC(═O)—, —OC(═O)—O—, —OC(═O)—NR′—, —NR′—, —NR′—C(═O)—, —NR′—C(═O)—O—, —NR′—C(═O)—NR′—, —C(═O)—O—, —C(═O)—NR′—, —SO—, —SONR′—, —C(OR′)R′—, or —C(OR′)(−)2.

[0199] Y O12may have at least an amide structure. Here, the amide structure may be a broad amide structure and may be selected from amide (acid amide), urea, urethane, imide, thioamide, thiourea, thiourethane, thioimide, sulfonamide, sulfoneurea, sulfoneurethane, sulfonimide, etc. The amide structure may be an amide structure selected from the group consisting of -(C=O)N(-)2, -(C=S)N(-)2, and -S(=O)2N(-)2 (each group may be inverted). Here, at least one of the bonds possessed by N in the amide structure may be bonded to a hydrogen atom. The amide structure is preferably -(C=O)N(-)2, and may be an amide structure in a group selected from the group consisting of an amide group, a urea group, a urethane group, and an imide group. The presence of an amide structure can improve liquid repellency.

[0200] (Z O ) Z O represents a monovalent hydrocarbon group or monovalent polysiloxane group having from 1 to 40 carbon atoms which may have a substituent, and the embodiments described above for (the monovalent hydrocarbon group which may have a substituent) and (the monovalent polysiloxane group) are applicable.

[0201] [Other modifying groups] The hydroxy group of the polyol is -Y O -Z O n The group may be substituted with a modifying group other than the following: Examples of the modifying group are anionic groups and / or cationic groups.

[0202] Examples of the anionic group include a monomer having a carboxyl group, a sulfonic acid group, or a phosphoric acid group.

[0203] Examples of salts of anionic groups include alkali metal salts, alkaline earth metal salts, and ammonium salts, such as methylammonium salts, ethanolammonium salts, and triethanolammonium salts.

[0204] The cationic group is an amino group, preferably a tertiary amino group or a quaternary amino group. In a tertiary amino group, two groups bonded to the nitrogen atom are the same or different and preferably an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (an aryl group), or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, such as a benzyl group (C6H5-CH2-)). In a quaternary amino group, three groups bonded to the nitrogen atom are the same or different and preferably an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (an aryl group), or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, such as a benzyl group (C6H5-CH2-)). In a tertiary amino group or a quaternary amino group, the remaining group bonded to the nitrogen atom may have a carbon-carbon double bond. The cationic group may be in the form of a salt.

[0205] The cationic group in the form of a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, such as carboxylic acids having 1 to 20 carbon atoms (particularly monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid) are preferred.

[0206] [Manufacturing method] The modified polyol may be prepared by reacting a modifying agent having a modifying group (or a precursor structure of the modifying group) with the hydroxy group of the polyol.

[0207] (Polyol) A polyol is a compound having two or more hydroxy groups and is a compound that serves as a raw material for a modified polyol. A polyol is a compound having two or more hydroxy groups in the molecule. The polyol may be aliphatic or aromatic, but is preferably aliphatic.

[0208] The polyol may have an ether bond. Preferably, the polyol may have two or more ether bonds. Specifically, the polyol is preferably a compound having two or more hydroxy groups and two or more ether bonds. In other words, the polyol is preferably a polyether having two or more hydroxy groups.

[0209] When the polyol is a polymer, the repeating structure of the monomer unit may contain a hydroxy group and an ether bond.

[0210] The polyol may be low molecular weight (e.g., weight average molecular weight less than 1000, 500 or less) and / or polymeric. The weight average molecular weight of the polyol may be 50 or more, 100 or more, 300 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more; or 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 5000 or less, 300,000 or less, 2,000 or less, 1,000 or less, or 500 or less.

[0211] The number of hydroxy groups in the polyol may 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 may be 3000 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.

[0212] The hydroxy group equivalent weight of the polyol may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, or 150 or more, and may be 1000 or less, 800 or less, 600 or less, 400 or less, 200 or less, 100 or less, or 75 or less. The hydroxy group equivalent weight of the polyol is the value obtained by dividing the weight average molecular weight of the polyol by the number of hydroxyl groups.

[0213] The polyol may be a natural product. The natural product may be a high molecular weight natural product, a low molecular weight natural product, or a derivative thereof. The above natural products also include compounds converted from microorganisms. Examples of polyols include monosaccharides, oligosaccharides, polysaccharides, sugar alcohols (reducing sugars), hydroxy acids, amino acids, vitamins, flavonols, hydroxy hydrocarbons, hydroxy group-containing compound polymers, polyether polyols, polymer polyols, polyester polyols, and other polyols.

[0214] Examples of monosaccharides include glucose, fructose, galactose, and xylose.

[0215] Examples of oligosaccharides include sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, and sucralose.

[0216] Examples of sugar alcohols (reducing sugars) include sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, and lactitol.

[0217] Examples of polysaccharides include starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa carrageenan, iota carrageenan, isomaltodextrin, gellan gum, and tamarind seed gum.

[0218] Examples of hydroxy acids include ascorbic acid, kojic acid, quinic acid, chlorogenic acid, and gluconic acid.

[0219] Examples of amino acids include glucosamine.

[0220] Examples of vitamins include ascorbic acid and inositol.

[0221] Examples of flavonols include catechin, quercetin, and anthocyanin.

[0222] Examples of hydroxy hydrocarbons include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerin, trimethylolpropane, trimethylolethane, etc. Hydroxy hydrocarbons are hydrocarbons having a hydroxy group and may be aromatic or aliphatic, but are preferably aliphatic. The term "hydroxy hydrocarbon" may also refer to hydroxy hydrocarbons other than compounds included in other groups such as polysaccharides (other hydroxy hydrocarbons).

[0223] Examples of the hydroxy group-containing compound polymer include polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, and hydroxybutyl (meth)acrylate polymer.

[0224] An example of a polyether polyol may be a compound obtained by addition polymerization of an alkylene oxide to an initiator. Examples of initiators include compounds having two or more functional hydroxy groups. Examples of initiators include propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, glycerin, polyglycerin, trimethylolpropane, triethanolamine, pentaerythritol, ethylenediamine, aromatic diamines, diethylenetriamine, sorbitol, and sucrose. Examples of alkylene oxides include ethylene oxide and propylene oxide. Polyether polyols obtained by addition polymerization of alkylene oxide to the above initiators are also referred to as polyoxyalkylene polyols or oxyalkylene derivatives of polyols. Representative examples of polyether polyols include polyoxypropylene triol, obtained by addition polymerization of propylene oxide to glycerin, and polyoxypropylene polyglyceryl ether, obtained by addition polymerization of propylene oxide to polyglycerin.

[0225] An example of a polymer polyol is a compound obtained by polymerizing at least a portion of a polyether polyol with an ethylenically unsaturated monomer, such as acrylonitrile or styrene.

[0226] Examples of polyester polyols include compounds obtained by dehydration condensation of a compound having two or more functional carboxyl groups with a compound having two or more functional hydroxyl groups. Examples of compounds having two or more functional carboxyl groups include terephthalic acid, isophthalic acid, phthalic acid, methylphthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, and acid anhydrides thereof. Examples of compounds having two or more functional hydroxyl groups include ethylene glycol, propylene glycol, propanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and polymers thereof.

[0227] (modifying agent) The modifying agent is preferably a compound that is reactive with polyol and has the above-mentioned monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group.

[0228] Examples of modifying agents are as follows: Acid halide G(O=)CZ O Acid anhydride O(C(=O)-Z O )2 Carboxylic acid HO(O=)CZ O Isocyanate O=C=NZ O Thioisocyanate S=C=NZ O Epoxy (CH2OCH)CH2O-Z O Halide GZ O Amine H2N-Z O Hydroxy HO-Z O [In the formula, Z O is as defined above, and G is a halogen atom (e.g., F, Cl, Br, or I).

[0229] Z in the structure of the above modifier O may be replaced with any group constituting the modifying group, for example, Z O may be a group having a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group, or, for example, Z O A-Y O -Z O n It may also be possible to use the following.

[0230] A modified polyol may be synthesized by reacting a polyol with a modifying agent. For example, a modified polyol can be synthesized by reacting a modifying agent such as an acid halide compound, an acid anhydride, or a carboxylic acid with a hydroxy group of a polyol to form an ester bond. Alternatively, a modified polyol can be produced by reacting a modifying agent such as a halide or an epoxy compound with a hydroxy group of a polyol to form an ether bond. Those skilled in the art can appropriately design the reaction conditions between a polyol and a modifying agent, such as by using a catalyst (e.g., an acid catalyst or a base catalyst) or a condensing agent, depending on the desired product.

[0231] [Polycarboxylic acid modified product] As an example of each of the hydrophobic compounds (A1) and (A2), a polycarboxylic acid modified product will be described. The polycarboxylic acid modified product is a compound obtained by chemically modifying a polycarboxylic acid so as to exhibit liquid repellency.

[0232] The melting point of the polycarboxylic acid modified product may be 30° C. or higher, 40° C. or higher, 60° C. or higher, 80° C. or higher, 100° C. or higher, or 120° C. or higher, preferably 40° C. or higher, 50° C. or higher, 60° C. or higher, 70° C. or higher, or 80° C. or higher, and may be 250° C. or lower, 225° C. or lower, 200° C. or lower, 150° C. or lower, 130° C. or lower, 120° C. or lower, 110° C. or lower, 100° C. or lower, 80° C. or lower, or 50° C. or lower, for example, 150° C. or lower or 100° C. The melting point of the polycarboxylic acid modified product may be measured in accordance with JIS K 2235-1991.

[0233] [Structure etc.] The polycarboxylic acid modification may be low molecular weight (for example, weight average molecular weight less than 1500, less than 1000, 500 or less) and / or high molecular weight. The weight average molecular weight of the polycarboxylic acid modified product may be 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more; or may be 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 9,000 or less, 8,000 or less, 7,000 or less, 6,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,000 or less, or 500 or less.

[0234] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polycarboxylic acid modified product may be values ​​measured by GFC analysis using polyethylene glycol / polyethylene oxide as a standard sample with the following equipment and conditions. Separation column: SB-806M (8 mm x 30 mm, Shodex) Column temperature: 40℃ Mobile phase solvent: ion-exchanged water Mobile phase flow rate: 1.0 mL / min Sample concentration: 0.5 wt% Injection volume: 50μL Detector: RI detector (Waters2414, Waters)

[0235] The weight average molecular weight (Mw), number average molecular weight (Mn) and polydispersity index (Mw / Mn) of the polycarboxylic acid modified product, calculated as polystyrene, may be determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent and Shodex KF400RL and KF400RH columns (polystyrene gel) manufactured by Showa Denko K.K.

[0236] The substitution rate of hydroxy groups for carboxyl groups in the modified polycarboxylic acid may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%, and is preferably 10% or more, for example, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, particularly 80% or more, and may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, for example, 95% or less. Here, the "substitution rate" refers to the proportion (mol %) of hydroxy groups of carboxyl groups derived from polycarboxylic acid that are modified, and may refer to the proportion (mol %) that are modified with monovalent hydrocarbon groups having 1 to 40 carbon atoms or monovalent polysiloxane groups that may have a substituent.

[0237] The residual hydroxyl group ratio of carboxyl groups in the modified polycarboxylic acid may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, for example, 5% or more, and may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, or 5% or less, for example, 50% or less, 30% or less, or 10% or less. Here, the "residual ratio" refers to the proportion (mol %) of unmodified hydroxyl groups in carboxyl groups derived from the polycarboxylic acid.

[0238] The number of modifying groups in the polycarboxylic acid modified product may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, or 50 or more, and may be 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent.

[0239] The modifying group equivalent of the polycarboxylic acid modified product may be 150 or more, 250 or more, 350 or more, 450 or more, 550 or more, 650 or more, 750 or more, or 1000 or more, and may be 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 400 or less. This is the value obtained by dividing the weight-average molecular weight of the polycarboxylic acid modified product by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent.

[0240] In the polycarboxylic acid modified product, one or more hydroxy groups of the polycarboxylic acid are substituted with a modifying group. The modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent. From the viewpoint of improving liquid repellency, the polycarboxylic acid modified product may have a structure in which a polycarboxylic acid is modified with an aliphatic hydrocarbon group having 3 to 40 carbon atoms (for example, 6 to 40 carbon atoms).

[0241] For details of the monovalent hydrocarbon group which may have a substituent and the monovalent polysiloxane group, the embodiments in the above description of the (monovalent hydrocarbon group which may have a substituent) and (monovalent polysiloxane group) are incorporated herein by reference.

[0242] (-Y C -Z C n ) In the present disclosure, the modified polycarboxylic acid is a polycarboxylic acid in which the hydroxy group of one or more carboxyl groups has the following formula: -Y C -Z C n [In the formula, Y C is Y C1 and Y C2 is a (1+n) valent group consisting of one or more members selected from the group consisting of Y C1is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)), Y C2 is a group consisting of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles, Z C represents a monovalent hydrocarbon group having from 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group, n is an integer between 1 and 3. It may be substituted with a group represented by the following formula:

[0243] (Y C ) Y C is Y C1 and Y C2 is a (1+n) valent group consisting of one or more members selected from the group consisting of Y C1 is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)), Y C2 is a group composed of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles.

[0244] n is Y C Z combines withC and may be an integer of 1 or more and 3 or less. n may be 1 or more, 2 or more, or 3 or more, or 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0245] Y C The molecular weight of may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more, and may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[0246] Y C may have at least an amide structure. Here, the amide structure may be a broad amide structure and may be selected from amide (acid amide), urea, urethane, imide, thioamide, thiourea, thiourethane, thioimide, sulfonamide, sulfoneurea, sulfoneurethane, sulfonimide, etc. The amide structure may be an amide structure selected from the group consisting of -(C=O)N(-)2, -(C=S)N(-)2, and -S(=O)2N(-)2 (each group may be inverted). Here, at least one of the bonds possessed by N in the amide structure may be bonded to a hydrogen atom. The amide structure is preferably -(C=O)N(-)2, and may be an amide structure in a group selected from the group consisting of an amide group, a urea group, a urethane group, and an imide group. The presence of an amide structure can improve liquid repellency.

[0247] ○ Y C1 Y C1 is a non-hydrocarbon linker.

[0248] Y C1 is a direct bond or a divalent or higher valent group. C1 The valence of Y may be 2 to 4, 2 to 3, or 2. C1 is preferably not only a direct bond.

[0249] Y C1The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0250] Y C1 may be one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2 (wherein R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)). Y C1 Examples include: direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, —NR′—C(═O)—O—, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, —C(═O)—NR′—, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2 etc. (In the formula, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) Examples include:

[0251] Y C1may have at least an amide structure. Here, the amide structure may be a broad amide structure and may be selected from amide (acid amide), urea, urethane, imide, thioamide, thiourea, thiourethane, thioimide, sulfonamide, sulfoneurea, sulfoneurethane, sulfonimide, etc. The amide structure may be an amide structure selected from the group consisting of -(C=O)N(-)2, -(C=S)N(-)2, and -S(=O)2N(-)2 (each group may be inverted). Here, at least one of the bonds possessed by N in the amide structure may be bonded to a hydrogen atom. The amide structure is preferably -(C=O)N(-)2, and may be an amide structure in a group selected from the group consisting of an amide group, a urea group, a urethane group, and an imide group. The presence of an amide structure can improve liquid repellency.

[0252] ○ Y C2 Y C2 is a linker composed of one or more members selected from the group consisting of a hydrocarbon group which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, and a heterocycle which may have a substituent.

[0253] Y C2 Y may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). C2 Y may be aliphatic or aromatic. C2 may be linear, branched or cyclic.

[0254] Y C2 is a divalent or higher valent group. C2 The valence of may be, for example, 2 to 4, 2 to 3, or 2.

[0255] Y C2 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more carbon atoms, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0256] Y C2 is composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles.

[0257] The di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight-chain hydrocarbon group. The di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may be 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less. The valence of the aliphatic hydrocarbon group may be 2 or more, 3 or more, or 4 or less, 4 or less, 3 or less, or 2.

[0258] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (wherein, 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). The substituent may or may not have an 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 substituted aliphatic hydrocarbon group, 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.

[0259] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0260] The hydrocarbon aromatic ring may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and a halogen atom (wherein 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). The substituent may or may not have an 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 substituted hydrocarbon aromatic ring, 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.

[0261] The divalent to tetravalent heterocycle may be an aliphatic group or an aromatic group. Examples of divalent to tetravalent heterocycles include groups obtained by removing 2 to 4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring-constituting atoms of the heterocycle is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the heterocycle may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0262] The heterocycle may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and a halogen atom (wherein 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). The substituent may or may not have an 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 substituted heterocycle, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more, and 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0263] Y C2 Examples include: -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali(-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or heterocycle.] etc.

[0264] Y C2 Specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond; a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms; -(CH2) q -Cy-(CH2) r -(q and r each independently represent a number from 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0265] (Y C (Example) Y C In the following, R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[0266] Y C An example of this is Y C If is bivalent, -Y C1 -, -Y C1 -Y C2 -, -Y C1 -Y C2 -Y C1 -, -Y C1 -Y C2 -Y C1 -Y C2 -, -Y C2 -, -Y C2 -Y C1 -, -YC2 -Y C1 -Y C2 -、-Y C2 -Y C1 -Y C2 -Y C1 - etc. can be mentioned.

[0267] Y C As an example of Y C when it is trivalent, -Y C1 (-)2, -Y C1 -Y C2 (-)2, -Y C1 -(Y C2 -)2, -Y C1 -Y C2 -Y C1 (-)2, -Y C1 -Y C2 (-Y C1 -)2, -Y C1 -(Y C2 -Y C1 -)2, -Y C1 -Y C2 -Y C1 -Y C2 (-)2, -Y C1 -Y C2 -Y C1 -(Y C2 -) 2、 -Y C1 -Y C2 -(Y C1 -Y C2 -) 2、 -Y C1 -(Y C2 -Y C1 -Y C2 -)2; -Y C2 (-)2, -Y C2 -Y C1 (-)2, -Y C2 -(Y C1 -)2, -Y C2 -Y C1 -Y C2 (-)2, -Y C2 -Y C1 (-Y C2 -)2, -Y C2 -(Y C1 -Y C2 -)2, -Y C2 -Y C1 -YC2 -Y C1 (-)2, -Y C2 -Y C1 -Y C2 -(Y C1 -) 2、 -Y C2 -Y C1 -(Y C2 -Y C1 -) 2、 -Y C2 -(Y C1 -Y C2 -Y C1 -)2, etc. can be mentioned.

[0268] Y C As an example of Y C When Y is tetravalent, -Y C1 (-)3, -Y C1 -Y C2 (-)3, -Y C1 -(Y C2 -)3, -Y C1 -Y C2 -Y C1 (-)3, -Y C1 -Y C2 (-Y C1 -)3, -Y C1 -(Y C2 -Y C1 -)3, -Y C1 -Y C2 -Y C1 -Y C2 (-)3, -Y C1 -Y C2 -Y C1 -(Y C2 -) 3、 -Y C1 -Y C2 -(Y C1 -Y C2 -) 3、 -Y C1 -(Y C2 -Y C1 -Y C2 -)3; -Y C2 (-)3, -Y C2 -Y C1 (-)3, -Y C2 -(Y C1 -)3, -Y C2 -Y C1 -YC2 (-)3, -Y C2 -Y C1 (-Y C2 -)3, -Y C2 -(Y C1 -Y C2 -)3, -Y C2 -Y C1 -Y C2 -Y C1 (-)3, -Y C2 -Y C1 -Y C2 -(Y C1 -) 3、 -Y C2 -Y C1 -(Y C2 -Y C1 -) 3、 -Y C2 -(Y C1 -Y C2 -Y C1 -)3; etc.

[0269] Y C Preferred examples of -Y C1 -, -Y C1 -Y C2 -, -Y C1 -Y C2 -Y C1 -, -Y C1 -Y C2 (-)2, -Y C2 -, -Y C2 -Y C1 -, -Y C2 -Y C1 -Y C2 -, -Y C2 -Y C1 (-)2, etc.

[0270] (Preferred Y C (Example) Preferably, Y C but -Y C11 -or -Y C11 -Y C21 -Y C12 - wherein each symbol represents independently at each occurrence: Y C11 is —O— or —NR′—; Y C21 is a hydrocarbon group having 1 to 40 carbon atoms, Y C12 is -O-, -OC(=O)-, -OC(=O)-O-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SON2NR'-, -C(OR')R'-, or -C(OR')(-)2; It may be.

[0271] Y C11 is a non-hydrocarbon linker, which is a direct bond or a divalent or higher valent group.

[0272] Y C11 The molecular weight of may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0273] Y C11 may be a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-.

[0274] Y C21 is a divalent hydrocarbon linker, which may be a hydrocarbon group having 1 to 40 carbon atoms.

[0275] Y C21 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more carbon atoms, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0276] Here, the hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched chain, or straight chain hydrocarbon group, and may be a saturated or unsaturated (for example, saturated) aliphatic hydrocarbon group.

[0277] Y C21 Specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond; a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms; -(CH2) q -Cy-(CH2) r -(q and r each independently represent a number from 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0278] Y C12 may be —O—, —OC(═O)—, —OC(═O)—O—, —OC(═O)—NR′—, —NR′—, —NR′—C(═O)—, —NR′—C(═O)—O—, —NR′—C(═O)—NR′—, —C(═O)—O—, —C(═O)—NR′—, —SO—, —SONR′—, —C(OR′)R′—, or —C(OR′)(−)2.

[0279] Y C12may have at least an amide structure. Here, the amide structure may be a broad amide structure and may be selected from amide (acid amide), urea, urethane, imide, thioamide, thiourea, thiourethane, thioimide, sulfonamide, sulfoneurea, sulfoneurethane, sulfonimide, etc. The amide structure may be an amide structure selected from the group consisting of -(C=O)N(-)2, -(C=S)N(-)2, and -S(=O)2N(-)2 (each group may be inverted). Here, at least one of the bonds possessed by N in the amide structure may be bonded to a hydrogen atom. The amide structure is preferably -(C=O)N(-)2, and may be an amide structure in a group selected from the group consisting of an amide group, a urea group, a urethane group, and an imide group. The presence of an amide structure can improve liquid repellency.

[0280] (Z C ) Z C represents a monovalent hydrocarbon group or monovalent polysiloxane group having from 1 to 40 carbon atoms which may have a substituent, and the embodiments described above for (the monovalent hydrocarbon group which may have a substituent) and (the monovalent polysiloxane group) are applicable.

[0281] [Other modifying groups] The hydroxy group of the carboxyl group of polycarboxylic acid is -Y C -Z C n The polyol may be substituted with a modifying group other than the above. Examples of the modifying group are anionic groups and / or cationic groups. The anionic groups and / or cationic groups are the same as those described above in the description of [Other modifying groups] for the polyol.

[0282] [Manufacturing method] The modified polycarboxylic acid may be produced by reacting a modifying agent having a modifying group (or a precursor structure of the modifying group) with the hydroxy group of the carboxyl group of the polycarboxylic acid.

[0283] (Polycarboxylic acid) Polycarboxylic acids are compounds having two or more carboxyl groups and are used as raw materials for modified polycarboxylic acids. Polycarboxylic acids are compounds having two or more carboxyl groups in the molecule. Polycarboxylic acids may be aliphatic or aromatic, but are preferably aliphatic.

[0284] The polycarboxylic acid may be low molecular weight (e.g., weight average molecular weight less than 1000, 500 or less) and / or high molecular weight. The weight average molecular weight of the polycarboxylic acid may be 100 or more, 300 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more; or 1,000,000 or less, 7,500,000 or less, 500,000 or less, 3,000,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 5000 or less, 3,000 or less, 2,000 or less, 1,000 or less, or 500 or less.

[0285] The number of carboxyl groups in the polycarboxylic acid may 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 may be 3000 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.

[0286] The carboxyl group equivalent of the polycarboxylic acid may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, or 150 or more, and may be 1000 or less, 800 or less, 600 or less, 400 or less, 200 or less, 100 or less, or 75 or less. The carboxyl equivalent of the polycarboxylic acid is the value obtained by dividing the weight average molecular weight of the polycarboxylic acid by the number of hydroxyl groups.

[0287] The polycarboxylic acid may be a natural product. The natural product may be a high molecular weight natural product, a low molecular weight natural product, or a derivative thereof. The natural product also includes compounds converted from microorganisms.

[0288] The polycarboxylic acid may be at least one selected from the group consisting of dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, carboxyl group-containing compound polymers, and salts thereof.

[0289] 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, aldaric acid, and salts thereof.

[0290] Tricarboxylic acids are compounds having three carboxyl groups, and examples thereof include citric acid, tricarballylic acid, t-aconitic acid, trimellitic acid, and salts thereof.

[0291] Tetracarboxylic acids are compounds having four carboxyl groups, and examples thereof include pyromellitic acid and salts thereof.

[0292] The carboxyl group-containing compound polymer is a compound having five or more carboxyl groups, and examples thereof include alginic acid, tragacanth gum, gum arabic, polyacrylic acid, polymethacrylic acid, polymaleic acid, polyaspartic acid, polyglutamic acid, hyaluronic acid, heparin, xanthan gum, gellan gum, carboxymethylcellulose alginate, galacturonic acid, mannuronic acid, and salts thereof.

[0293] (modifying agent) The modifying agent is preferably a compound that is reactive with polycarboxylic acid and has the above-mentioned monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group, which may have a substituent.

[0294] Examples of modifying agents are as follows: Epoxy (CH2OCH)CH2O-Z C Amine H2N-Z C Hydroxy HO-Z C [In the formula, ZC is as described above.]

[0295] Z in the structure of the above modifier C may be replaced with any group constituting the modifying group, for example, Z C may be a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or may be, for example, Z C A-Y C -Z C n It may also be possible to use the following.

[0296] The modified polycarboxylic acid may be synthesized by reacting a polycarboxylic acid with a modifying agent. For example, the modifying agent, which is an epoxy compound, may be reacted with the carboxyl group of the polycarboxylic acid to form an ester bond, thereby producing the modified polycarboxylic acid. Those skilled in the art can appropriately design the reaction conditions between the polycarboxylic acid and the modifying agent, such as by using a catalyst (e.g., an acid catalyst or a base catalyst) or a condensing agent, depending on the desired product.

[0297] 〔oil〕 An oil will be described as an example of each of the hydrophobic compounds (A1) and (A2). The oil may be liquid or solid (wax) at room temperature. The oil may be selected from synthetic oils, mineral oils, animal oils, and vegetable oils. The oil may be a hydrocarbon oil or a non-hydrocarbon oil, and is typically a compound having a higher hydrocarbon structure (e.g., 10 or more, 20 or more, or 30 or more carbon atoms). The hydrocarbon group that the oil may have is as described above. The oil may be different from the amine-modified, polyol-modified, and polycarboxylic acid-modified compounds described above. The oil is a non-volatile oily compound, and the boiling point may be, for example, 200°C or higher, 250°C or higher, or 300°C or higher.

[0298] The melting point of the oil may be -100°C or higher, -75°C or higher, -50°C or higher, 0°C or higher, 30°C or higher, 40°C or higher, 60°C or higher, 80°C or higher, 100°C or higher, or 120°C or higher, preferably 40°C or higher, 50°C or higher, 60°C or higher, 70°C or higher, or 80°C or higher, and may be 250°C or lower, 225°C or lower, 200°C or lower, 150°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, 80°C or lower, 50°C or lower, 25°C or lower, 0°C or lower, -25°C or lower, -50°C or lower, -75°C or lower, or -100°C or lower, for example, 150°C or lower, 100°C or lower, 50°C or lower, 0°C or lower, or -50°C or lower. The melting point of the oil may be measured in accordance with JIS K 2235-1991.

[0299] The oil may be low molecular weight (e.g., molecular weight of 1000 or less, or 500 or less) or high molecular weight. When the oil is high molecular weight, its weight average molecular weight may be 1000 or more, 3000 or more, 5000 or more, 7500 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more; or 10000000 or less, 75000000 or less, 50000000 or less, 3000000 or less, 1000000 or less, 750000 or less, 5000000 or less, 300000 or less, 100000 or less, 750000 or less, 5 ... or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 100000 or less, 75000 or less,

[0300] [Synthetic oil] Synthetic oils are oils (oily compounds) obtained by chemical synthesis and may be liquid or solid (wax) at room temperature. Examples of synthetic oils include hydrocarbon oils, ester oils, ether oils, amide oils, and silicone oils.

[0301] [Mineral oil] The mineral oil may be liquid or solid (wax) at room temperature. Examples of the mineral oil include petrolatum, liquid paraffin, paraffin wax, microcrystalline wax, montan wax, ozokerite wax, ceresin wax, and petrolatum wax.

[0302] [Vegetable oil / Animal oil] Vegetable and animal oils may be liquid or solid (wax) at room temperature. These include soybean oil, rapeseed oil, sunflower oil, safflower oil, peanut oil, corn oil, cottonseed oil, rice bran oil, kapok oil, sesame oil, olive oil, linseed oil, castor oil, jojoba oil, cocoa oil, palm oil, palm kernel oil, coconut oil, hemp seed oil, rice oil, tea seed oil, castor oil, sesame oil, fish oil, shark liver oil, squalene oil, beef tallow, lard (pork fat), mutton tallow, beef foot oil, whale oil, salmon oil, bonito oil, herring oil, cod oil, and their hardened and hydrogenated oils; rice wax, carnauba wax, sunflower wax, candelilla wax, sumac wax, beeswax, lanolin, spermaceti, privet wax, etc.; fatty acids such as stearic acid, capric acid, caproic acid, linoleic acid, linolenic acid, palmitic acid, lauric acid, and eleostearic acid; fatty alcohols such as lauryl alcohol, cetostearyl alcohol, stearyl alcohol, cetyl alcohol, and myristyl alcohol; fatty acid esters such as glycerol monostearate, glycerol monooleate, acetylated monoglyceride, tristearin, tripalmitin, and cetyl ester glyceryl palmitostearate; glyceryl behenate; medium-chain triglycerides; and the like.

[0303] [Examples of hydrophobic compounds (A1) and (A2)]

[0304] The hydrophobic compound (A1) may be, for example, an amine-modified compound as described above, in particular an aliphatic amine-modified compound.

[0305] The hydrophobic compound (A1) may be, for example, an amine-modified compound or a wax (e.g., a hydrocarbon wax) as described above, and in particular an amine-modified compound (especially an aliphatic amine-modified compound). JPEG0007787456000009.jpg86101 Paraffin wax with carbon number 20 to 40 etc.

[0306] Examples of the hydrophobic compound (A2) include monoester compounds, diester compounds, triester compounds, tetraester compounds, polyester compounds, monoamide compounds, diamide compounds, triamide compounds, and polyamide compounds. Examples of the ester compound include glycerin esters, polyglycerin esters, sucrose esters, sorbitan esters, pentaerythritol esters, trimellitic acid esters, phthalic acid esters, adipic acid esters, pyromellitic acid esters, citrate esters, benzoic acid esters, and CH3(CH2) n ester compounds obtained by condensing an alcohol represented by OH (n=0 to 30, linear or branched structure) with a fatty acid; and the like. Examples of the amide compound include condensates of fatty acids and monoamines, condensates of fatty acids and diamines, condensates of fatty acids and triamines, condensates of fatty acids and tetraamines, and condensates of fatty acids and pentaamines.

[0307] The hydrophobic compound (A2) may be, for example, a polycarboxylic acid modified product, a polyol modified product, or an oil as explained above, and may particularly be a compound having a plurality of (e.g., 2 to 10, 2 to 6, or 2 to 4) monovalent aliphatic hydrocarbon structures (e.g., fatty acid ester structures). Examples of the hydrophobic compound (A2) include fatty acid-modified polyols (e.g., fatty acid-modified sugars, etc.), oils and fats, and long-chain aliphatic alcohol-modified polycarboxylic acids (e.g., long-chain alcohol-modified polyvalent aromatic rings, etc.). Specific examples include: Examples include JPEG0007787456000010.jpg13483.

[0308] [Dispersant] The composition of the present disclosure may contain a dispersant. The dispersant may be at least one selected from an organic dispersant and an inorganic dispersant. The dispersant may be at least one selected from an anionic dispersant, a nonionic dispersant, a cationic dispersant, an amphoteric dispersant, and an inorganic dispersant.

[0309] As the dispersant, an organic dispersant and an inorganic dispersant may be used individually, or a combination of an organic dispersant and an inorganic dispersant may be used.

[0310] An organic dispersant may be used as the dispersant. The organic dispersant can be classified into a nonionic dispersant, an anionic dispersant, a cationic dispersant, and an amphoteric dispersant, and the organic dispersant may refer to a surfactant.

[0311] The dispersant may be fluorine-free.

[0312] [Nonionic dispersant] The dispersant may include a nonionic dispersant, which may be a nonionic surfactant.

[0313] The nonionic dispersant may be a low molecular weight or a high molecular weight dispersant. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 100,000 or less, 25,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2500 or less, 750 or less, or 250 or less.

[0314] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols and amine oxides.

[0315] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0316] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a mono- to trideca-hydric (particularly di- to deca-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0317] An example of an ester ether is a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. An example of an alcohol is a mono- to trideca-hydric (particularly di- to deca-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0318] An example of an alkanolamide is formed from a fatty acid and an alkanolamine. The alkanolamide may be a monoalkanolamide or a dialkanolamine. An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, and having 1 to 3 amino groups and 1 to 5 hydroxy groups.

[0319] The polyol may be a di- to penta-hydric alcohol having 10 to 30 carbon atoms. The amine oxide may be an oxide (having, for example, 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0320] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic dispersant is generally preferably 2 to 100.

[0321] The nonionic dispersant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyols and amine oxides, and is preferably a nonionic dispersant having an oxyalkylene group.

[0322] The nonionic dispersant may be an alkylene oxide adduct of a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sorbitan ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a glycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyglycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sucrose ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, or the like. Among these, those in which the structure of the alkylene oxide adduct moiety and the polyalkylene glycol moiety is polyoxyethylene (POE) or polyoxypropylene (POP) or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Additionally, the nonionic dispersant may be free of aromatic groups.

[0323] The nonionic dispersant has the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [In the formula, R 1 is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or acyl group having 2 to 22 carbon atoms, R 2 are independently the same or different and are alkylene groups having 3 or more carbon atoms (e.g., 3 to 10), R 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number greater than or equal to 2, q is a number of 0 or 1 or more. The compound may be a compound represented by the formula:

[0324] R 1R preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. 1 Preferred specific examples include an octyl group, a nonyl group, a trimethylnonyl group, a lauryl group, a tridecyl group, an oleyl group, and a stearyl group. R 2 Examples of the alkyl group include a propylene group and a butylene group. In the nonionic dispersant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R 2 O) q - may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) at the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, with the oxypropylene chain being preferred.

[0325] Specific examples of nonionic dispersants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkanes (C 12 -C 16 ) Thiol, Sorbitan Mono Fatty Acid (C7-C 19 ) or alkyl (C 12 -C 18 ) amines, etc., sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan 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, polyethyleneimine ethoxylate, etc.

[0326] The proportion of the polyoxyethylene block can be 5 to 80% by weight, for example 30 to 75% by weight, particularly 40 to 70% by weight, based on the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of the nonionic dispersant is generally 300 to 5,000, for example, 500 to 3,000. The nonionic dispersant may be a single type or a mixture of two or more types. The nonionic dispersant may be a mixture of a compound having an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. Specifically, it is preferable to select from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, and polyoxypropylenes having an HLB value of 1 to 18, and sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, and polyoxyethylene sorbitan fatty acid esters having an HLB value of less than 7.

[0327] [Cationic dispersant] The dispersant may include a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a compound having no amide group.

[0328] The cationic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the cationic dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, or may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 25,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 750 or less, or 250 or less.

[0329] The cationic dispersant may be aliphatic or aromatic, and examples thereof include ammonium salts (e.g., quaternary ammonium salts). The cationic dispersant may be an oxyethylene adduct ammonium salt. Specific examples include amine salt-type dispersants such as alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines; quaternary ammonium salt-type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, and benzethonium chloride; and polymeric cationic dispersants such as polyquaternium-1 to -47. Examples of cationic dispersants include alkylamine salts and quaternary ammonium salts.

[0330] Low molecular weight cationic dispersants are R 21 -N + (-R 22 )(-R 23 )(-R 24 )X - [In the formula, R 21 , R 22 , R 23 and R 24 is 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 are alkyl groups (e.g., methyl, butyl, stearyl, and palmityl). Specific examples of X are halogens (e.g., chlorine) and acids (e.g., hydrochloric acid and acetic acid). The cationic dispersant may be a monoalkyltrimethylammonium salt (alkyl having 4 to 40 carbon atoms).

[0331] Specifically, the low molecular weight cationic dispersant is represented by the formula: R 1 p -N + R 2 q X - [In the formula, R 1 is C12 or higher (e.g., C 12 ~C 50 ) is a linear and / or branched aliphatic (saturated and / or unsaturated) group of R 2 is H or a C1-4 alkyl group, a benzyl group, or a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, especially 3) to 50) (CH3 and C2H5 are particularly preferred), X is a halogen atom (e.g., chlorine), or 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 may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0332] Low molecular weight cationic dispersants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride, and the like.

[0333] The polymeric cationic dispersant may be any of various polymers (e.g., polyquaternium-1 to 47) having cationic groups (e.g., ammonium groups, quaternary ammonium groups). Examples of polymeric cationic dispersants include cationic natural products (particularly cationic sugars) such as cationic starch, cationic cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propylhydroxyethylcellulose chloride), cationic guar gum, cationic xanthan gum, and chitosan; and polymers of cationic group-containing monomers such as aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternized dimethylammonium ethyl methacrylate, diallyldimethylammonium chloride, dimethylaminopropylamine, and quaternized vinylimidazole.

[0334] [Anionic dispersant] The dispersant may include an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may be free of an anionic dispersant.

[0335] The anionic dispersant may be a low molecular weight or a high molecular weight dispersant, and may have a molecular weight of 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may have a molecular weight of 100,000 or less, 25,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2500 or less, 750 or less, or 250 or less.

[0336] Examples of anionic dispersants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonic acid salts, N-acylamino acid dispersants, phosphate mono- or diester dispersants, and sulfosuccinates. An example of an anionic dispersant is a carboxylate (e.g., a fatty acid salt).

[0337] [Amphoteric dispersant] The dispersant may comprise an amphoteric dispersant, which may be an amphoteric surfactant.

[0338] The amphoteric dispersant may be a low molecular weight or a high molecular weight dispersant, and may have a molecular weight of 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may have a molecular weight of 100,000 or less, 25,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2500 or less, 750 or less, or 250 or less.

[0339] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amido betaines, and acetic acid betaine, and specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetic acid betaine, and fatty acid amidopropyl dimethylamino acetic acid betaine.

[0340] [Inorganic dispersant] The dispersant may include an inorganic dispersant.

[0341] The average primary particle size of the inorganic dispersant may be 5 nm or more, 30 nm or more, 100 nm or more, 1 μm or more, 10 μm or more, or 25 μm or more, and may be 100 μm or less, 50 μm or less, 10 μm or less, 1 μm or less, 500 nm or less, or 300 nm or less. The average primary particle size can be measured, for example, by observation with a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant may be hydrophilic particles.

[0342] Examples of inorganic dispersants include polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and hydroxyapatite; carbonates such as calcium carbonate and magnesium carbonate; silicates such as calcium metasilicate; sulfates such as calcium sulfate and barium sulfate; and hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

[0343] [Amount of dispersant] The amount of the dispersant may be, relative to 100 parts by weight of the hydrophobic compound (A), 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

[0344] [Liquid medium] The composition of the present disclosure may include a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The composition of the present disclosure may include at least water, and may be an aqueous dispersion.

[0345] Examples of organic solvents include esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate and butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically, naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxy group (e.g., alcohol, polyol such as glycol-based solvent, ether form of polyol (e.g., monoether form), etc.). These may be used alone or in combination of two or more.

[0346] [Amount of liquid medium] The amount of the liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the hydrophobic compound (A).

[0347] The amount of water may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the hydrophobic compound (A).

[0348] The amount of the organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the hydrophobic compound (A).

[0349] [Organic acid] The composition of the present disclosure may contain an organic acid. Known organic acids can be used. Preferred organic acids include carboxylic acids, sulfonic acids, sulfinic acids, etc., with carboxylic acids being particularly preferred. Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, and citric acid, with formic acid or acetic acid being particularly preferred. In the present disclosure, one organic acid may be used, or two or more organic acids may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0350] [Amount of organic acid] The amount of organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of hydrophobic compound (A). It may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of organic acid may be adjusted so that the pH of the composition is 3 to 10, for example, 5 to 9, particularly 6 to 8. The composition may be acidic (pH 7 or less, for example, 6 or less).

[0351] [Curing agent] The compositions of the present disclosure may include a curing agent (an active hydrogen-reactive compound or an active hydrogen-containing compound).

[0352] The curing agent (crosslinking agent) in the composition can effectively cure the hydrophobic compound (A). The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen-reactive groups of the hydrophobic compounds (A1) and (A2). Examples of active hydrogen-reactive compounds include isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of active hydrogen-containing compounds include hydroxy group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0353] The curing agent may contain an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. A polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound functions as a crosslinking agent. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (for example, a blocked polyisocyanate compound). A blocked isocyanate compound is a compound in which the isocyanate group of an isocyanate compound is masked with a blocking agent to inhibit reaction.

[0354] Examples of aliphatic polyisocyanates are trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate, Aliphatic diisocyanates such as cyanatomethyl caproate, and aliphatic triisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane. These may be used alone or in combination of two or more.

[0355] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used alone or in combination of two or more.

[0356] Examples of araliphatic polyisocyanates include araliphatic diisocyanates and araliphatic triisocyanates. Specific examples of araliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used alone or in combination of two or more.

[0357] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used alone or in combination of two or more.

[0358] Examples of the polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, uretimines, isocyanurates, and iminooxadiazinediones. These may be used alone or in combination of two or more.

[0359] These polyisocyanates can be used alone or in combination of two or more. As the polyisocyanate compound, it is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of a polyisocyanate compound is blocked with a blocking agent.The use of a blocked polyisocyanate compound is preferable because it is relatively stable even in solution.

[0360] The blocking agent blocks free isocyanate groups. When the blocked polyisocyanate compound is heated to, for example, 100°C or higher, e.g., 130°C or higher, the isocyanate groups are regenerated and can easily react with hydroxy groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. The polyisocyanate compounds can be used alone or in combination.

[0361] The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. The chloromethyl group-containing compound is a compound having a chloromethyl group. Examples of the chloromethyl group-containing compound include chloromethyl polystyrene. The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound include (poly)acrylic acid and (poly)methacrylic acid.

[0362] Specific examples of the ketone group-containing compound include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of the hydrazide compound include hydrazine, carbohydrazide, and adipic acid hydrazide. Specific examples of the melamine compound include melamine resins and methyl etherified melamine resins.

[0363] [Amount of hardener] The amount of the curing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the hydrophobic compound (A), and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0364] [Other ingredients] The composition may contain other components in addition to the above components. Examples of the other components include polysaccharides, paper strength agents, flocculants, retention aids, coagulants, binder resins, antislip agents, sizing agents, paper strength agents, fillers, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorizers, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above ingredients, other ingredients may include other water and / or oil repellents, dispersants, texture adjusters, softeners, flame retardants, paint fixatives, wrinkle inhibitors, drying speed adjusters, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity adjusters, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage inhibitors, anti-wrinkle agents after washing, shape retention agents, drape retention agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, dye transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain release agents, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Ciba Specialty Chemicals' Tinopal CBS-X), dye fixatives, and anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine. The following may be blended: stain removers, enzymes such as cellulase, amylase, protease, lipase, and keratinase as fiber surface modifiers; foam inhibitors; and agents capable of imparting silk texture and functionality such as moisture absorption and release. These include silk protein powder, surface-modified products, or emulsified dispersions thereof (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemicals), hydrolyzed silk liquid (Jomo), Silkgen G Soluble S (Ichimaru Falcos)). Stain inhibitors (e.g., nonionic polymeric compounds consisting of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by GOO Chemical Industry Co., Ltd., SRC-1 manufactured by Clariant Japan, etc.) can also be blended. These may be used alone or in combination of two or more.

[0365] [Amount of other ingredients] The amount of each or the total amount of the other components may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the hydrophobic compound (A), and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0366] <Papermaking additive kit> Although the composition containing the hydrophobic compound (A) has been described above, the hydrophobic compound (A1) and the hydrophobic compound (A2) may be used as separate treatment agents (additive kits) to treat the substrate. The papermaking additive kit according to the present disclosure includes a first agent and a second agent, the first agent contains a hydrophobic compound (A1), the second agent contains a hydrophobic compound (A2) which is a compound different from the hydrophobic compound (A1), The first agent and the second agent may be added and mixed separately to the pulp base material. The first agent may be added and mixed to the pulp base material first, and then the second agent may be added and mixed, or the addition order may be reversed.

[0367] The components in the first and second agents may include the components in the composition described above, and the aspects in the description of the composition above are also applicable to the first and second agents.

[0368] <Pulp composition> The pulp composition of the present disclosure comprises pulp and a hydrophobic compound (A). The pulp composition of the present disclosure is obtained by treating pulp with the above-described composition containing the hydrophobic compound (A) as a treatment agent.

[0369] 〔pulp〕 The pulp composition contains pulp, and the pulp has been treated with a composition (treatment agent) containing the hydrophobic compound (A) described above as a pulp base material. The pulp base material may be in the form of pulp alone, pulp slurry, pulp product, etc. Examples of pulp base materials include pulp such as bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp or thermomechanical pulp, pulp slurries containing the above pulp, and pulp products such as paper, paper containers, and molded paper products made from recycled paper pulp such as recycled newspaper, recycled magazine paper, recycled corrugated cardboard, and deinked recycled paper. Specific examples of pulp products include food packaging materials, food containers, gypsum board base paper, coated base paper, medium-quality paper, general liners and corrugating media, neutral white roll paper, neutral liners, rust-proof liners and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc. Suitable examples of pulp products include food packaging materials and food containers, and particularly pulp molded products for food contact applications.

[0370] [Amount of pulp] The amount of pulp in the pulp composition may be 0.1% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, 75% by weight or more, or 90% by weight or more, and may be 99% by weight or less, 75% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 4% by weight or less, or 3% by weight or less. Typically, when the pulp composition is prepared by internal addition, the amount of pulp in the pulp composition is 30% by weight or less, and when the pulp composition is prepared by external addition, the amount of pulp in the pulp composition may be 75% by weight or more.

[0371] [Liquid medium] The pulp composition may include a liquid medium, which may be water, an organic solvent, or a mixture of water and an organic solvent, typically an aqueous medium, particularly water, and may include a liquid medium derived from a treatment agent.

[0372] [Amount of liquid medium] The amount of the liquid medium in the pulp composition may be 0.1% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, 75% by weight or more, 90% by weight or more, or 95% by weight or more, and may be 99% by weight or less, 75% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 4% by weight or less, or 3% by weight or less. Typically, when the pulp composition is prepared by internal addition, the amount of the liquid medium in the pulp composition is 50% by weight or more, particularly 90% by weight or more, and when the pulp composition is prepared by external addition, the amount of the liquid medium in the pulp composition may be 30% by weight or less, particularly 10% by weight or less.

[0373] [Hydrophobic compound (A)] The pulp composition may comprise a hydrophobic compound (A) in the treatment agent.

[0374] [Amount of hydrophobic compound (A)] The amount of the treatment agent added to the pulp base material may be adjusted so that the desired amount of hydrophobic compound (A) is obtained. The amount of hydrophobic compound (A) may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, preferably 5.0% by weight or less, more preferably 3.0% by weight or less, based on the pulp.

[0375] In the external addition treatment, the amount of the hydrophobic compound (A) contained in the coating layer is 0.01 g / m 2 More than 0.03g / m 2 More than 0.05g / m 2 More than 0.1g / m 2 More than 0.3g / m 2More than 0.5g / m 2 or more, or 1.0 g / m 2 It is more than 5.0g / m 2 Below 4.0g / m 2 Below 3.0g / m 2 Below 2.0g / m 2 Below 1.0g / m 2 Below 0.5g / m 2 Below 0.3g / m 2 or less, or 0.1 g / m 2 It may be the following:

[0376] [Paper strength agent] The pulp composition may include a strength agent. Examples of strength agents include: Polyacrylamide-based paper strength agents such as cationic polyacrylamide, anionic polyacrylamide, and amphoteric polyacrylamide; polysaccharide-based paper strength agents such as starch, enzyme-modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (e.g., hydroxyethylated starch), aldehyde starch, cationized starch, starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, chitin nanofiber, cellulose nanofiber, and pullulan, and modified polysaccharides thereof (e.g., modified polysaccharides into which hydroxyl groups or cationic groups have been introduced); Polyamide-based paper strength agents such as polyamide resins, polyamine resins, polyamide-polyamine resins, polyamide-epichlorohydrin resins, polyamide-polyamine-epichlorohydrin resins, polyamide-polyurea-formaldehyde resins, and epoxidized polyamide resins; Urea / melamine-based paper strength agents such as urea resin, melamine resin, urea-formaldehyde resin, and melamine-formaldehyde resin; polyvinyl alcohol-based paper strength agents such as polyvinyl alcohol, fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, and terminal alkyl-modified polyvinyl alcohol; Examples of the paper strength agent include styrene-butadiene copolymer, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyacrylic acid ester, fatty acid diamide, polyethyleneimine resin, ketone aldehyde resin, etc. The paper strength agent in the present disclosure is preferably a polyacrylamide-based paper strength agent, a polysaccharide-based paper strength agent, or a polyamide-based paper strength agent.

[0377] [Amount of paper strength agent] The amount of the paper strength agent may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, and is preferably 5.0% by weight or less, based on the pulp.

[0378] [Sizing agent] The pulp composition may contain a sizing agent. Examples of the sizing agent include cationic sizing agents, anionic sizing agents, neutral sizing agents, and amphoteric sizing agents, such as rosin-based sizing agents (e.g., acidic rosin-based sizing agents and neutral rosin-based sizing agents), alkyl ketene dimers, and alkenyl succinic anhydrides.

[0379] [Amount of sizing agent] The amount of sizing agent may be 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, based on the pulp.

[0380] [Other additives] In addition to the above, the pulp composition may contain additives used in the production of pulp products, such as fixing agents (aluminum sulfate, etc.), organic acids (formic acid, acetic acid, etc.), flocculants, retention aids, dyes, fluorescent dyes, slime control agents, defoamers, etc. The pulp composition contains components of a composition (treatment agent) containing the hydrophobic compound (A), but each of the components that can be contained in the composition containing the hydrophobic compound (A) described above may also be added to the pulp composition as an additive.

[0381] The amount of each of the above additives may be 0.1% by weight or more, 1% by weight or more, 3% by weight or more, or 5% by weight or more, and may be 30% by weight or less, 20% by weight or less, 10% by weight or less, or 5% by weight or less, based on the weight of the pulp.

[0382] <Product manufacturing method> The method for producing a product according to the present disclosure may include a step of treating a substrate with a composition containing the hydrophobic compound (A) according to the present disclosure as a treatment agent (particularly a repellent agent).

[0383] The substrate to be treated with the treatment agent of the present disclosure is not limited, but is preferably a fibrous substrate (fiber substrate), and may be a textile substrate or a pulp substrate, particularly a pulp substrate.

[0384] Examples of fiber substrates include natural fibers of animal or plant origin such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber, or mixtures of these fibers. Fiber products include woven fabrics, knitted fabrics, and nonwoven fabrics, as well as cloth in the form of clothing (for example, water-repellent clothing such as raincoats) and carpets, but the treatment may also be applied to fibers, yarns, and intermediate fiber products (for example, slivers or rovings) in a state prior to being made into cloth.

[0385] Substrates that can be treated with the treatment agent of the present disclosure are not limited to fibrous substrates, but also include stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster.

[0386] When the substrate is glass, the glass product produced may be an optical component. A layer (or film), such as a hard coat layer or an anti-reflection layer, may be formed on the surface (outermost layer) of the glass substrate. The anti-reflection layer may be either a single-layer or a multi-layer. Examples of inorganic substances that can be used for the anti-reflection layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, YO3, SnO2, MgF2, and WO3. These inorganic substances may be used alone or in combination (e.g., as a mixture) of two or more of these. When a multi-layer anti-reflection layer is used, it is preferable to use SiO2 and / or SiO for the outermost layer. When the article to be produced is an optical glass component for a touch panel, a transparent electrode, such as a thin film using indium tin oxide (ITO) or indium zinc oxide, may be formed on a portion of the surface of the substrate (glass). In addition, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomizing film layer, a hard coating film layer, a polarizing film, a phase difference film, and a liquid crystal display module, etc., depending on its specific specifications.

[0387] [Method for manufacturing pulp products] The method for producing a product according to the present disclosure is preferably a method for producing a pulp product, and may include a step of treating a pulp base material with a repellent. The pulp base material is treated with the repellent to obtain a pulp composition. The obtained pulp composition can be subjected to treatment steps such as drying, heating, and molding, as necessary, to obtain a pulp product.

[0388] The types and compositions of the pulp substrate and repellent agent are the same as those described above for the "pulp composition." The composition of the present disclosure can be applied to the substrate as a treatment agent (particularly a repellent agent) by a conventionally known method. The treatment method may involve dispersing and diluting the repellent agent of the present disclosure in an organic solvent or water, as needed, and applying it to the interior and / or surface of the pulp substrate by a known method such as dip coating, spray coating, or foam coating, followed by drying. After drying, a pulp product is obtained with the solid components of the repellent agent attached. If necessary, the repellent agent may be applied together with an appropriate crosslinking agent and cured. The concentration of the repellent agent in the treatment agent to be contacted with the pulp substrate may be varied depending on the application, but may be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0389] The repellent agent can be applied to the pulp substrate by any of the known methods for treating a pulp substrate with a liquid. The pulp substrate may be immersed in the repellent agent, the pulp substrate and the repellent agent may be mixed, or the solution may be applied or sprayed onto the pulp substrate. The treated pulp substrate is preferably dried and cured by heating to develop liquid repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes.

[0390] The pulp base material can be treated by an internal treatment method in which a repellent is added to pulp (e.g., pulp slurry) before papermaking, or an external treatment method in which a repellent is applied to pulp (e.g., pulp product) after papermaking. Examples of internal treatment methods include mixing and immersion, and may include a step of adding a repellent to pulp slurry and stirring and mixing. Examples of external treatment methods include spraying and application, and specific examples include pond-type two-roll size presses, gate-roll type, and rod-metering size presses. The treatment may be an external treatment or an internal treatment. For example, when the pulp base material is paper, the repellent may be coated on the paper, or the solution may be attached or sprayed on the paper, or the repellent may be mixed with the pulp slurry before papermaking.

[0391] The treatment method may be an internal addition treatment in which a repellent is added to the pulp slurry before papermaking. The internal addition treatment may include, but is not limited to, one or more of the following steps: adding the repellent to the pulp slurry and stirring and mixing it; suction-dehydrating the pulp composition prepared in the above step through a mesh of a predetermined shape to deposit the pulp composition and form a molded pulp product intermediate; and molding and drying the molded pulp product intermediate in a heated mold to obtain a molded pulp product. The treated paper may be briefly dried at room temperature or at an elevated temperature, and then optionally subjected to a heat treatment depending on the paper's properties. The heat treatment temperature may be 150°C or higher, 180°C or higher, or 210°C or higher, or 300°C or lower, 250°C or lower, or 200°C or lower, and particularly preferably 80°C to 180°C. Heat treatment within this temperature range can exhibit excellent oil resistance, water resistance, etc. The internally treated pulp base material may be treated with an external additive to be treated with a repellent, and additional wax and additional paper strength agent may be attached to the surface.

[0392] The treatment method may be an external addition treatment in which a repellent agent is applied to the pulp base material after papermaking. Size presses for external addition treatment can also be classified as follows based on the application method. One application method is the so-called pond-type two-roll size press, in which a coating liquid (size liquid) is supplied to the nip formed by passing paper between two rubber rolls, creating a coating liquid pool called a pond, and the paper is passed through this coating liquid pool to apply the sizing liquid to both sides of the paper. Other application methods include the gate roll type, in which the sizing liquid is applied using a surface transfer method, and the rod metering size press. In the pond-type two-roll size press, the sizing liquid easily penetrates into the paper, while in the surface transfer type, the sizing liquid components tend to remain on the paper surface. In the surface transfer type, the coating layer tends to remain on the paper surface compared to the pond-type two-roll size press, and the coating layer formed on the surface is larger than in the pond-type two-roll size press. In the present disclosure, performance can be imparted to paper even when the former pond-type two-roll size press is used. Papers treated in this way can exhibit excellent oil and / or water resistance etc., after simple drying at room temperature or at elevated temperatures, optionally followed by a heat treatment which, depending on the properties of the paper, can range from 300°C, e.g. up to 200°C, in particular from 80°C to 180°C.

[0393] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims. [Example]

[0394] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0395] <Test Method> The test procedure is as follows:

[0396] [Preparation of hydrophobic compound (A)] As the hydrophobic compound (A), a mixture obtained by melt-mixing the hydrophobic compound (A1) and the hydrophobic compound (A2) at a temperature equal to or higher than the melting point and allowing the mixture to cool at room temperature was used.

[0397] [Mold creation] A mold was formed using an automatic molding machine. A mesh-like body was placed on a metal pulp mold mold with numerous suction holes at the bottom, and a metal tank was placed on top, with the pulp slurry being placed in the upper metal tank. A vacuum pump was used to suck and dehydrate the pulp-containing aqueous composition through the pulp mold mold and mesh-like body from the side opposite the mesh-like body of the pulp mold mold at 0.1 to 1 MPa, depositing the solids (pulp, etc.) contained in the pulp-containing aqueous composition on the mesh-like body to obtain a pulp-molded intermediate. The obtained pulp-molded intermediate was then dried from above and below in a male-female metal mold heated to 60 to 200°C under a pressure of 0.1 to 1 MPa. This produced a pulp-molded product molded into the shape of a container.

[0398] [Practical oil resistance test (25℃)] The mold was pretreated by storing it at 23°C and 50% humidity for 12 hours. 100 ml of corn oil at 25°C was poured into the mold, and after leaving it at room temperature for 45 minutes, the corn oil was removed from the mold and the degree of oil staining on the mold was evaluated. The following evaluation values ​​were set depending on the degree of staining. 5: No stains inside 4: There is a stain on the inside. No stain on the back. 3: Stain on the inside. Slight bleeding on the back. 2: Stain on the inside, with less than 50% of the area bleeding to the back. 1: Stain on the inside. Stain on the backside is 50% or more but less than 100% of the area. 0: Seeped through to the entire back side.

[0399] [Practical oil resistance test (65℃)] The mold was pretreated by storing it at 23°C and 50% humidity for 12 hours. 100 ml of corn oil at 65°C was poured into the mold, and after leaving it at room temperature for 45 minutes, the corn oil was removed from the mold and the degree of oil staining on the mold was evaluated. The following evaluation values ​​were set depending on the degree of staining. 5: No stains inside 4: There is a stain on the inside. No stain on the back. 3: Stain on the inside. Slight bleeding on the back. 2: Stain on the inside, with less than 50% of the area bleeding to the back. 1: Stain on the inside. Stain on the backside is 50% or more but less than 100% of the area. 0: Seeped through to the entire back side.

[0400] [Practical water resistance test (100℃)] The mold was pretreated by storing it at 23°C and 50% humidity for 12 hours. 100 ml of 100°C water was poured into the mold, and after leaving it at room temperature for 30 minutes, the water was removed from the mold and the degree of staining on the mold was evaluated. The following evaluation values ​​were set depending on the degree of staining. 5: No stains inside 4: There is a stain on the inside. No stain on the back. 3: Stain on the inside. Slight bleeding on the back. 2: Stain on the inside, with less than 50% of the area bleeding to the back. 1: Stain on the inside. Stain on the backside is 50% or more but less than 100% of the area. 0: Seeped through to the entire back side.

[0401] [Hexadecane contact angle (HD contact angle)] A solution (dispersion) of the hydrophobic compound (A1) or the hydrophobic compound (A2) with a solid content concentration of 1.0% was prepared, and the prepared solution was subjected to a sonication treatment at 40° C. for 60 minutes. This solution (dispersion) was spin-coated onto a silicon wafer at 2500 rpm for 25 seconds to obtain a spin-coated film. This was then heated at 140°C for 1 minute to produce a compound-treated silicon wafer. Chloroform was used as the solvent or dispersion medium. 2 μL of HD (hexadecane) was dropped onto the compound-treated silicon wafer, and the static contact angle measured 1 second after the drop was applied was used as the HD contact angle for each hydrophobic compound.

[0402] [Water contact angle] A solution (dispersion) of the hydrophobic compound (A1) or the hydrophobic compound (A2) with a solid content concentration of 1.0% was prepared. The prepared solution was subjected to a sonication treatment at 40° C. for 60 minutes. This solution (dispersion) was spin-coated onto a silicon wafer at 2500 rpm for 25 seconds to obtain a spin-coated film. This was then heated at 140°C for 1 minute to produce a compound-treated silicon wafer. Chloroform was used as the solvent or dispersion medium. 2 μL of water was dropped onto the compound-treated silicon wafer, and the static contact angle measured 1 second after the drop was applied was used as the water contact angle for each hydrophobic compound.

[0403] [Low temperature shift of the endothermic peak of hydrophobic compound (A1)] The temperature of each of the hydrophobic compound (A) and the hydrophobic compound (A1) was raised from -20°C to 180°C at 10°C / min under a nitrogen atmosphere, and the low-temperature shift (°C) of the endothermic peak on the highest temperature side in the measurement range of the hydrophobic compound (A1) was determined when the hydrophobic compound (A1) was used as the hydrophobic compound (A).

[0404] [Method of measuring melting point] The melting point was calculated by differential scanning calorimetry (DSC). For DSC measurements, the sample was cooled to -20°C at a rate of 10°C / min under a nitrogen atmosphere (nitrogen flow rate 50 mL / min), then heated to 180°C at a rate of 10°C / min, and then cooled to -20°C at a rate of 10°C / min. The endothermic peak observed during the second heating step to 180°C at a rate of 10°C / min was then measured.

[0405] [Calculation method of solubility parameter (SP value) by Fedors method] The solubility parameter (SP value) according to the Fedors method was calculated at 25°C using the Fedors method (Polym. Eng. Sci., 14 (2), 147-154 (1974)) by the Fedors group contribution method (addition of atomic groups).

[0406] [Penetration test of compounds] The hydrophobic compound (A) was placed in an iron container having a width of 30 mm, a length of 30 mm, and a depth of 20 mm, and the container was heated at 180°C for 30 minutes to melt the compound. The container was then allowed to cool to 25°C to prepare a test piece, which was then measured in accordance with JIS K 2235 6.4.

[0407] [Residue penetration test] The aqueous dispersion of hydrophobic compound (A) was heated at 100°C for 2 days to remove the liquid medium, thereby obtaining a residue. The resulting residue was placed in an iron container measuring 30 mm in width, 30 mm in length, and 20 mm in depth, and heated at 180°C for 30 minutes to melt it, and then allowed to cool to 25°C to prepare a test piece, which was then measured in accordance with JIS K 2235 6.4.

[0408] [Method for measuring Shore A hardness of compounds] Hydrophobic compound (A) and hydrophobic compound (A1) were placed in an iron container measuring 30 mm wide, 30 mm long, and 20 mm deep. They were heated to 180°C for 30 minutes until melted, and then allowed to cool to 25°C to prepare test specimens. Using a Kobunshi Keiki Automatic Rubber Hardness Tester P2-A, the Shore A hardness after 1 second [1s], the Shore A hardness after 3 seconds [3s], and the peak Shore A hardness [PEAK] were calculated. The difference in Shore A hardness ([Shore A hardness of hydrophobic compound (A1)] - [Shore A hardness of hydrophobic compound (A)]) was also calculated from the results.

[0409] [Method for measuring Shore A hardness of residue] An aqueous dispersion of hydrophobic compound (A) was heated at 100°C for two days to remove the liquid medium, yielding a residue. The resulting residue was placed in an iron container 30 mm wide, 30 mm long, and 20 mm deep. It was heated to 180°C for 30 minutes to melt, and then allowed to cool to 25°C to prepare a test specimen. Using a Kobunshi Keiki Automatic Rubber Hardness Tester P2-A, the Shore A hardness after 1 second [1s], the Shore A hardness after 3 seconds [3s], and the peak Shore A hardness [PEAK] were calculated.

[0410] Example 1 2 g of N,N'-ethylenebisoctadecaneamide (biobased content: 97%, melting point: 143°C, hexadecane contact angle: 36.1°, Fedors SP value: 9.6) as hydrophobic compound (A1), 1.4 g of corn oil (Japanese cornstarch, liquid at 25°C) as hydrophobic compound (A2), 0.16 g of polyethylene glycol trimethyl nonyl ether (HLB 13.1), and 0.04 g of polyethylene glycol trimethyl nonyl ether (HLB 8.1) were mixed and heated at 180°C for 30 minutes to obtain a melted and mixed solid. 10 g of water was added to this solid, and the mixture was pulverized with a spatula. 6.6 g of water was then added, and the mixture was homogenized at 10,000 rpm for 20 minutes to obtain an aqueous dispersion of a composition containing hydrophobic compound (A) (volume proportion of particles of 100 μm or larger: 21%, volume median diameter: 53.3 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 3 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to a practical oil resistance test (25°C), a practical oil resistance test (65°C), and a practical water resistance test (100°C), and was evaluated as 4 points in all cases.

[0411] The Shore A hardness-1 was measured using a mixture obtained by mixing 100 parts by mass of N,N'-ethylenebisoctadecaneamide (biobased content: 97%, melting point: 143°C, hexadecane contact angle: 36.1°, Fedors SP value: 9.6) as the hydrophobic compound (A1) with 70 parts by mass of corn oil (Japanese cornstarch, liquid at 25°C) as the hydrophobic compound (A2).

[0412] <Example 2> An aqueous dispersion composition of a composition containing hydrophobic compound (A) was obtained in the same manner as in Example 1, except that the amount of corn oil used as hydrophobic compound (A2) was changed to 0.70 g (volume proportion of particles of 100 μm or more: 19%, volume median diameter: 47.9 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 3 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to a practical oil resistance test (25°C), a practical oil resistance test (65°C), and a practical water resistance test (100°C), and was evaluated as 4 points in all cases.

[0413] The Shore A hardness-1 was measured using a mixture obtained by mixing 100 parts by mass of N,N'-ethylenebisoctadecaneamide (biobased content: 97%, melting point: 143°C, hexadecane contact angle: 36.1°, Fedors SP value: 9.6) as the hydrophobic compound (A1) with 35 parts by mass of corn oil (Japanese cornstarch, liquid at 25°C) as the hydrophobic compound (A2).

[0414] Example 3 An aqueous dispersion composition of a composition containing hydrophobic compound (A) was obtained in the same manner as in Example 1, except that corn oil was replaced with triolein (liquid at 25°C, Fedors SP value: 8.93) as the hydrophobic compound (A2) (volume proportion of particles of 100 μm or more: 23%, volume median diameter: 47.9 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 3 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to a practical oil resistance test (25°C), a practical oil resistance test (65°C), and a practical water resistance test (100°C), and was evaluated as 4 points in all cases.

[0415] Example 4 An aqueous dispersion composition of a composition containing hydrophobic compound (A) was obtained in the same manner as in Example 1, except that corn oil was replaced with triolein (liquid at 25°C, Fedors SP value: 8.93) as the hydrophobic compound (A2) and the amount used was changed to 0.70 g (volume proportion of particles of 100 μm or more: 24%, volume median diameter: 49.3 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 3 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to a practical oil resistance test (25°C), a practical oil resistance test (65°C), and a practical water resistance test (100°C), and was evaluated as 4 points in all cases.

[0416] <Example 5> An aqueous dispersion composition of a composition containing hydrophobic compound (A) was obtained in the same manner as in Example 1, except that corn oil was replaced with trilinolein (liquid at 25°C, Fedors SP value: 8.951) as the hydrophobic compound (A2) (volume proportion of particles of 100 μm or more: 22%, volume median diameter: 52.3 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 3 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to a practical oil resistance test (25°C), a practical oil resistance test (65°C), and a practical water resistance test (100°C), and was evaluated as 4 points in all cases.

[0417] Example 6 A water dispersion composition of a composition containing hydrophobic compound (A) was obtained in the same manner as in Example 1, except that corn oil was replaced with trilinolein (liquid at 25°C, Fedors SP value: 8.951) as the hydrophobic compound (A2) and the amount used was changed to 0.70 g (volume proportion of particles of 100 μm or more: 19%, volume median diameter: 47.9 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 3 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to a practical oil resistance test (25°C), a practical oil resistance test (65°C), and a practical water resistance test (100°C), and was evaluated as 4 points in all cases.

[0418] Example 7 2 g of N,N'-ethylenebisoleic acid amide (biobased content: 97%, melting point: 116°C, hexadecane contact angle: 42.7°) as the hydrophobic compound (A1), 1.4 g of corn oil (Japanese cornstarch, liquid at 25°C) as the hydrophobic compound (A2), 0.16 g of polyethylene glycol trimethylnonyl ether (HLB 13.1) and 0.04 g of polyethylene glycol trimethylnonyl ether (HLB 8.1) were mixed together and heated at 180°C for 30 minutes to obtain a melted and mixed solid. 10 g of water was added to this solid, and the mixture was pulverized with a spatula. 6.6 g of water was then added, and the mixture was homogenized at 10,000 rpm for 20 minutes to obtain an aqueous dispersion of a composition containing hydrophobic compound (A) (volume proportion of particles of 100 μm or larger: 18%, volume median diameter: 47.3 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 7 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to practical oil resistance tests (25°C) and (65°C), and was evaluated as 4 points in both tests.

[0419] Example 8 An aqueous dispersion composition of a composition containing hydrophobic compound (A) was obtained in the same manner as in Example 7, except that the amount of corn oil used as hydrophobic compound (A2) was changed to 0.70 g (volume proportion of particles of 100 μm or more: 19%, volume median diameter: 46.2 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 7 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to a practical oil resistance test (25°C), a practical oil resistance test (65°C), and a practical water resistance test, and was evaluated as 4 points in all cases.

[0420] Example 9 An aqueous dispersion composition of a composition containing hydrophobic compound (A) was obtained in the same manner as in Example 1, except that the amount of corn oil used as hydrophobic compound (A2) was changed to 2.2 g (volume ratio of particles of 100 μm or more: 17%, volume median diameter: 45.6 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 3 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to a practical oil resistance test (25°C), a practical oil resistance test (65°C), and a practical water resistance test, and was evaluated as 4 points in all cases.

[0421] Example 10 2 g of N,N'-ethylenebisoctadecanamide (biobased content: 97%, melting point: 143°C, hexadecane contact angle: 36.1°) as the hydrophobic compound (A1), 1.4 g of glyceryl tridecanoate (liquid at 25°C, Fedors SP value: 9.138) as the hydrophobic compound (A2), 0.16 g of polyethylene glycol trimethyl nonyl ether (HLB 13.1), and 0.04 g of polyethylene glycol trimethyl nonyl ether (HLB 8.1) were mixed and heated at 180°C for 30 minutes to obtain a melted and mixed solid. 10 g of water was added to this solid, and the mixture was pulverized with a spatula. 6.6 g of water was then added, and the mixture was homogenized at 7500 rpm for 20 minutes using a homogenizer to obtain an aqueous dispersion of a composition containing hydrophobic compound (A) (volume proportion of particles of 100 μm or larger: 23%, volume median diameter: 40.35 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 5 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to a practical oil resistance test (65°C) and scored 4 points.

[0422] Example 11 2 g of N,N'-ethylenebisoctadecanamide (biobased content: 97%, melting point: 143°C, hexadecane contact angle: 36.1°) as the hydrophobic compound (A1), 1.4 g of glyceryl trioctanoate (liquid at 25°C, Fedors SP value: 9.251) as the hydrophobic compound (A2), 0.16 g of polyethylene glycol trimethyl nonyl ether (HLB 13.1), and 0.04 g of polyethylene glycol trimethyl nonyl ether (HLB 8.1) were mixed and heated at 180°C for 30 minutes to obtain a melted and mixed solid. 10 g of water was added to this solid, and the mixture was pulverized with a spatula. 6.6 g of water was then added, and the mixture was homogenized at 7500 rpm for 20 minutes using a homogenizer to obtain an aqueous dispersion of a composition containing hydrophobic compound (A) (volume proportion of particles of 100 μm or larger: 26%, volume median diameter: 57.06 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 5 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to a practical oil resistance test (65°C) and scored 4 points.

[0423] Example 12 2 g of N,N'-ethylenebisoctadecaneamide (biobased content: 97%, melting point: 143°C, hexadecane contact angle: 36.1°) as the hydrophobic compound (A1), 1.4 g of tributyl trimellitate (liquid at 25°C, Fedors SP value: 10.185) as the hydrophobic compound (A2), 0.16 g of polyethylene glycol trimethyl nonyl ether (HLB 13.1), and 0.04 g of polyethylene glycol trimethyl nonyl ether (HLB 8.1) were mixed and heated at 180°C for 30 minutes to obtain a melted and mixed solid. 10 g of water was added to this solid, and the mixture was pulverized with a spatula. 6.6 g of water was then added, and the mixture was homogenized at 7500 rpm for 20 minutes using a homogenizer to obtain an aqueous dispersion of a composition containing hydrophobic compound (A) (volume proportion of particles of 100 μm or larger: 17%, volume median diameter: 44.58 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 5 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to a practical oil resistance test (25°C), a practical oil resistance test (65°C), and a practical water resistance test (100°C), and was evaluated as 4 points in all cases.

[0424] Example 13 2 g of N,N'-ethylenebisoctadecaneamide (biobased content: 97%, melting point: 143°C, hexadecane contact angle: 36.1°) as the hydrophobic compound (A1), 0.7 g of sucrose oleate (liquid at 25°C, HLB: 1), 0.16 g of polyethylene glycol trimethylnonyl ether (HLB 13.1), and 0.04 g of polyethylene glycol trimethylnonyl ether (HLB 8.1) as the hydrophobic compound (A2) were mixed and heated at 180°C for 30 minutes to obtain a melted and mixed solid. 10 g of water was added to this solid, and the mixture was pulverized with a spatula. 6.6 g of water was then added, and the mixture was homogenized at 7500 rpm for 20 minutes using a homogenizer to obtain an aqueous dispersion of a composition containing hydrophobic compound (A) (volume proportion of particles of 100 μm or larger: 17%, volume median diameter: 44.58 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 5 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to practical oil resistance tests (25°C) and (65°C), and was evaluated as 4 points in both tests.

[0425] Example 14 2 g of N,N'-ethylenebisoctadecaneamide (biobased content: 97%, melting point: 143°C, hexadecane contact angle: 36.1°) as the hydrophobic compound (A1), 0.7 g of sucrose erucate (liquid at 40°C, HLB: 2), 0.16 g of polyethylene glycol trimethyl nonyl ether (HLB 13.1), and 0.04 g of polyethylene glycol trimethyl nonyl ether (HLB 8.1) as the hydrophobic compound (A2) were mixed and heated at 180°C for 30 minutes to obtain a melted and mixed solid. 10 g of water was added to this solid, and the mixture was pulverized with a spatula. 6.6 g of water was then added, and the mixture was homogenized at 7500 rpm for 20 minutes using a homogenizer to obtain an aqueous dispersion of a composition containing hydrophobic compound (A) (volume proportion of particles of 100 μm or larger: 17%, volume median diameter: 44.58 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 5 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to practical oil resistance tests (25°C) and (65°C), and was evaluated as 4 points in both tests.

[0426] Example 15 2 g of N,N'-ethylenebisoctadecaneamide (biobased content: 97%, melting point: 143°C, hexadecane contact angle: 36.1°) as the hydrophobic compound (A1), 0.7 g of decaglycerin decaoleate (degree of polymerization: 10, hydroxy substitution rate: 10 / 12*100 [83.3%], state at 25°C: liquid, HLB: 3.3) as the hydrophobic compound (A2), 0.16 g of polyethylene glycol trimethylnonyl ether (HLB 13.1), and 0.04 g of polyethylene glycol trimethylnonyl ether (HLB 8.1) were mixed and heated at 180°C for 30 minutes to obtain a melt-mixed solid. 10 g of water was added to this solid, and the mixture was pulverized with a spatula. 6.6 g of water was then added, and the mixture was homogenized at 7500 rpm for 20 minutes using a homogenizer to obtain an aqueous dispersion of a composition containing hydrophobic compound (A) (volume proportion of particles of 100 μm or larger: 17%, volume median diameter: 44.58 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 5 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to practical oil resistance tests (25°C) and (65°C), and was evaluated as 4 points in both tests.

[0427] Example 16 2 g of N,N'-ethylenebisoctadecaneamide (biobased content: 97%, melting point: 143°C, hexadecane contact angle: 36.1°) as the hydrophobic compound (A1), 0.7 g of hexaglycerin pentaoleate (degree of polymerization: 6, hydroxy substitution rate: 5 / 8*100 [62.5%], state at 25°C: liquid, HLB: 4.7) as the hydrophobic compound (A2), 0.16 g of polyethylene glycol trimethylnonyl ether (HLB 13.1), and 0.04 g of polyethylene glycol trimethylnonyl ether (HLB 8.1) were mixed and heated at 180°C for 30 minutes to obtain a melted and mixed solid. 10 g of water was added to this solid, and the mixture was pulverized with a spatula. 6.6 g of water was then added, and the mixture was homogenized at 7500 rpm for 20 minutes using a homogenizer to obtain an aqueous dispersion of a composition containing hydrophobic compound (A) (volume proportion of particles of 100 μm or larger: 17%, volume median diameter: 44.58 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 5 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to practical oil resistance tests (25°C) and (65°C), and was evaluated as 4 points in both tests.

[0428] Example 17 2 g of N,N'-ethylenebisoctadecaneamide (biobased content: 97%, melting point: 143°C, hexadecane contact angle: 36.1°) as the hydrophobic compound (A1), 0.7 g of decaglycerol octaerucate (degree of polymerization: 10, hydroxy substitution rate: 8 / 12*100 [66.7%], liquid at 25°C, HLB: 3.7) as the hydrophobic compound (A2), 0.16 g of polyethylene glycol trimethylnonyl ether (HLB 13.1), and 0.04 g of polyethylene glycol trimethylnonyl ether (HLB 8.1) were mixed and heated at 180°C for 30 minutes to obtain a melt-mixed solid. 10 g of water was added to this solid, and the mixture was pulverized with a spatula. 6.6 g of water was then added, and the mixture was homogenized at 7500 rpm for 20 minutes using a homogenizer to obtain an aqueous dispersion of a composition containing hydrophobic compound (A) (volume proportion of particles of 100 μm or larger: 17%, volume median diameter: 44.58 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 5 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to practical oil resistance tests (25°C) and (65°C), and was evaluated as 4 points in both tests.

[0429] Example 18 2 g of N,N'-ethylenebisoctadecaneamide (biobased content: 97%, melting point: 143°C, hexadecane contact angle: 36.1°) as the hydrophobic compound (A1), 1.4 g of diisononyl adipate (liquid at 25°C, Fedors SP value: 9.00) as the hydrophobic compound (A2), 0.16 g of polyethylene glycol trimethylnonyl ether (HLB 13.1), and 0.04 g of polyethylene glycol trimethylnonyl ether (HLB 8.1) were mixed and heated at 180°C for 30 minutes to obtain a melted and mixed solid. 10 g of water was added to this solid, and the mixture was pulverized with a spatula. 6.6 g of water was then added, and the mixture was homogenized at 7500 rpm for 20 minutes using a homogenizer to obtain an aqueous dispersion of a composition containing hydrophobic compound (A) (volume proportion of particles of 100 μm or larger: 17%, volume median diameter: 44.58 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 5 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to practical oil resistance tests (25°C) and (65°C), and was evaluated as 4 points in both tests.

[0430] <Comparative Example 1> 2 g of N,N'-ethylenebisoctadecaneamide (biobased content: 97%, melting point: 143°C, hexadecane contact angle: 36.1°) that had been dry-milled to an average particle size of 18 μm as the hydrophobic compound (A1), 0.16 g of polyethylene glycol trimethyl nonyl ether (HLB 13.1), 0.04 g of polyethylene glycol trimethyl nonyl ether (HLB 8.1), and 17.8 g of water were added and stirred to obtain an aqueous dispersion composition (volume abundance ratio of particles of 100 μm or more: 4.3%, volume median diameter: 18 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 3 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to a practical oil resistance test (25°C), a practical oil resistance test (65°C), and a practical water resistance test, and the oil resistance in the practical oil resistance test (25°C) was 1 point.

[0431] The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt % so that the ratio of the hydrophobic compound (A1) to the pulp was 5 wt % in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to a practical oil resistance test (25°C), a practical oil resistance test (65°C), and a practical water resistance test, and the oil resistance in the practical oil resistance test (25°C) was 1 point.

[0432] <Comparative Example 2> 2 g of N,N'-ethylenebisoleic acid amide (biobased content: 97%, melting point: 116°C, hexadecane contact angle: 42.7°) that had been dry-milled to an average particle size of 7.4 μm as the hydrophobic compound (A1), 0.16 g of polyethylene glycol trimethyl nonyl ether (HLB 13.1), 0.04 g of polyethylene glycol trimethyl nonyl ether (HLB 8.1), and 17.8 g of water were added and stirred to obtain an aqueous dispersion composition (volume abundance ratio of particles of 100 μm or more: 1.4%, volume median diameter: 7.8 μm). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 3 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to a practical oil resistance test (25°C), a practical oil resistance test (65°C), and a practical water resistance test. The oil resistance in the practical oil resistance test (25°C) was 1 point, and the oil resistance in the practical oil resistance test (65°C) was 4 points.

[0433] <Comparative Example 3> An aqueous dispersion composition was obtained in the same manner as in Example 1, except that tripropylene glycol (liquid at 25°C, octanol / water partition coefficient: -0.50, Fedors SP value: 12.385), a water-miscible liquid non-hydrophobic compound, was used instead of the hydrophobic compound (A2). The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 3 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to a practical oil resistance test (25°C) and scored 1 point.

[0434] <Comparative Example 4> An aqueous dispersion composition was obtained in the same manner as in Example 1, except that the hydrophobic compound (A2) was replaced with tripropylene glycol (liquid at 25°C, octanol / water partition coefficient: -0.50, Fedors SP value: 12.385), a water-miscible liquid non-hydrophobic compound, and the amount used was changed to 0.70 g. The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 3 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to a practical oil resistance test (25°C) and scored 1 point.

[0435] <Comparative Example 5> A water-dispersed composition was obtained in the same manner as in Example 1, except that the hydrophobic compound (A2) was replaced with 3-methoxy-3-methyl-1-butanol (liquid at 25°C, octanol / water partition coefficient: 1.07, Fedors SP value: 10.489), a water-miscible liquid non-hydrophobic compound. The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 3 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to a practical oil resistance test (25°C) and scored 1 point.

[0436] <Comparative Example 6> A water-dispersed composition was obtained in the same manner as in Example 1, except that the hydrophobic compound (A2) was replaced with 3-methoxy-3-methyl-1-butanol (liquid at 25°C, octanol / water partition coefficient: 1.07, Fedors SP value: 10.489), a water-miscible liquid non-hydrophobic compound, and the amount used was changed to 0.70 g. The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 3 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was then placed in an automatic molding machine to prepare a mold. The mold was subjected to a practical oil resistance test (25°C) and scored 1 point.

[0437] <Comparative Example 7> An aqueous dispersion was obtained by mixing 2 g of paraffin wax (melting point 69.8°C) as a hydrophobic compound (A1), 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 to 16, HLB: 7), and 17.8 g of water. This aqueous dispersion was heated to 85°C and then treated with an ultrasonic homogenizer for 20 minutes to obtain an aqueous dispersion composition. The obtained aqueous dispersion composition exhibited the following properties. Median diameter D50: 0.8 μm Volume ratio of particles 100 μm or larger: 0% Volume ratio of particles 10 μm or larger: 12% A water dispersion composition of a hydrophobic compound (A1) was added to a pulp slurry having a concentration of 0.5 wt% so that the ratio of the hydrophobic compound (A1) to the pulp was 10 wt% in terms of solid content, to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was placed in an automatic molding machine to produce a mold. The mold was subjected to a practical oil resistance test (25°C) and scored 1 point.

[0438] <Examples 19 to 24 / Comparative Example 8> The test was carried out in the same manner as in Example 1, except that the hydrophobic compound (A) was prepared according to the composition shown in Table 3 and tested.

[0439] The results are summarized in the table below. [Table 1] TIFF0007787456000011.tif250146

[0440] [Table 2] TIFF0007787456000012.tif213167

[0441] [Table 3] TIFF0007787456000013.tif250167

[0442] The properties of the compound are summarized below. [Table 4] TIFF0007787456000014.tif123169

Claims

1. A repellent comprising a hydrophobic mixture (A) consisting of a hydrophobic compound (A1) and a hydrophobic compound (A2) different from the hydrophobic compound (A1), The hydrophobic compound (A1) is a non-hydrocarbon compound, The Shore A hardness [PEAK] of the hydrophobic mixture (A) is smaller than the Shore A hardness [PEAK] of the hydrophobic compound (A1) by 10 or more and 100 or less, The hydrophobic compound (A1) and the hydrophobic compound (A2) are each independently a compound having a hydrocarbon group having 6 to 40 carbon atoms.

2. The repellent according to claim 1 , which is a water-dispersed composition.

3. The repellent according to claim 1 or 2, wherein the hydrophobic compound (A1) has a contact angle with hexadecane of 30° or more.

4. The repellent according to claim 1 or 2, wherein the Shore A hardness [PEAK] of the hydrophobic mixture (A) is 4.0 or more and 70 or less.

5. the hydrophobic compound (A1) and the hydrophobic compound (A2) are each independently a compound selected from the group consisting of an amine-modified compound, a polyol-modified compound, a polycarboxylic acid-modified compound, and other liquid or solid oils; The amine-modified compound is a compound obtained by modifying an amine compound with an aliphatic hydrocarbon group having 10 to 40 carbon atoms, and the aliphatic hydrocarbon group is -OR', -N(R') ２ , —COOR′, and a halogen atom (wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms); The modified polyol is a compound obtained by modifying a polyol with an aliphatic hydrocarbon group having 10 to 40 carbon atoms, and the aliphatic hydrocarbon group is -OR', -N(R') ２ , —COOR′, and a halogen atom (wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms); The polycarboxylic acid modified product is a compound obtained by modifying a polycarboxylic acid with an aliphatic hydrocarbon group having 10 to 40 carbon atoms, and the aliphatic hydrocarbon group is -OR', -N(R') ２ 3. The repellent according to claim 1 or 2, which may have one substituent selected from the group consisting of -COOR', -COOR', and a halogen atom (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms).

6. the hydrophobic compound (A1) has an amide structure, The repellent according to claim 1 or 2, wherein the hydrophobic compound (A2) does not have an amide structure.

7. the hydrophobic compound (A1) is a compound selected from the group consisting of an amine-modified compound, a polyol-modified compound, and a polycarboxylic acid-modified compound; The amine-modified compound is an amine skeleton, and The following formula: -Y Ｎ -Z Ｎ ｎ [In the formula, Y Ｎ Is Y Ｎ１ and Y Ｎ２ is a (1+n) valent group consisting of one or more groups selected from the group consisting of Y Ｎ１ represents a direct bond, —O—, —C(═O)—, —C(═NR′)—, —C(═S)—, —S—, —S(═O) ２ -, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , and -N(-) ２ (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), Y Ｎ２ is a group consisting of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles, Z Ｎ is -OR', -N(R') ２ a monovalent aliphatic hydrocarbon group having from 10 to 40 carbon atoms, optionally having one substituent selected from —COOR′, —COOR′, and a halogen atom (wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms); n is an integer of 1 or more and 3 or less. and having one or more groups represented by At least one -Y Ｎ -Z Ｎ ｎ is bonded to a nitrogen atom of the amine skeleton; The polyol modification may be achieved by modifying one or more hydroxy groups of the polyol to the following formula: -Y Ｏ -Z Ｏ ｎ [In the formula, Y Ｏ Is Y Ｏ１ and Y Ｏ２ is a (1+n) valent group consisting of one or more groups selected from the group consisting of Y Ｏ１ represents a direct bond, —O—, —C(═O)—, —C(═NR′)—, —C(═S)—, —S—, —S(═O) ２ -, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , and -N(-) ２ (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), Y Ｏ２ is a group consisting of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles, Z Ｏ is -OR', -N(R') ２ a monovalent aliphatic hydrocarbon group having from 10 to 40 carbon atoms, optionally having one substituent selected from —COOR′, —COOR′, and a halogen atom (wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms); n is an integer of 1 or more and 3 or less. is a compound substituted with a group represented by The polycarboxylic acid modified product is a polycarboxylic acid modified product in which a hydroxy group of one or more carboxyl groups of the polycarboxylic acid is substituted by the following formula: -Y Ｃ -Z Ｃ ｎ [In the formula, Y Ｃ Is Y Ｃ１ and Y Ｃ２ is a (1+n) valent group consisting of one or more groups selected from the group consisting of Y Ｃ１ represents a direct bond, —O—, —C(═O)—, —C(═NR′)—, —C(═S)—, —S—, —S(═O) ２ -, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , and -N(-) ２ (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), Y Ｃ２ is a group consisting of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles, Z Ｃ is -OR', -N(R') ２ a monovalent aliphatic hydrocarbon group having from 10 to 40 carbon atoms, optionally having one substituent selected from —COOR′, —COOR′, and a halogen atom (wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms); n is an integer of 1 or more and 3 or less. A compound substituted with a group represented by the formula: The repellent according to claim 1 or 2.

8. the hydrophobic compound (A2) has a hydrocarbon group having 3 or more carbon atoms, The repellent according to claim 1 or 2, wherein the melting point of the hydrophobic compound (A2) is 40°C or lower.

9. The repellent according to claim 1 or 2, wherein the amount of the hydrophobic compound (A1) is 15% by weight or more and 95% by weight or less relative to the hydrophobic mixture (A).

10. The repellent according to claim 1 or 2, wherein the amount of the hydrophobic compound (A2) is 5 parts by weight or more and 500 parts by weight or less per 100 parts by weight of the hydrophobic compound (A1).

11. The melting point of the hydrophobic compound (A1) is 50°C or higher, The repellent according to claim 1 or 2, wherein the melting point of the hydrophobic compound (A2) is 40°C or lower.

12. The repellent according to claim 1 or 2, wherein the melting point of the hydrophobic compound (A1) is higher than the melting point of the hydrophobic compound (A2) by 30° C. or more.

13. the repellent agent comprises a dispersant; The repellent according to claim 1 or 2, wherein the amount of the dispersant is 0.1 parts by weight or more and 100 parts by weight or less relative to 100 parts by weight of the hydrophobic mixture (A).

14. A papermaking repellent kit comprising a first agent and a second agent, the first agent contains a hydrophobic compound (A1), the second agent contains a hydrophobic compound (A2) that is a compound different from the hydrophobic compound (A1), the Shore A hardness [PEAK] of the hydrophobic mixture (A) consisting of the hydrophobic compound (A1) and the hydrophobic compound (A2) is smaller by 10 or more and 100 or less than the Shore A hardness [PEAK] of the hydrophobic compound (A1); the hydrophobic compound (A1) and the hydrophobic compound (A2) are each independently a compound having a hydrocarbon group having from 6 to 40 carbon atoms, A papermaking repellent kit in which the first agent and the second agent are added separately and mixed to a pulp base material.

15. A method for manufacturing an article, comprising treating a substrate with the repellent agent of claim 1 or 2.

16. The substrate is a pulp substrate, 16. The method of claim 15, wherein the product is a pulp product.

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