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 hydrophobic compound (A1) is a compound selected from the group consisting of an amine-modified compound, a polycarboxylic acid-modified compound, paraffin wax, and microcrystalline wax, and the hydrophobic compound (A2) is a liquid or solid oil other than the compound selected from the group consisting of an amine-modified compound, a polycarboxylic acid-modified compound, paraffin wax, and microcrystalline wax.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a composition, particularly a composition capable of imparting liquid repellency to a substrate.

Background Art

[0002] Patent Document 1 discloses a powdery papermaking composition capable of improving paper quality such as bulkiness and sizeability and workability.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Patent Document 1 does not describe or suggest the use of a combination of a plurality of hydrophobic compounds. Further, Patent Document 1 has not examined the imparting of liquid repellency to a substrate.

[0005] An object of the present disclosure is to provide a novel composition capable of imparting liquid repellency to a substrate.

Means for Solving the Problems

[0006] The present disclosure includes the following aspects: [Item 1] A composition comprising a hydrophobic compound (A) composed of a hydrophobic compound (A1) and a hydrophobic compound (A2) different from the hydrophobic compound (A1), wherein the hydrophobic compound (A1) is a compound selected from the group consisting of an amine-modified product, a polycarboxylic acid-modified product, paraffin wax, and microcrystalline wax, A composition wherein the hydrophobic compound (A2) is a liquid or solid oil that does not correspond to a compound selected from the group consisting of an amine-modified product, a polycarboxylic acid-modified product, paraffin wax, and microcrystalline wax. [Item 2] The composition according to Item 1, which is a water-dispersible composition. [Item 3] The composition according to Item 1 or 2, which is a water repellent. [Item 4] The composition according to any one of Items 1 to 3, wherein the hexadecane contact angle of the hydrophobic compound (A1) is 30° or more. [Item 5] The composition according to any one of Items 1 to 4, wherein the hydrophobic compound (A1) and the hydrophobic compound (A2) are each independently a compound having a hydrocarbon group with 3 to 40 carbon atoms. [Item 6] The composition according to any one of Items 1 to 5, wherein the hydrophobic compound (A1) is a compound selected from the group consisting of an amine-modified product, paraffin wax, and microcrystalline wax. [Item 7] The composition according to any one of Items 1 to 6, wherein the hydrophobic compound (A1) is an amine-modified product. [Item 8] The hydrophobic compound (A1) has an amide structure, The composition according to any one of Items 1 to 7, wherein the hydrophobic compound (A2) does not have an amide structure. [Item 9] The hydrophobic compound (A1) is a compound selected from the group consisting of an amine-modified product, a polycarboxylic acid-modified product, paraffin wax, and microcrystalline wax; The amine-modified product is an amine skeleton, and the following formula: -Y N -Z N n [In the formula, Y N is Y N1 and Y N2is a 1 + n-valent group composed of one or more selected from the group consisting of Y N1 is a group composed 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’ is independently, in each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms). Y N2 is a group composed of one or more selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms and 2 to 4 valences, an optionally substituted hydrocarbon aromatic ring, and an optionally substituted heterocyclic ring having 2 to 4 valences. Z N is an optionally substituted monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group. n is an integer of 1 or more and 3 or less.] has one or more groups represented by at least one -Y N -Z N n is bonded to the nitrogen atom of the amine skeleton; the polycarboxylic acid modifier is obtained by replacing the hydroxy group of one or more carboxyl groups of a polycarboxylic acid with the following formula: -Y C -Z C n [wherein, Y C is a 1 + n-valent group composed of one or more selected from the group consisting of Y C1 and Y C2 is a group composed of one or more selected from the group consisting of Y C1 is a group composed 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’ is independently, in each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms). YC2 is a group composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a divalent to tetravalent hydrocarbon aromatic ring which may have a substituent, and a divalent to tetravalent heterocyclic ring which may have a substituent, Z C is a monovalent hydrocarbon group having 1 or more and 40 or less carbon atoms which may have a substituent or a monovalent polysiloxane group, n is an integer of 1 or more and 3 or less.] is a compound substituted with the group represented by; The composition according to any one of items 1 to 8. [Item 10] The hydrophobic compound (A2) has a hydrocarbon group having 3 or more carbon atoms, The melting point of the hydrophobic compound (A2) is 40°C or lower, The composition according to any one of items 1 to 9. [Item 11] The melting point of the hydrophobic compound (A1) is 50°C or higher, The composition according to any one of items 1 to 10, wherein the melting point of the hydrophobic compound (A2) is 40°C or lower. [Item 12] The composition according to any one of items 1 to 11, wherein the melting point of the hydrophobic compound (A1) is 30°C or higher than the melting point of the hydrophobic compound (A2). [Item 13] The composition according to any one of items 1 to 12, wherein the amount of the hydrophobic compound (A1) is 15% by weight or more and 95% by weight or less based on the hydrophobic compound (A). [Item 14] The composition according to any one of items 1 to 13, wherein the amount of the hydrophobic compound (A2) is 5 parts by weight or more and 500 parts by weight or less based on 100 parts by weight of the hydrophobic compound (A1). [Item 15] The composition contains a dispersant, The composition according to any one of items 1 to 14, wherein the amount of the dispersant is 0.1 part by weight or more and 100 parts by weight or less based on 100 parts by weight of the hydrophobic compound (A). [Item 16] A papermaking additive kit comprising a first agent and a second agent, wherein 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), which is used by separately adding and mixing the first agent and the second agent to a pulp base material, wherein the hydrophobic compound (A1) is a compound selected from the group consisting of an amine-modified product, a polycarboxylic acid-modified product, paraffin wax, and microcrystalline wax, and the hydrophobic compound (A2) is a liquid or solid oil that does not fall within the group of compounds selected from the group consisting of an amine-modified product, a polycarboxylic acid-modified product, paraffin wax, and microcrystalline wax; a papermaking additive kit. [Item 17] a base material, and a hydrophobic compound (A) composed of a hydrophobic compound (A1) and a hydrophobic compound (A2) different from the hydrophobic compound (A1), a product comprising wherein the hydrophobic compound (A1) is a compound selected from the group consisting of an amine-modified product, a polycarboxylic acid-modified product, paraffin wax, and microcrystalline wax, and the hydrophobic compound (A2) is a liquid or solid oil that does not fall within the group of compounds selected from the group consisting of an amine-modified product, a polycarboxylic acid-modified product, paraffin wax, and microcrystalline wax; a product. [Item 18] wherein the base material is a pulp base material, and the product is a pulp product; the product according to Item 17. [Item 19] A method for manufacturing a product, comprising the step of treating a base material with the composition according to any one of Items 1 to 15 or the papermaking additive kit according to Item 16. [Advantages of the Invention]

[0007] According to the present disclosure, liquid repellency can be favorably imparted to a base material. [Embodiments for Carrying Out the Invention]

[0008] <Definition of Terms> As used herein, the term "n-valent group" means a group having n bonds, i.e., a group that forms n bonds. Further, the term "n-valent organic group" means an n-valent group containing carbon. Such an organic group is not particularly limited, and may be a hydrocarbon group or a derivative thereof. The derivative of a hydrocarbon group means a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc. at the terminal or molecular chain of the hydrocarbon group.

[0009] As used herein, the term "hydrocarbon group" means a group containing carbon and hydrogen, and is a group obtained by removing a hydrogen atom from a hydrocarbon. Such a hydrocarbon group is not particularly limited, but is C 1-20 Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The above "aliphatic hydrocarbon group" may be linear, branched or cyclic, and may be saturated or unsaturated. Further, the hydrocarbon group may contain one or more ring structures. The hydrocarbon group may be substituted by one or more substituents when explicitly described.

[0010] In this specification, whether or not expressions such as "independently at each occurrence", "independently of each other", "independently of one another" or similar expressions are explicitly described, unless there is a description to the contrary, when a term (symbol) that may appear multiple times in a chemical structure is defined, the definition is applied independently for each occurrence.

[0011] The chemical structures described in this specification should be understood not to include chemical structures that are recognized by those skilled in the art as being chemically impossible or extremely unstable.

[0012] <Composition> The composition in the present disclosure contains a hydrophobic compound (A) composed of a hydrophobic compound (A1) and a hydrophobic compound (A2) different from the hydrophobic compound (A1). The composition in the present disclosure can be used as a treatment agent (for example, a barrier coating agent, a surface treatment agent, a repellent (liquid repellent), particularly a repellent), adheres to a substrate (particularly a pulp substrate), and can impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or antifouling property to the substrate, and can also function as a water repellent, an oil repellent, a water repellent, an oil repellent, and / or an antifouling agent. For example, the repellent in the present disclosure is excellent in oil resistance (for example, normal temperature oil resistance, high temperature oil resistance, antifouling property), etc., and it is possible to reduce the required addition amount.

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

[0014] The composition in the present disclosure may not have any selected from the group consisting of a compound having a fluoroalkyl group with 8 or more carbon atoms, a compound having a perfluoroalkyl group with 8 or more carbon atoms, a compound having a fluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The composition in the present disclosure can impart liquid repellency to the substrate even without containing these fluorine compounds.

[0015] The volume occupancy ratio of particles of 100 μm or more measured by the laser diffraction scattering method in the composition of the present disclosure may be 0.1% or more, 0.3% or more, 0.5% or more, 1% or more, 1.5% or more, 3% or more, 4% or more, 5% or more, or 10% or more, and may also be 50% or less, 30% or less, 20% or less, 15% or less, 10% or less, 5% or less, 3% or less, or 1.5% or less. The method for setting the volume occupancy ratio of particles of 100 μm or more measured by the laser diffraction scattering method within the above range is not limited, but for example, a pulverizer, a homogenizer, etc. may be used to refine the particles in the raw material and / or the dispersion liquid.

[0016] The volume median diameter measured by the laser diffraction scattering method in the composition of the present disclosure 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, and may also 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 the volume-based particle size distribution by the laser diffraction scattering method.

[0017] When the composition contains a liquid medium (for example, the composition is an aqueous dispersion), the penetration at 25 °C 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 also be 200 or less, 150 or less, 125 or less, or 100 or less. The measurement conditions for the penetration may be as described in JIS K 2235 6.4 for the penetration.

[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 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 also 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 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, and may also 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 also 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 composed 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, adheres to a substrate (especially a pulp substrate), and can impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or antifouling properties to the substrate.

[0020] [Properties, etc.] The properties that the hydrophobic compound (A), the hydrophobic compound (A1), and the hydrophobic compound (A2) may have are shown below. In the following, when referring to the properties of the hydrophobic compound (A) itself, the hydrophobic compound (A) is intended to be a mixture obtained by melting and mixing the hydrophobic compound (A1) and the hydrophobic compound (A2) at a temperature equal to or higher than the melting point and then cooling to room temperature.

[0021] (Dissolution properties) 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 or less, for example, 1.0 g / l or less. The water solubility can be calculated from the amount of dissolution at the time when a small amount of the compound is added little by little to a predetermined amount of water (25°C) until it no longer dissolves (such as when floating, precipitation, deposition, or cloudiness is observed). A compound with high water solubility (such as a water-miscible liquid compound) cannot be called 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 may each independently 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 determined by 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 satisfy the above range.

[0023] The difference in the SP values between the hydrophobic compound (A1) and the hydrophobic compound (A2) may be more than 0, 0.1 or more, 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, 1.0 or more, 2.0 or more, 3.0 or more, 4.0 or more, or 5.0 or more, and may also 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 there are a plurality of compounds in each of the hydrophobic compounds (A1) and (A2), a weighted average based on the weight ratio may be used for the calculation of each value. In this specification, unless otherwise specified, the difference is the 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 also 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 ranges, preferably both satisfy the above ranges.

[0025] The difference in the octanol / water partition coefficients (logPow) between the hydrophobic compound (A1) and the hydrophobic compound (A2) may be more than 0, 0.1 or more, 0.3 or more, 0.5 or more, 1.0 or more, 1.5 or more, or 2.0 or more, and may also 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 there are multiple compounds in each of the hydrophobic compounds (A1) and (A2), a weighted average based on the weight ratio may be used for calculating each value.

[0026] The HLB value (hydrophile-lipophile balance) of the hydrophobic compound (A2) may be 0.5 or more, or 1.0 or more, and may also 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 below the above upper limit value, the effects of the present disclosure can be exhibited well. The HLB value (hydrophile-lipophile balance) is a value conceived by W.C. Griffin and given to nonionic surfactants, which numerically represents the balance between the strength of the lipophilic group (such as an alkyl group) and the hydrophilic group (such as a polyoxyalkylene chain) of the nonionic surfactant. In the present invention, the HLB value adopts the calculated value by the Griffin method (reference documents: W.G. Griffin, J. Soc. Cosmetic Chemists, 1, 311 (1949) and W.G. Griffn, J. Soc. Cosmetic Chemists, 5, 249 (1954)). For those with catalog values, the catalog value may be adopted as a simple judgment method, but when the catalog value is different from the calculated value, the calculated value shall be adopted. The HLB value of the hydrophobic compound (A1) may have a value larger than that of the hydrophobic compound (A2), or the hydrophobic compound (A2) may have a larger value. In each of the hydrophobic compounds (A1) and (A2), when there are multiple compounds, a weighted average based on the weight ratio may be used for the calculation of each value.

[0027] (Thermal properties) The endothermic peak in the DSC of the hydrophobic compound (A1) (alone) may shift to a lower temperature when it is mixed with the hydrophobic compound (A2) to form the hydrophobic compound (A) (mixture). The endothermic peak temperature in the differential scanning calorimetry of the hydrophobic compound (A1) may shift to a lower temperature by 2 °C or more and 80 °C or less in the differential scanning calorimetry of the hydrophobic compound (A). The endothermic peak that shifts to a lower temperature may be any peak of the hydrophobic compound (A1) (for example, the maximum peak, any endothermic peak with the top 30% peak intensity, etc.), and at least 1 (for example, 50% or more, 70% or more, 100%) of all the peaks in the range of -50 °C to 300 °C (for example, -30 °C to 240 °C, particularly -20 °C to 180 °C, particularly 0 °C to 180 °C) may shift to a lower temperature. The lower temperature shift width 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 also 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. In one aspect, 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. By combining two kinds of hydrophobic compounds, it is considered that the thermal properties change and a lower temperature shift of the endothermic peak in DSC occurs. The hydrophobic compound (A1) may have one or more endothermic peaks at 45 °C or more, and the endothermic peak may shift to a lower temperature. Preferably, the endothermic peak of the hydrophobic compound (A1) that shifts to a lower temperature is the endothermic peak on the highest temperature side 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 the endothermic peak due to the decomposition of the compound, and is the endothermic peak within the range where the compound does not decompose. In the case of a compound that decomposes without melting, it is understood that the melting point of the compound is at least the decomposition temperature or higher.

[0028] The measurement conditions of DSC may be as follows. After cooling to -20°C or lower under a nitrogen atmosphere, DSC measures the endothermic peak observed during the heating process to 180°C or higher at a rate of 10°C / min. The endothermic heat quantity is calculated by calculating the heat quantity in the range of ±10°C of 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 may 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 ranges, preferably both satisfy the above ranges. The hydrophobic compound (A1) may be a solid at room temperature (melting point 30°C or higher), for example 50°C or higher, and the melting point of the hydrophobic compound (A2) may be 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 points between the hydrophobic compound (A1) and the hydrophobic compound (A2) may be more than 0°C, 5°C or more, 10°C or more, 15°C or more, 20°C or more, 25°C or more, 30°C or more, 50°C or more, 70°C or more, 90°C or more, 110°C or more, 130°C or more, 150°C or more, 175°C or more, or 200°C or more, for example, 30°C or more, 50°C or more, 70°C or more, or 90°C or more, preferably 30°C or more, more preferably 70°C or more, still more preferably 90°C or more, and may also be 300°C or less, 250°C or less, 200°C or less, 150°C or less, 100°C or less, 80°C or less, 60°C or less, 50°C or less, 40°C or less, 30°C or less, 20°C or less, or 10°C or less. The hydrophobic compound (A1) may have a larger value, or the hydrophobic compound (A2) may have a larger value, and particularly preferably the hydrophobic compound (A1) has a larger value. When there are a plurality of compounds in each of the hydrophobic compounds (A1) and (A2), a weighted average based on the weight ratio may be used for calculating each value. For example, the hydrophobic compound (A1) may have a melting point with a larger value than the hydrophobic compound (A2), 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 also be 200 or less, 150 or less, 125 or less, or 100 or less. The measurement conditions for penetration may be as described in JIS K 2235 6.4.

[0032] The penetration at 25°C of the hydrophobic compound (A) may be smaller than the larger value of the penetration at 25°C of the hydrophobic compound (A1) or (A2), and the difference ([(the larger value of the penetration at 25°C of the hydrophobic compound (A1) or (A2)) - (the penetration at 25°C of the hydrophobic compound (A))]) may be more 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, and may also 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 Shore A hardness [PEAK] at the peak during 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 5.0 or more, and may also 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 also 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 also 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 value of the Shore A hardness of the hydrophobic compound (A1) or (A2), and the difference may be as follows. [(The value of the higher Shore A hardness [PEAK] of the hydrophobic compound (A1) or (A2)) - (the Shore A hardness [PEAK] of the hydrophobic compound (A)) may be more 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 also 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 aspect is 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 value of the higher Shore A hardness [1s] of the hydrophobic compound (A1) or (A2)) - (the Shore A hardness [1s] of the hydrophobic compound (A)) may be more 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 also 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 aspect is 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 value of the higher Shore A hardness [3s] of the hydrophobic compound (A1) or (A2)) - (the Shore A hardness [3s] of the hydrophobic compound (A)) is It may be 0 or more, 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. Also, 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. In one aspect, it is 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 Shore A hardness of the hydrophobic compound (A1) may be greater than the Shore A hardness of the hydrophobic compound (A2).

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

[0036] The difference in the HD contact angle between the hydrophobic compound (A1) and the hydrophobic compound (A2) may be more than 0°, 5° or more, 10° or more, 15° or more, 20° or more, 25° or more, or 30° or more, and may also 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 there are a plurality of compounds in each of the hydrophobic compounds (A1) and (A2), a weighted average based on the weight ratio may be used for calculating 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. By the hydrophobic compounds (A1) and (A2) each independently having a water contact angle of not less than the above lower limit, good liquid repellency (particularly water repellency) can be imparted to the substrate. The water contact angle is the static contact angle with respect to the spin-coated film of the hydrophobic compound (A), and means the contact angle obtained by dropping 2 μL of water onto the spin-coated film and measuring the contact angle 1 second after the drop adheres. 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 the water contact angle between the hydrophobic compound (A1) and the hydrophobic compound (A2) may be more than 0°, 5° or more, 10° or more, 15° or more, 20° or more, 25° or more, or 30° or more, and may also 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 there are a plurality of compounds in each of the hydrophobic compounds (A1) and (A2), a weighted average based on the weight ratio may be used for calculating each value.

[0039] (Other properties) The hydrophobic compounds (A1) and (A2) are preferably bio-based compounds having carbon of bio-based origin. The bio-based content is measured in accordance with ASTM D6866. The bio-based content of the hydrophobic compounds (A1) and (A2) may each independently be 20% or more, preferably 30% or more, more preferably 50% or more, still more preferably 60% or more, still more preferably 70% or more, most preferably 80% or more or 90% or more, for example 100%. A high bio-based content means a small amount of use of fossil resource-based materials typified by petroleum and the like. From such a viewpoint, it can be said that the higher the bio-based content of the hydrophobic compound (A), the more preferable. 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) at 180 days each independently preferably has a biodegradability of 5% or more. Since the environmental load is reduced, the higher such biodegradability is, the more preferable. The biodegradability of the hydrophobic compounds (A1) and (A2) at 180 days may each independently be, for example, 10% or more, 20% or more, 30% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, preferably 30% or more, more preferably 50% or more, still more preferably 70% or more, and most preferably 80% or more. The biodegradability of the hydrophobic compounds (A1) and (A2) at 60 days each independently preferably has a biodegradability of 5% or more. Since the environmental load is reduced, the higher such biodegradability is, the more preferable. The biodegradability of the hydrophobic compounds (A1) and (A2) at 60 days may each independently 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 defined in JIS K 6953-1 or ASTM D6400. Only the hydrophobic compound (A1), only the 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) at 180 days preferably has a biodegradability of 5% or more. Since the environmental load is reduced, such a high biodegradability is more preferable. The biodegradability of the hydrophobic compound (A) at 180 days may be, for example, 10% or more, 20% or more, 30% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, preferably 30% or more, more preferably 50% or more, still more preferably 70% or more, and most preferably 80% or more. The biodegradability of the hydrophobic compound (A) at 60 days preferably has a biodegradability of 5% or more. Since the environmental load is reduced, such a high biodegradability is more preferable. The biodegradability of the hydrophobic compound (A) at 60 days may be, for example, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, or 45% or more, preferably 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 compound with the lower biodegradability among the hydrophobic compound (A1) and the hydrophobic compound (A2), and the difference may be more than 0%, 5% or more, 10% or more, 15% or more, 20% or more, 25% or more, or 30% or more, and may also be 60% or less, 50% or less, 40% or less, 30% or less, 20% or less, or 10% or less.

[0042] The biodegradability of the hydrophobic compound (A) at 180 days may be higher than the biodegradability of the hydrophobic compound (A1) at 180 days, or may also be higher than the biodegradability of the hydrophobic compound (A2) at 180 days. The difference between the biodegradability of the hydrophobic compound (A) at 180 days and the biodegradability of the hydrophobic compound (A1) at 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 also be 90% or less, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, 20% or less. The difference between the biodegradability of the hydrophobic compound (A) at 180 days and the biodegradability of the hydrophobic compound (A2) at 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 also be 90% or less, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, 20% or less.

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

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

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

[0046] (A monovalent hydrocarbon group which may have a substituent) 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 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 an alkyl group, a group having 1 to 4 carbon-carbon double bonds (for example, 1 to 2 carbon-carbon double bonds), and the like. The hydrocarbon group may be branched, cyclic or linear, and more preferably linear. It is preferable that one or both of the hydrophobic compounds (A1) and (A2) have an unsaturated hydrocarbon group.

[0048] The number of carbon atoms of 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. Further, it 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 substituents, preferably the number of substituents is 4 or less, more preferably the number of substituents is 1 or unsubstituted. Examples of the substituents include -OR’, -N(R’)2, -COOR’, and halogen atoms, etc. (wherein, R’ is, independently at 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 substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon group having substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, the hydrocarbon group may have 1 to 3 (e.g., 1) -OR’ (especially -OH) as substituents (e.g., other than at the terminal).

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

[0051] The polysiloxane group has the following formula: -[-Si(R s )2-O-] a - [wherein, R s is, independently at each occurrence, a hydrocarbon group having 1 to 40 carbon atoms or a reactive group, a is an integer of 5 or more and 10000 or less.] It may also be represented by

[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 methyl group, ethyl group, propyl group, butyl group, pentyl group, etc. (particularly aliphatic hydrocarbon groups, particularly alkyl groups, such as methyl group or ethyl group, particularly 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, 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 of 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 the reactive group are groups having a functional group (for example, hydroxy group, amino group, mercapto group, epoxy group, carboxyl group, halogen-substituted alkyl group, vinyl group, (meth)acrylic group, (meth)acryloyloxy group, and (meth)acrylamide group, hydrogen atom directly bonded to a silicon atom, etc.). These functional groups may be directly bonded to the silicon atom or may be bonded to an organic group directly bonded to the silicon atom. The organic group may be a hydrocarbon group, for example, an alkylene group or a divalent aromatic group. The hydrocarbon group may have 2 to 12 carbon atoms, and as the alkylene group, those having 2 to 10 carbon atoms are preferred. As the divalent aromatic group, those having 6 to 12 carbon atoms are preferred. The reactive group may be a group selected from the group consisting of a hydroxy 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 hydroxy 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, preferably 10 or more, and may be 10000 or less, 7500 or less, 5000 or less, 3000 or less, 1500 or less, 1000 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less, preferably 500 or less.

[0058] R, which is a hydrocarbon group having 1 to 5 carbon atoms in the polysiloxane group s The amount of s R may be 20 mol% or more, 40 mol% or more, 60 mol% or more, or 80 mol% or more, preferably 50 mol% or more, based on the total of R, and may be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less. For example, 50 mol% or more of the total amount of R groups may be a methyl group or an ethyl group (especially a methyl group). s

[0059] R, which is a hydrocarbon group having 6 to 40 carbon atoms in the polysiloxane group s The amount of s R may be 3 mol% or more, 10 mol% or more, 20 mol% or more, or 30 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.

[0060] R, which is a reactive group in the polysiloxane group s The amount of s R 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 R.

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

[0062] The terminal structure of the above-mentioned polysiloxane group is not limited, but is -OR​s , -Si(R s )3, etc. The R of the terminal structure s may have one or more reactive groups. Examples of the reactive groups 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 the linker. Such a linker is, but not limited to, a hydrocarbon group having 1 to 40 (for example, 1 to 20) carbon atoms which may be interrupted by an oxygen atom, for example, a (poly)oxyalkylene group having 1 to 40 (for example, 1 to 20) carbon atoms.

[0064] Examples of the polysiloxane group 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 -O-L s1 -[-Si(R s )2-O-] a -R s -L s1 -[-Si(R s )2-O-] a -Si(R s )3 -L s1 -O-L 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 [wherein, R s is, independently at 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 in the total of the groups, 50 mol% or more is a methyl group, L s1 is a hydrocarbon group having 1 to 20 carbon atoms, a is 5 or more and 10,000 or less.], TIFF2025094940000001.tif2069[wherein, 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. may be mentioned.

[0065] [Examples of the hydrophobic compound (A)] As an example of the hydrophobic compound (A), hydrocarbon compounds and compounds having a hydrocarbon group may be mentioned. Examples and preferred ranges of the hydrocarbon group are as described above.

[0066] Examples of the hydrophobic compound (A) include compounds selected from the group consisting of amine-modified products, polyol-modified products, polycarboxylic acid-modified products, and other liquid or solid oils (detailed below). For example, the hydrophobic compound (A1) is a compound selected from the group consisting of amine-modified products, polyol-modified products, polycarboxylic acid-modified products, paraffin wax, and microcrystalline wax (for example, a compound selected from the group consisting of amine-modified products, polycarboxylic acid-modified products, paraffin wax, and microcrystalline wax; particularly an amine-modified product), and the hydrophobic compound (A2) is a liquid or solid oil not corresponding to the compound (A1) (for example, a liquid or solid oil other than an amine-modified product; particularly a liquid or solid oil not being a compound selected from the group consisting of amine-modified products, polycarboxylic acid-modified products, paraffin wax, and microcrystalline wax; in one aspect, a liquid or solid oil not being a compound selected from the group consisting of amine-modified products, polyol-modified products, polycarboxylic acid-modified products, paraffin wax, and microcrystalline wax).

[0067] The hydrophobic compound (A) may be a hydrocarbon, or may be a non-hydrocarbon compound having a functional group such as an ester group, an ether group, an amide group (amide structure), etc. For example, the hydrophobic compound (A) may include a compound having an amide structure. Here, the amide structure may be an amide structure in a broad sense, and may be selected from amide structures in amide (carboxylic acid amide), urea, urethane, imide, thioamide, thiourea, thiourethane, thioimide, sulfonamide, sulfourea, sulfourethane, 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 in the direction reversed left and right). Here, at least one of the bonds of 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, per 100 parts by weight of the hydrophobic compound (A2), and may also 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 also 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).

[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 with respect to 100 parts by weight of the hydrophobic compound (A1), and may also 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) may be 0.01% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, or 30% by weight or more in the composition, and may also 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 product] As an example of each of the hydrophobic compounds (A1) and (A2), the amine-modified product will be described. The amine-modified product is a compound obtained by chemically modifying an amine compound so as to exhibit liquid repellency.

[0075] Due to its structure, the amine-modified product in the present disclosure is excellent in dispersibility in a liquid medium, and the composition of the present disclosure can have stable performance. In the case of a composition using a polymer-type compound as an active ingredient, the molecular weight distribution is wide and it tends to contain a relatively large amount of impurity components. On the other hand, the amine-modified product can be made into a low molecular weight and the molecular weight distribution can be narrowed (made single), and the performance can be improved.

[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 also 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 higher, 300 or higher, 350 or higher, 400 or higher, 500 or higher, 550 or higher, or 750 or higher, and may also be 3000 or lower, 2500 or lower, 2000 or lower, 1500 or lower, 1000 or lower, 900 or lower, 800 or lower, 750 or lower, or 500 or lower.

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

[0079] The amine-modified product in the present disclosure may be a polyamide having a plurality of amide groups, for example, a polyamide in which a plurality of modifying groups (for example, Z N ) are modified via amide groups with respect to an amine (raw material amine compound, for example, a polyamine). 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 material amine compound) with a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group, which may have a substituent.

[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 aliphatic hydrocarbon group having 3 or more and 40 or less carbon atoms (for example, 6 or more and 40 or less carbon atoms) is modified with respect to the amine.

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

[0083] (Amine skeleton) The amine-modified product in the present disclosure has an amine skeleton. The amine skeleton has one or more amino groups having a predetermined number of bonds (valences), which are obtained by removing a predetermined number of atoms or atomic groups (for example, hydrogen) from an amine compound. The amino group in the amine skeleton means a group selected from the group consisting of -NH2, -NH-, and -N(-)2, and also includes an amino group adjacent to a carbonyl group contained in an amide group, a urethane group, a urea group, an imide, etc. Note that the amine skeleton may be an aliphatic group or an 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 also 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 of 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 also 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 group is a mono- to trivalent amino group and is one or more groups selected from the group consisting of -NH2, -NH-, and -N(-)2. The number of amino groups in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, preferably 2 or more, and may also 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 (aliphatic hydrocarbon group or aromatic hydrocarbon group). The hydrocarbon group may be cyclic, branched, or linear. The hydrocarbon group may be saturated or unsaturated (for example, saturated). Here, the hydrocarbon group may be interrupted by an oxygen atom and / or a sulfur atom, or may consist only of carbon atoms, nitrogen atoms, and hydrogen atoms. The hydrocarbon group may be a hydrocarbon group that may be interrupted by an oxygen atom and / or a sulfur atom (for example, a chain-like saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings), or may be a general hydrocarbon group (for example, a chain-like saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings). When the hydrocarbon group is interrupted by an oxygen atom and / or a sulfur atom, it will have 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 also 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 mono- to trivalent amino group and a chain-like saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group that 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 also be 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, or 2 or less, preferably 6 or less or 4 or less.

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

[0091] The number of -Y N -Z N n in the amine-modified product 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 also 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 N -Z N n in the amine-modified product is bonded to the nitrogen atom of the amine skeleton. All of the -Y N -Z N n in the amine-modified product, the ratio of the number of -Y N -Z N n bonded to the nitrogen atom of the amine skeleton may be 10% or more, 30% or more, 60% or more, 80% or more, or 100%, and may also be 75% or less, 50% or less, or 25% or less. -Y not bonded to the nitrogen atom of the amine skeleton N -Z Nn binds to other groups (e.g., hydrocarbon groups) having an amine backbone.

[0093] (Y N ) Y N is a direct bond or a (1 + n)-valent group, preferably a (1 + n)-valent group. Y N functions as a linker connecting the amine backbone and n Z N s.

[0094] n is the number of Z N s that bind to Y N and may be an integer from 1 to 3. n may be 1 or more, 2 or more, or 3 or more, and may also be 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 aliphatic group) or an aromatic group.

[0096] Y N may have a molecular weight of 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more, and may also 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. Y 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 one or more selected from the group consisting of an amide group, a urea group, a urethane group, and an imide together with the amino group in the amine backbone. Examples of such amide groups, urea groups, urethane groups, and imide groups include -O-C(=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 (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms).] etc. are exemplified. Y N is preferably bonded to the nitrogen atom in the amine skeleton via a -(C=O)- group.

[0098] Y N is a direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -C(=S)-, -NR’-, -C(OR’)R’-, -C(OR’)(-)2, -N(-)2, an aliphatic hydrocarbon group having 1 to 20 carbon atoms with a valence of 2 to 4, a hydrocarbon aromatic ring with a valence of 2 to 4, and a heterocyclic ring with a valence of 2 to 4 [In the formula, R’ is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms).] and may be a 1+n-valent group composed of one or more selected from the group consisting of.

[0099] Y N is Y N1 and Y N2 and may be a 1+n-valent group composed of one or more selected from the group consisting of, Y N1 is 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, in each occurrence, R’ is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms).) and is a group composed of one or more selected from the group consisting of, Y N2 is a group composed of one or more selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms with a valence of 2 to 4, a hydrocarbon aromatic ring with a valence of 2 to 4, and a heterocyclic ring with a valence of 2 to 4, and may be a 1+n-valent group composed of one or more selected from the group consisting of. In the present specification, Y N The group described as is such that the left side is the amine skeleton and the right side is Z Nis coupled to.

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

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

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

[0103] Y N1 Y may be composed 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, -N(-)2 (wherein R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms)). Y N1 Examples of Y include a direct bond, -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=O)-NR’-, -NR’-, -NR’-C(=O)-, -NR’-C(=O)-O-, -NR’-C(=O)-NR’-, -C(=O)-, -C(=O)-O-, -C(=O)-NR’-, -C(=O)-NR’-C(=O)-, -C(=NR’)-, -S-, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2 etc. [In the formula, R' is, independently at 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).] Examples include. Note that when Y N1 is bonded to the nitrogen atom of the amine skeleton, the nitrogen atom is regarded as part of the amine skeleton (amino group).

[0104] 〇 Y N2 Y N2 is a linker composed of one or more 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 may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). Y N2 may be aliphatic or aromatic. Y N2 may be linear, branched, or cyclic.

[0106] Y N2 is a group with a valence of two or more. The valence of Y N2 may be, for example, 2 to 4, 2 to 3, or 2.

[0107] Y N2 The number of carbon atoms of 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 also 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 a 2- to 4-valent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a 2- to 4-valent hydrocarbon aromatic ring which may have a substituent, and a 2- to 4-valent heterocycle which may have a substituent.

[0109] The aliphatic hydrocarbon group having a valence of 2 to 4 and 1 to 40 carbon atoms may be a cyclic, branched, or linear hydrocarbon group. The aliphatic hydrocarbon group having a valence of 2 to 4 and 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 also 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, and may also be 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, etc. (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 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the aliphatic hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0111] Examples of the hydrocarbon aromatic ring having a valence of 2 to 4 include groups obtained by removing 2 to 4 hydrogens from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms in the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, and may also be 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, etc. (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 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon aromatic ring having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0113] The 2- to 4-valent heterocyclic ring may be an aliphatic group or an aromatic group. Examples of the 2- to 4-valent heterocyclic ring include groups obtained by removing 2 to 4 hydrogens 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 heterocyclic ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the heterocyclic ring may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0114] The heterocycle may have substituents. Examples of the substituents include -R’, -OR’, -N(R’)2, -COOR’, and a halogen atom, etc. (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 substituents may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the heterocycle having substituents, 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 may also be 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 of -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali(-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- [wherein, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or a heterocycle.] etc. are included.

[0116] Y N2 Specific examples of -(CH2) p -(p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(q and r are each independently 0 to 20, for example 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring) etc. can be mentioned.

[0117] ·Y N Examples of Y N Examples of Y will be described. In the following, R’ is, in each occurrence, independently 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 Examples of Y include, when Y N is divalent, -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. can be mentioned.

[0119] Y N Examples of Y include, when Y N 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 -), 2, etc. can be mentioned.

[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 N2 (-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 N1 -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 N2 -Y N1 -Y N2 -Y N1 (-), 3, -Y N2 -Y N1 -Y N2 -(Y N1 -), 3、 -Y N2 -Y N1 -(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, etc. In the amine-modified product, one or more Y N is preferably such that the amine backbone side terminal is -(C=O)- and is bonded to the nitrogen atom in the amine backbone.

[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 is, in each occurrence, independently a direct bond, -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=O)-NR’-, -NR’-, -NR’-C(=O)-, -NR’-C(=O)-O-、 -NR’-C(=O)-NR’-、 -C(=O)-、 -C(=O)-O-、 or -C(=O)-NR’- -C(=O)-NR’-C(=O)- (In the formula, R’ is, independently at 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).) is, Y N2 is an aliphatic hydrocarbon group having 2 to 4 valences and 1 to 10 carbon atoms, or a divalent aromatic group (for example, a divalent phenyl group, a divalent triazole group).] is a group represented by this. Thereby, liquid repellency can be favorably imparted to the base material.

[0123] Y N As further specific examples of *-(C=O)- -O-(C=O)-NR’- [In the formula, * means being bonded to the nitrogen atom of the 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. are exemplified.

[0124] (Z N ) Z N is a monovalent hydrocarbon group having 1 or more and 40 or less carbon atoms which may have a substituent, or a monovalent polysiloxane group, and the aspects in the descriptions of the above (monovalent hydrocarbon group which may have a substituent) and (monovalent polysiloxane group) are incorporated.

[0125] [Examples of amine-modified products] (Amine-modified product example 1) As an example of the amine-modified product, 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 [wherein, Y N is, independently at each occurrence, a direct bond or a group having a valence of 1 + n, Z N is, independently at each occurrence, a linear or branched monovalent hydrocarbon group having 3 to 40 carbon atoms which may have a substituent, L 1 is, independently at each occurrence, a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by an oxygen atom and / or a sulfur atom, n is, independently at each occurrence, an integer of 1 or more and 3 or less, p is, independently at each occurrence, an integer of 0 or more and 2 or less, q is, independently at each occurrence, an integer of 0 or more and 2 or less, p + q is 2 in each N(-Y N -Z N n ) p (-H) q and is 2, r is, independently at each occurrence, 0 or 1, s is, independently at each occurrence, 0 or 1, r + s is 1 in each N(-Y N -Z N n ) r (-H) s and is 1, the sum of all p and all r is 1 or more, t is an integer of 0 or more and 10 or less.] Examples thereof include the compound represented by (amine-modified example 1).

[0126] In the amine modification form 1, Y N , Z N , and for the details of n, the aspects in the above description are incorporated by reference.

[0127] In the amine modification form 1, L 1 is a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be interrupted by an oxygen atom and / or a sulfur atom, and may be a cyclic, branched, or linear hydrocarbon group, preferably a chain hydrocarbon group or an aromatic hydrocarbon. L 1 may incorporate the hydrocarbon groups in the description of the [amine skeleton] described above, and the hydrocarbon group may be interrupted by an oxygen atom and / or a sulfur atom, or may consist only of carbon atoms, nitrogen atoms, and hydrogen atoms. L 1 is, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings. L 1 is preferably a cyclic group having both a ring (e.g., aromatic ring) and a chain structure (e.g., linear structure, ether oxygen, thioether sulfur), and specific examples include 1,3-phenylenebisalkylene group, 1,4-phenylenebisalkylene group, diphenyl ether diyl group, diphenyl thioether diyl group, etc. L 1 The number of carbon atoms of L may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and may also 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.

[0128] In the amine modification form 1, p is, independently at each occurrence, an integer of 0 or more and 2 or less, q is, independently at each occurrence, an integer of 0 or more and 2 or less, and p + q is 2 in each N(-Y N -Z N n ) p (-H) q . Preferably, p may be 1 or more, for example 2, independently at each occurrence.

[0129] In amine modification system 1, r is, independently at each occurrence, 0 or 1, s is, independently at each occurrence, 0 or 1, and r + s is 1 for each N(-Y N -Z N n ) r (-H) s In, it is 1. Preferably, p may be, independently at each occurrence, 1 or more, for example 2.

[0130] The sum of all p and all r is 1 or more, that is, amine modification system 1 has one or more -Y N -Z N n . The sum of all p and all r may be 1 or more, 3 or more, 5 or more, 7 or more, 9 or more, 12 or more (the sum of all q and all s may be 0), and may also be 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, or 4 or less.

[0131] In amine modification system 1, t is an integer from 0 to 10. 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 also 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 system 2) As an example of other amine modification forms, the following formula: N(-Y N -Z N n ) p (-H) q -L 2 (-Y N -Z N n ) u [Wherein, Y N is, independently at each occurrence, a direct bond or a 1 + n-valent group, Z N is, independently at each occurrence, a linear or branched monovalent hydrocarbon group having 3 to 40 carbon atoms which may have a substituent, L2 is an aliphatic hydrocarbon group or aromatic hydrocarbon group having a valence of 1 + u and 2 to 20 carbon atoms, which may be interrupted by an oxygen atom and / or a sulfur atom, n is, independently in each occurrence, an integer of 1 or more and 3 or less, p is an integer of 0 or more and 2 or less, q is an integer of 0 or more and 2 or less, p + q is 2, u is an integer of 1 or more and 3 or less, The sum of p and u is 1 or more.] Examples include compounds represented by (Amine modification example 2).

[0133] In Amine modification example 2, Y N , Z N For details of and n, the aspects in the above description are incorporated by reference.

[0134] In Amine modification example 2, L 2 is an aliphatic hydrocarbon group or aromatic hydrocarbon group having a valence of 1 + u and 2 to 20 carbon atoms, which may be interrupted by an oxygen atom and / or a sulfur atom, and may be a cyclic, branched, or linear hydrocarbon group, preferably a chain hydrocarbon group or an aromatic hydrocarbon. L 2 As L, the hydrocarbon groups in the description of the above [amine skeleton] may be incorporated by reference. The hydrocarbon group may be interrupted by an oxygen atom and / or a sulfur atom, or may consist only of carbon atoms, nitrogen atoms, and hydrogen atoms. L 2 For example, it may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings. L 2 is preferably a cyclic group having both a ring (e.g., aromatic ring) and a chain structure (e.g., linear structure, ether oxygen, thioether sulfur). Specific examples include 1,3-phenylenebisalkylene group, 1,4-phenylenebisalkylene group, diphenyl ether diyl group, diphenyl thioether diyl group, etc. L 2The number of carbon atoms may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and may also 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.

[0135] In amine modification form 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 amine modification form 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 amine modification form 2, the sum of p and u is 1 or more, that is, amine modification form 2 has one or more -Y N -Z N n and has. The sum of all p and u may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more (the sum of all q may be 0), and may also be 5 or less, 4 or less, 3 or less, or 2 or less.

[0138] (Specific examples) As specific examples of the amine-modified product, compounds represented by the following formula can be mentioned. Regarding the details of Z in the following formula, the aspects in the above description of Z N are incorporated by reference.

[0139] TIFF2025094940000002.tif3340

[0140] TIFF2025094940000003.tif2757

[0141] TIFF2025094940000004.tif3042

[0142] TIFF2025094940000005.tif1843

[0143] TIFF2025094940000006.tif1755

[0144] TIFF2025094940000007.tif1851

[0145] TIFF2025094940000008.tif1660

[0146] The amine-modified product may be a synthetic wax derived from animal and vegetable oils and fats. The synthetic wax may be obtained by condensing a fatty acid derived from animal and vegetable oils and fats with an aliphatic amine or an amine containing an aromatic group. Examples of the synthetic wax include fatty acid amide compounds such as hydroxy fatty acid amide compounds, palmitic 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] Examples of the method for producing the amine-modified product include, but are not limited to, a method of synthesizing by reacting a Z N group-containing carboxylic acid with various amines (starting amines) in the presence of a condensing agent if necessary, and a method of synthesizing by reacting various amines with an acid chloride, acid anhydride, isocyanate, etc. of a Z N group-containing carboxylic acid. The condensing agent may be a known condensing agent, and examples thereof include DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA, Py-Bop, etc.

[0148] (Amine (starting amine)) Examples of amines (raw material amines) that are precursors of the amine skeleton include alkylamines such as methylamine, ethylamine, propylamine, butylamine, dibutylamine, etc. that can form the amine skeleton; alkylene diamines such as ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine, cyclohexanediamine, methylenebiscyclohexylamine, etc.; polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tris(2-aminoethyl)amine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tris(2-aminopropyl)amine, tetrapropylenepentamine, pentapropylenehexamine, iminobispropylamine, dibutylenetriamine, bis(2-aminoethoxy)ethane, bis(2-aminoethyl)ether, bis[2-(2-aminoethoxy)ethyl]ether, bis[2-(3-aminopropoxy)ethyl]ether, spermine, spermidine, etc.; oxygen- or sulfur-containing aliphatic amines such as 1-aminopropanediol, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, polyoxypropylenediamine, polyoxyethylenediamine, etc.; aromatic monoamines such as aniline, 1- or 2-naphthylamine, 1-, 2-, or 9-aminoanthracene, 9-aminophenanthrene, 2-, 3- or 4-aminobiphenyl, etc.; monocyclic aromatic polyamines such as o-, m- or p-phenylenediamine, o-, m- or p-xylylenediamine, diaminotoluene, 2,3-, 2,4- or 2,5-tolylenediamine, etc.Polycyclic aromatic polyamines such as diaminobiphenyl, bisaminophenoxyphenylpropane, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl sulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenylphenylethane, bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, aminophenoxybiphenyl, aminophenoxyphenyl ketone, 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, 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, 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, 4,4'-diaminodiphenyl sulfide, etc.;2-Hydroxyethyl ethylenediamine, 2-hydroxyethyl propylenediamine, di-2-hydroxyethyl ethylenediamine, di-2-hydroxyethyl propylenediamine, 2-hydroxypropyl ethylenediamine, di-2-hydroxypropyl ethylenediamine, and other hydroxyl group-containing polyamines, etc. may be mentioned. The polyamine may be one obtained by polymerizing a polymerizable compound such as allylamine.;

[0149] [Polyol-modified product] As an example of each of the hydrophobic compounds (A1) and (A2), the polyol-modified product will be described. The polyol-modified product 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 also 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 1 or more. From the viewpoint of improving liquid repellency, the degree of polymerization of the polyol-modified product may be 2 or more, 3 or more, 5 or more, 6 or more, preferably 7 or more, more preferably 8 or more, still more preferably 9 or more, and from the viewpoint of improving the handleability of the composition, it may be 100 or less, preferably 50 or less, more preferably 30 or less, still more preferably 15 or less. The degree of polymerization means the number of repeating monomer units constituting the polymer.

[0152] The degree of polymerization in the present disclosure means the average degree of polymerization. The average degree of polymerization in the present disclosure means the 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 means the average degree of polymerization of the above polyglycerol. The average degree of polymerization of polyglycerol is the average degree of polymerization (n) calculated from the hydroxyl value by the end group analysis method. 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 (Formula 2) Hydroxyl value = 56110(n + 2) / Average molecular weight The hydroxyl value in the above (Formula 2) is a numerical value that serves as an index of the number of hydroxyl groups contained in polyglycerol. The hydroxyl value is calculated from the amount of potassium hydroxide required to neutralize acetic acid necessary for acetylating the free hydroxy groups contained in 1 g of polyglycerol, and is calculated in accordance with "Standard Oil Analysis Test Methods (I) Established by the Japanese Oil Chemists' Society, 2003 Edition" compiled by the Japanese Oil Chemists' Society. The hydroxyl value of the raw material polyglycerol is actually measured according to the above standard oil analysis test method, and the average degree of polymerization and the average molecular weight of polyglycerol can be calculated from the above relational expressions.

[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 means the average degree of polymerization of the above polyvinyl alcohol. The average degree of polymerization of polyvinyl alcohol can be measured in accordance with JIS K 6726 Polyvinyl Alcohol Test Method.

[0154] When the polyol-modified product in the present disclosure is a polysaccharide-modified product obtained by modifying a polysaccharide, the degree of polymerization of the polyol-modified product means the average degree of polymerization of the above polysaccharide. The analysis of the average degree of polymerization of the polysaccharide can be carried out as follows. The degree of polymerization is the number of monosaccharide units (fructose and glucose units) in the polysaccharide, and the average degree of polymerization is, for example, the top of the peaks of each analysis result obtained by ordinary analysis methods such as HPLC, GC, and HPAEC as follows. As the column, for example, ULTRON PS-80N (8×300 mm) manufactured by Shinwa Chemical Industries Co., Ltd. (solvent: water, flow rate: 0.5 ml / min, temperature: 50°C) or TSK-GEL G30000 PWXL (7.8×300 mm) manufactured by TOSOH (solvent: water, flow rate: 0.5 ml / min, temperature: 50°C) is used, and it can be measured by using a differential refractometer as a detector.

[0155] The polyol-modified product 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 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, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may also be 10000000 or less, 3000000 or less, 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 9000 or less, 8000 or less, 7000 or less, 6000 or less, 5000 or less, 3000 or less, 2000 or less, 1000 or less, or 500 or less.

[0156] The substitution rate of the hydroxy groups in the modified polyol 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, or 70% or more, particularly 80% or more, and may also 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, or 15% or less, for example 95% or less. Here, the "substitution rate" means the proportion (mol%) of the hydroxy groups derived from the polyol that are modified, and may mean the proportion (mol%) modified by a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group that may have a substituent.

[0157] The remaining rate of the hydroxy groups in the modified polyol 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 also 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 "remaining rate" means the proportion (mol%) of the hydroxy groups derived from the polyol that are not modified.

[0158] The number of modifying groups in the modified polyol 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 also 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 that may have a substituent.

[0159] The equivalent weight of the modifying group 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 also be 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 400 or less. It 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 by 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 an aliphatic hydrocarbon group having 3 to 40 carbon atoms (for example, 6 to 40 carbon atoms) is used to modify the polyol.

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

[0162] (-Y O -Z O n ) In the polyol-modified product in the present disclosure, one or more hydroxy groups of the polyol are represented by the following formula: -Y O -Z O n [wherein, Y O is a 1 + n-valent group composed of one or more selected from the group consisting of Y O1 and Y O2 , Y O1is a group composed of one or more selected from the group consisting of 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’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms)). Y O2 is a group composed of one or more selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms and 2 to 4 valences, an optionally substituted hydrocarbon aromatic ring, and an optionally substituted heterocyclic ring having 2 to 4 valences. Z O is an optionally substituted monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group. n is an integer of 1 or more and 3 or less.] may be substituted by a group represented by.

[0163] (Y O ) Y O is Y O1 and Y O2 is a (1 + n)-valent group composed of one or more selected from the group consisting of. Y O1 is a group composed of one or more selected from the group consisting of 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’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms)). Y O2 is a group composed of one or more selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms and 2 to 4 valences, an optionally substituted hydrocarbon aromatic ring, and an optionally substituted heterocyclic ring having 2 to 4 valences.

[0164] n is Z O bonded to YO is a number 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, and may also be 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 also 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 Y may have an amide structure. Here, the amide structure may be an amide structure in a broad sense, and may be selected from amide structures in amide (acid amide), urea, urethane, imide, thioamide, thiourea, thiourethane, thioimide, sulfonamide, sulfourea, sulfourethane, 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 in the reversed orientation). Here, at least one of the bonds of 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. By having an amide structure, the liquid repellency can be improved.

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

[0168] Y O1 is a direct bond or a group with a valence of two or more. Y O1 The valence of may be 2 to 4, 2 to 3, or 2. Y O1 It 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 also be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0170] Y O1 may be composed of 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’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms)). O1 Examples of Y include a direct bond, -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=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 and the like (wherein R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms)). are included.

[0171] Y O2It may have at least an amide structure. Here, the amide structure may be an amide structure in a broad sense, and may be selected from amide structures in amide (acid amide), urea, urethane, imide, thioamide, thiourea, thiourethane, thioimide, sulfonamide, sulfourea, sulfourethane, 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 in the reversed orientation). Here, at least one of the bonds possessed by N of 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. By having an amide structure, the liquid repellency can be improved.

[0172] ○ Y O2 Y O2 is a linker composed of one or more 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 heterocyclic ring which may have a substituent.

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

[0174] Y O2 is a group with a valence of two or more. Y O2 The valence of may be, for example, 2 to 4, 2 to 3, or 2.

[0175] Y O2 The number of carbon atoms of 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 also 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 a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a divalent to tetravalent hydrocarbon aromatic ring which may have a substituent, and a divalent to tetravalent heterocyclic ring which may have a substituent.

[0177] The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or linear hydrocarbon group. The divalent 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 of 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 also 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, and may also be 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, etc. (wherein, in each occurrence, R’ 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 aliphatic hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0179] Examples of the 2- to 4-valent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogens 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, preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, and may be 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, etc. (wherein R’ is, independently at 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 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon aromatic ring having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0181] The divalent to tetravalent heterocyclic rings may be aliphatic groups or aromatic groups. Examples of the divalent to tetravalent heterocyclic rings include groups obtained by removing 2 to 4 hydrogens 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 heterocyclic ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the heterocyclic ring may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0182] The heterocyclic ring may have a substituent. Examples of the substituent include -R’, -OR’, -N(R’)2, -COOR’, and a halogen atom, etc. (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 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the heterocyclic ring having a substituent, 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 may also be 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 of -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 a heterocyclic ring.] etc. may be mentioned.

[0184] Y O2 Specific examples of -(CH2) p -(p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(q and r are each independently 0 to 20, for example 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring) etc. may be mentioned.

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

[0186] Y O Examples of are, when Y O is divalent, -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 -Y O2 -(Y O1 -Y O2 -) 2、 -Y O1 -(Y O2 -Y O1 -Y O2 -)2; -Y O2 (-)2, -Y O2 -Y O1 (-)2, -Y O2 -(Y O1 -)2, -Y O2 -Y O1 -Y O2 (-)2, -Y O2 -Y O1 (-Y O2 -)2, -Y O2 -(Y O1 -Y O2 -)2, -Y O2 -Y O1 -Y O2 -YO1 (-)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 As an example of, Y O when it is tetravalent, -Y O1 (-)3, -Y O1 -Y O2 (-)3, -Y O1 -(Y O2 )3, -Y O1 -Y O2 -Y O1 (-)3, -Y O1 -Y O2 (-Y O1 )3, -Y O1 -(Y O2 -Y O1 )3, -Y O1 -Y O2 -Y O1 -Y O2 (-)3, -Y O1 -Y O2 -Y O1 -(Y O2 ) 3、 -Y O1 -Y O2 -(Y O1 -Y O2 ) 3、 -Y O1 -(Y O2 -Y O1 -Y O2 )3; -Y O2 (-)3, -Y O2 -Y O1 (-)3, -Y O2 -(Y O1 )3, -Y O2 -Y O1 -Y O2 (-)3, -YO2 -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. can be mentioned.

[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. can be mentioned.

[0190] (Preferred Y O example) Preferably, Y O is -O-Y O11 -, or -O-Y O11 -Y O21 -Y O12 - [Wherein, each symbol is independent 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-, -O-C(=O)-, -O-C(=O)-O-, -C(=O)-NR’-, -O-C(=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’-, or -C(OR’)(-)2.], may be

[0191] Y O11 is a non-hydrocarbon linker, which is a direct bond or a polyvalent 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 also 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 and may be a hydrocarbon group having 1 to 40 carbon atoms.

[0195] Y O21 The number of carbon atoms of 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 also 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, or linear hydrocarbon group, and may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group.

[0197] Y O21 Specific examples of -(CH2) p -(where p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(where q and r are each independently 0 to 20, e.g., 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring) and the like can be mentioned.

[0198] Y O12 may be -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=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’-, or -C(OR’)(-)2.

[0199] Y O12It may have at least an amide structure. Here, the amide structure may be an amide structure in a broad sense, and may be selected from amide structures in amide (acid amide), urea, urethane, imide, thioamide, thiourea, thiourethane, thioimide, sulfonamide, sulfourea, sulfourethane, 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 in the reversed orientation). Here, at least one of the bonds of 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. By having an amide structure, the liquid repellency can be improved.

[0200] (Z O ) Z O is a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group, and the aspects in the above descriptions of (the monovalent hydrocarbon group which may have a substituent) and (the monovalent polysiloxane group) are incorporated.

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

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

[0203] Examples of the salt of the anionic group include an alkali metal salt, an alkaline earth metal salt, or an ammonium salt, such as a methylammonium salt, an ethanolammonium salt, a triethanolammonium salt, etc.

[0204] Examples of the cationic group include an amino group, preferably a tertiary amino group and a quaternary amino group. In the case of a tertiary amino group, the two groups bonded to the nitrogen atom are the same or different and are preferably an aliphatic group having 1 to 5 carbon atoms (especially an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (especially an aralkyl group such as a benzyl group (C6H5-CH2-)). In the case of a quaternary amino group, the three groups bonded to the nitrogen atom are the same or different and are preferably an aliphatic group having 1 to 5 carbon atoms (especially an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (especially an aralkyl group such as a benzyl group (C6H5-CH2-)). In the case of a tertiary amino group and a quaternary amino group, the remaining one 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 which is 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 (especially monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid) are preferred.

[0206] [Production method] The polyol-modified product may be produced by reacting a modifier having a modifying group (or a precursor structure of the modifying group) with the hydroxy group of the polyol.

[0207] (Polyol) The polyol is a compound having two or more hydroxy groups and is a compound serving as a raw material for the polyol-modified product. The 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, it may have a hydroxy group and an ether bond in the repeating structure of the monomer unit.

[0210] The polyol may be a low molecular weight (for example, weight average molecular weight less than 1000, 500 or less) and / or a high molecular weight. 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, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may also be 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 5000 or less, 3000 or less, 2000 or less, 1000 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 also 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 of the polyol may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, 150 or more, and may also 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 of the polyol is the value obtained by dividing the weight average molecular weight of the polyol by the number of hydroxy groups.

[0213] The polyol may be a natural product. The natural product may be a high-molecular natural product, a low-molecular natural product, or a derivative thereof. The 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, etc.

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

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

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

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

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

[0219] Examples of amino acids include glucosamine, etc.

[0220] Examples of vitamins include ascorbic acid, inositol, etc.

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

[0222] Examples of hydroxyhydrocarbons include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerin, trimethylolpropane, trimethylolethane, etc. Hydroxyhydrocarbons are hydrocarbons having a hydroxy group and may be aromatic or aliphatic, but are preferably aliphatic. When referring to hydroxyhydrocarbons, it may mean hydroxyhydrocarbons other than compounds included in other groups such as polysaccharides (other hydroxyhydrocarbons).

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

[0224] Examples of polyether polyols may be compounds obtained by addition polymerization of alkylene oxides to an initiator. Examples of the initiator include compounds having a hydroxy group with two or more functional groups. For example, the initiator includes propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, glycerin, polyglycerin, trimethylolpropane, triethanolamine, pentaerythritol, ethylenediamine, aromatic diamine, diethylenetriamine, sorbitol, and sucrose. Examples of the alkylene oxide include ethylene oxide and propylene oxide. The polyether polyol obtained by addition polymerization of the alkylene oxide to the initiator is also referred to as a polyoxyalkylene polyol or an oxyalkylene derivative of a polyol. Representative examples of the polyether polyol 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] Examples of polymer polyols are compounds obtained by polymerizing at least a part of the polyether polyol with an ethylenically unsaturated monomer in the polyether polyol. Examples of the ethylenically unsaturated monomer include acrylonitrile and styrene.

[0226] Examples of the polyester polyol may be compounds obtained by dehydrative condensation of a compound having two or more functional carboxyl groups and a compound having two or more functional hydroxy groups. Examples of the compound 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 the compound having two or more functional hydroxy groups include ethylene glycol, propylene glycol, propanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and polymers thereof etc.

[0227] (Modifier) The modifier is a compound having reactivity with the polyol, and is preferably a compound having a monovalent hydrocarbon group having 1 or more and 40 or less carbon atoms which may have a substituent or a monovalent polysiloxane group as described above.

[0228] Examples of the modifier are as follows. Acid halide G(O=)C-Z O Acid anhydride O(C(=O)-Z O )2 Carboxylic acid HO(O=)C-Z O Isocyanate O=C=N-Z O Thiocyanate S=C=N-Z O Epoxy (CH2OCH)CH2O-Z O Halide G-Z O Amine H2N-Z O Hydroxy HO-Z O [Wherein, Z O is as described above, and G is a halogen atom (for example, 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 monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a group having a monovalent polysiloxane group. For example, Z O may be -Y O -Z O n as well.

[0230] The polyol modified product may be synthesized by reacting a polyol with a modifier. For example, a modifier which is an acid halogen compound, an acid anhydride, or a carboxylic acid is reacted with the hydroxy group of the polyol to form an ester bond, thereby synthesizing a polyol modified product. Further, a modifier which is a halide or an epoxy compound is reacted with the hydroxy group of the polyol to form an ether bond, thereby producing a polyol modified product. The reaction conditions for the polyol and the modifier can be appropriately designed by those skilled in the art according to the target product, such as the use of a catalyst (for example, an acid catalyst or a base catalyst) and the use of a condensing agent.

[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. Further, it 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, it is 150°C or lower, or 100°C or lower. 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-modified product may be a low molecular weight (for example, weight average molecular weight less than 1500, less than 1000, 500 or less) and / or a 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, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may also be 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 9000 or less, 8000 or less, 7000 or less, 6000 or less, 5000 or less, 3000 or less, 2000 or less, 1000 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 under the following apparatus and conditions. Separation column: SB-806M (8 mm × 30 mm, Shodex) Column temperature: 40 °C Mobile phase solvent: Ion-exchanged water Mobile phase flow rate: 1.0 mL / min Sample concentration: 0.5 wt% Injection volume: 50 μL Detector: RI detector (Waters2414, Waters)

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

[0236] The substitution rate of the hydroxyl group for the carboxyl group in the polycarboxylic acid 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 also 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" means the proportion (mol%) of the hydroxyl groups of the carboxyl groups derived from the polycarboxylic acid that are modified, and may mean the proportion (mol%) modified by a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group that may have a substituent.

[0237] The remaining rate of the hydroxyl group for the carboxyl group in the polycarboxylic acid 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 also 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 "remaining rate" means the proportion (mol%) of the hydroxyl groups of the carboxyl groups derived from the polycarboxylic acid that are not modified.

[0238] The number of modifying groups possessed by 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 also 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 that may have a substituent.

[0239] The modified group equivalent of the polycarboxylic acid modifier 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 also be 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 400 or less. It is the value obtained by dividing the weight average molecular weight of the polycarboxylic acid modifier by the number of modified groups. Here, the modified group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent.

[0240] In the polycarboxylic acid modifier, one or more hydroxy groups of the polycarboxylic acid are substituted by a modified group. The modified 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 modifier may have a structure in which an aliphatic hydrocarbon group having 3 to 40 carbon atoms (for example, 6 to 40 carbon atoms) is modified with respect to the polycarboxylic acid.

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

[0242] (-Y C -Z C n ) In the polycarboxylic acid modifier in the present disclosure, the hydroxy group of one or more carboxyl groups of the polycarboxylic acid has the following formula: -Y C -Z C n [wherein, Y C is a 1 + n-valent group composed of one or more selected from the group consisting of Y C1 and Y C2 , Y C1is a group composed of one or more selected from the group consisting of 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’ is, independently at 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).), Y C2 is a group composed of one or more selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms and 2 to 4 valences, an optionally substituted hydrocarbon aromatic ring having 2 to 4 valences, and an optionally substituted heterocyclic ring having 2 to 4 valences, Z C is an optionally substituted monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group, n is an integer of 1 or more and 3 or less.] may be substituted by a group represented by

[0243] (Y C ) Y C is Y C1 and Y C2 is a (1 + n)-valent group composed of one or more selected from the group consisting of Y C1 is a group composed of one or more selected from the group consisting of 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’ is, independently at 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).), Y C2 is a group composed of one or more selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms and 2 to 4 valences, an optionally substituted hydrocarbon aromatic ring having 2 to 4 valences, and an optionally substituted heterocyclic ring having 2 to 4 valences.

[0244] n is Z C bonded to YC is a number and may be an integer from 1 to 3. n may be 1 or more, 2 or more, or 3 or more, and may also be 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 also 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 Y may have at least an amide structure. Here, the amide structure may be an amide structure in a broad sense and may be selected from amide structures in amide (acid amide), urea, urethane, imide, thioamide, thiourea, thiourethane, thioimide, sulfonamide, sulfourea, sulfourethane, 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 in the reversed orientation). Here, at least one of the bonds of 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. By having an amide structure, the liquid repellency can be improved.

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

[0248] Y C1 is a direct bond or a group with a valence of two or more. Y C1 The valence of may be 2 to 4, 2 to 3, or 2. Y C1 It 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 also be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0250] Y C1 may be composed of 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’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms)). C1 Examples of Y include a direct bond, -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=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. (wherein R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms)). are exemplified.

[0251] Y C1may have at least an amide structure. Here, the amide structure may be an amide structure in a broad sense, and may be selected from amide structures in amide (acid amide), urea, urethane, imide, thioamide, thiourea, thiourethane, thioimide, sulfonamide, sulfourea, sulfourethane, 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 in a direction reversed left and right). Here, at least one of the bonds possessed by N of 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. By having an amide structure, the liquid repellency can be improved.

[0252] ○ Y C2 Y C2 is a linker composed of one or more 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 heterocyclic ring which may have a substituent.

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

[0254] Y C2 is a group with a valence of two or more. Y C2 The valence of may be, for example, 2 to 4, 2 to 3, or 2.

[0255] Y C2 The number of carbon atoms of 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 also 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 a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a divalent to tetravalent hydrocarbon aromatic ring which may have a substituent, and a divalent to tetravalent heterocyclic ring which may have a substituent.

[0257] The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight-chain hydrocarbon group. The divalent 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 of 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 also 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, and may also be 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, etc. (wherein, R’ is independently at 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 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the aliphatic hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0259] Examples of the 2- to 4-valent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogens 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, preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, and may also be 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, etc. (wherein, in each occurrence, R’ 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 hydrocarbon aromatic ring having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0261] The divalent to tetravalent heterocyclic ring may be an aliphatic group or an aromatic group. Examples of the divalent to tetravalent heterocyclic ring include groups obtained by removing 2 to 4 hydrogens 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 heterocyclic ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the heterocyclic ring may be 2 or more, 3 or more, or 4, and may also be 4 or less, 3 or less, or 2.

[0262] The heterocyclic ring may have a substituent. Examples of the substituent include -R’, -OR’, -N(R’)2, -COOR’, and a halogen atom, etc. (wherein R’ is, independently at 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 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the heterocyclic ring having a substituent, 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 may also be 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 of -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 a heterocyclic ring.] etc. can be mentioned.

[0264] Y C2 Specific examples of -(CH2) p -(p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(q and r are each independently 0 to 20, for example 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring) etc. can be mentioned.

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

[0266] Y C Examples of are, when Y C is divalent, -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 Y 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 it 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. can be mentioned.

[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. can be mentioned.

[0270] (Preferred Y C example) Preferably, Y C is -Y C11 - or -Y C11 -Y C21 -Y C12 - [wherein, each symbol is independent 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-, -O-C(=O)-, -O-C(=O)-O-, -C(=O)-NR’-, -O-C(=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’-, or -C(OR’)(-)2.], may be.

[0271] Y C11 is a non-hydrocarbon linker, a direct bond or a polyvalent 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 also 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 and may be a hydrocarbon group having 1 to 40 carbon atoms.

[0275] Y C21 The number of carbon atoms of 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 also 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, or straight-chain hydrocarbon group, and may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group.

[0277] Y C21 Specific examples of -(CH2) p -(where p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(where q and r are each independently 0 to 20, e.g., 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring) and the like can be mentioned.

[0278] Y C12 may be -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=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’-, or -C(OR’)(-)2.

[0279] Y C12may have at least an amide structure. Here, the amide structure may be an amide structure in a broad sense, and may be selected from amide structures in amide (acid amide), urea, urethane, imide, thioamide, thiourea, thiourethane, thioimide, sulfonamide, sulfourea, sulfourethane, 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 in the reversed orientation). Here, at least one of the bonds of 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. By having an amide structure, the liquid repellency can be improved.

[0280] (Z C ) Z C is a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group, and the aspects in the description of the above (monovalent hydrocarbon group which may have a substituent) and (monovalent polysiloxane group) are incorporated.

[0281] [Other modifying groups] The hydroxy group of the carboxyl group of the polycarboxylic acid may be substituted with a modifying group other than -Y C -Z C n . Examples of the modifying group are an anionic group and / or a cationic group. As the anionic group and / or the cationic group, the aspects in the description of [Other modifying groups] in the above polyol are incorporated.

[0282] [Production method] The polycarboxylic acid modified product may be produced by reacting a modifier 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) A polycarboxylic acid is a compound having two or more carboxyl groups and is a compound serving as a raw material for a polycarboxylic acid modified product. A polycarboxylic acid is a compound having two or more carboxyl groups in the molecule. The polycarboxylic acid may be aliphatic or aromatic, but is preferably aliphatic.

[0284] The polycarboxylic acid may be low molecular weight (for example, 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, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may also be 1000000 or less, 7500000 or less, 500000 or less, 3000000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 5000 or less, 3000 or less, 2000 or less, 1000 or less, or 500 or less.

[0285] The number of carboxyl groups that the polycarboxylic acid has 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 also 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, 150 or more, and may also 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 a 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 above natural products also include 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] The dicarboxylic acid is a compound having two carboxyl groups, and examples thereof include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid, terephthalic acid, malic acid, tartaric acid, aldic acid, and salts thereof.

[0290] The tricarboxylic acid is a compound having three carboxyl groups, and examples thereof include citric acid, tricarballylic acid, t-aconitic acid, trimellitic acid, and salts thereof.

[0291] The tetracarboxylic acid is a compound 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] (Modifier) The modifier is a compound having reactivity with the polycarboxylic acid, and it is preferably a compound having a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent as described above.

[0294] Examples of the modifier are as follows. Epoxy (CH2OCH)CH2O-Z C Amine H2N-Z C Hydroxy HO-Z C [Wherein, ZC is as described above.]

[0295] Z in the structure of the above-mentioned 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. For example, Z C may be -Y C -Z C n and the like.

[0296] The polycarboxylic acid modified product may be synthesized by reacting a polycarboxylic acid with a modifier. For example, a modifier which is an epoxy compound is reacted with a carboxy group of a polycarboxylic acid to form an ester bond, thereby generating a polycarboxylic acid modified product. Those skilled in the art can appropriately design the reaction conditions between the polycarboxylic acid and the modifier, such as the use of a catalyst (for example, an acid catalyst or a base catalyst) and the use of a condensing agent, according to the target product.

[0297] [Oil] An example of each of the hydrophobic compounds (A1) and (A2) will be described with respect to oil. 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 (for example, having 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 above-mentioned amine modified product, polyol modified product, and polycarboxylic acid modified product. Note that the oil is a non-volatile oily compound, and the boiling point may be, for example, 200 degrees or higher, 250 degrees or higher, or 300 degrees 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 (for example, having a 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 higher, 3000 or higher, 5000 or higher, 7500 or higher, 10000 or higher, 30000 or higher, 100000 or higher, 300000 or higher, or 500000 or higher, and may also be 10000000 or lower, 7500000 or lower, 5000000 or lower, 3000000 or lower, 1000000 or lower, 750000 or lower, 500000 or lower, 300000 or lower, 100000 or lower, 75000 or lower, 50000 or lower, 30000 or lower, 10000 or lower, 7500 or lower, 5000 or lower, or 3000 or lower.

[0300] [Synthetic oil] Synthetic oil is an oil (oily compound) 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; silicone oils, etc.

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

[0302] [Vegetable oil and animal oil] Vegetable oil and animal oil may be liquid or solid (wax) at room temperature. Examples 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 butter, 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, squalene, beef tallow, lard (pork fat), mutton fat, beef foot oil, whale oil, salmon oil, bonito oil, herring oil, cod oil, etc., and their hydrogenated oils; rice wax, carnauba wax, sunflower wax, candelilla wax, sumac wax, beeswax, lanolin, whale wax, ibex wax, etc.; fatty acids such as stearic acid, capric acid, caproic acid, linoleic acid, linolenic acid, palmitic acid, lauric acid, eleostearic acid, etc.; fatty alcohols such as lauryl alcohol, cetostearyl alcohol, stearyl alcohol, cetyl alcohol, myristyl alcohol, etc.; 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] [An example of the hydrophobic compounds (A1) and (A2)]

[0304] The hydrophobic compound (A1) may be, for example, the amine-modified product described above, particularly an aliphatic amine-modified product.

[0305] The hydrophobic compound (A1) may be, for example, the amine-modified product or wax (e.g., hydrocarbon wax) described above, particularly an amine-modified product (particularly an aliphatic amine-modified product). As a specific example, TIFF2025094940000009.tif69101 Paraffin wax having 20 to 40 carbon atoms and the like.

[0306] Examples of the hydrophobic compound (A2) include monoester compounds, diester compounds, triester compounds, tetraester compounds, polyester compounds, monoamide compounds, diamide compounds, triamide compounds, polyamide compounds, and the like. 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, citric acid esters, benzoic acid esters, or esters obtained by condensing an alcohol represented by CH3(CH2) n OH (n = 0 to 30, linear or branched structure) and 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, condensates of fatty acids and pentamines; and the like.

[0307] The hydrophobic compound (A2) may be, for example, a polycarboxylic acid modifier, a polyol modifier, or an oil described above, and particularly may be a compound having a plurality (for example, 2 to 10, 2 to 6, 2 to 4) of monovalent aliphatic hydrocarbon structures (particularly fatty acid ester structures). Examples of the hydrophobic compound (A2) include fatty acid-modified polyols (for example, fatty acid-modified saccharides, etc.), oils and fats, long-chain aliphatic alcohol-modified polycarboxylic acids (for example, long-chain alcohol-modified polyvalent aromatic rings, etc.). As a specific example, TIFF2025094940000010.tif13483 and the like.

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

[0309] The dispersant may use each of an organic dispersant and an inorganic dispersant, or may be a combination of an organic dispersant and an inorganic dispersant.

[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 mean a surfactant.

[0311] The dispersant may be non-fluorine.

[0312] [Nonionic dispersant] The dispersant may contain a nonionic dispersant. The nonionic dispersant may be a nonionic surfactant.

[0313] The nonionic dispersant may be of low molecular weight or high molecular weight. 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 also be 100000 or less, 25000 or less, 10000 or less, 7500 or less, 5000 or less, 2500 or less, 750 or less, or 250 or less.

[0314] Examples of the nonionic dispersant include ether, ester, ester ether, alkanolamide, polyol, and amine oxide.

[0315] An example of the 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. Examples of the alcohol are alcohols having 1 to 30 valences (especially 2 to 10 valences) and 1 to 50 carbon atoms (especially 10 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of the fatty acid are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0317] Examples of ester ethers are compounds in which an alkylene oxide (especially ethylene oxide) is added to an ester of an alcohol and a fatty acid. Examples of alcohols are alcohols having 1 to 30 valences (especially 2 to 10 valences) and 1 to 50 carbon atoms (especially 3 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0318] Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or a dialkanolamine. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 1 to 3 amino groups and 1 to 5 hydroxy groups and 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0319] The polyol may be an alcohol having 2 to 5 valences and 10 to 30 carbon atoms. The amine oxide may be an oxide of an amine (secondary amine or preferably tertiary amine) (for example having 5 to 50 carbon atoms).

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

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

[0322] Nonionic dispersants may be alkylene oxide adducts of linear and / or branched aliphatic (saturated and / or unsaturated) groups, polyalkylene glycol esters of linear and / or branched fatty acids (saturated and / or unsaturated), sorbitan esters of linear and / or branched fatty acids (saturated and / or unsaturated), glycerin esters of linear and / or branched fatty acids (saturated and / or unsaturated), polyglycerin esters of linear and / or branched fatty acids (saturated and / or unsaturated), sucrose esters of linear and / or branched fatty acids (saturated and / or unsaturated), polyoxyethylene (POE) / polyoxypropylene (POP) copolymers (random copolymers or block copolymers), alkylene oxide adducts of acetylene glycols, etc. Among these, those in which the structure of the alkylene oxide adduct portion and the polyalkylene glycol portion is polyoxyethylene (POE) or polyoxypropylene (POP) or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Also, the nonionic dispersant may not contain an aromatic group.

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

[0324] R 1is preferably 8 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms. R 1 Preferred specific examples of 1 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 2 are 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) in the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, a styrene chain, etc., and among them, an oxypropylene chain is preferable.

[0325] Specific examples of the nonionic dispersant include condensation products of ethylene oxide with hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkane (C 12 -C 16 ) thiol, sorbitan monofatty acid (C7-C 19 ) or alkyl (C 12 -C 18 ) amine, 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 the nonionic dispersant include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycols, polyethyleneimine ethoxylates, 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 kind, or may be a mixture of two or more kinds. The nonionic dispersant may be a mixture of a compound having an HLB (hydrophilic-lipophilic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. Specifically, it is preferably selected from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, polyoxypropylene having an HLB 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, polyoxyethylene sorbitan fatty acid esters having an HLB value of less than 7.

[0327] [Cationic dispersant] The dispersant may contain 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 of a low molecular weight type (for example, having a molecular weight of 2,000 or less, particularly 10,000 or less), or may be of a high molecular weight type (for example, having a molecular weight of 2,000 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, and may also 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-added type ammonium salt. Specifically, amine salt type dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, etc.; quaternary ammonium salt type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, benzethonium chloride, etc.; polymeric cationic dispersants such as polyquaternium-1 to 47, etc. Examples of the cationic dispersant include alkylamine salts, quaternary ammonium salts, etc.

[0330] The low molecular weight type cationic dispersant is R 21 -N + (-R 22 )(-R 23 )(-R 24 )X - [In the formula, R 21 , R 22 , R 23 and R 24 are hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and X is an anionic group.] It may be a compound represented by. R 21 , R 22 , R 23 and -R 24 Specific examples are alkyl groups (e.g., methyl group, butyl group, stearyl group, palmityl group). Specific examples of X are halogen (e.g., chlorine), acid (e.g., hydrochloric acid, acetic acid). The cationic dispersant may be a monoalkyltrimethylammonium salt (alkyl having 4 to 40 carbon atoms).

[0331] Specifically, the low molecular weight type cationic dispersant has the formula: R 1 p -N + R 2 q X - [Wherein, R 1 is a linear and / or branched aliphatic (saturated and / or unsaturated) group having 12 or more carbon atoms (for example, C 12 ~C 50 ), and R 2 is H or an alkyl group having 1 to 4 carbon atoms, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, especially 3) to 50) (CH3, C2H5 are particularly preferred), and X is a halogen atom (for example, chlorine), or a fatty acid salt having 1 to 4 carbon atoms, or a sulfonate having 1 to 4 carbon atoms, and p is 1 or 2, q is 2 or 3, and p + q = 4.] It may be an ammonium salt represented by R 1 may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0332] Examples of the low-molecular cationic dispersant may 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 various polymers having cationic groups (for example, ammonium group, quaternary ammonium group) (for example, polyquaternium-1 to 47). Examples of the polymeric cationic dispersant include cationized starches, cationized celluloses (for example, O-(2-hydroxy-3-(trimethylammonio)propyl) hydroxyethyl cellulose chloride), cationized guar gums, cationized xanthan gums, cationized natural products such as chitosan (especially cationized saccharides); 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, quaternized vinylimidazole, and the like.

[0334] [Anionic dispersant] The dispersant may contain an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may not contain an anionic dispersant.

[0335] The anionic dispersant may be of low molecular weight or high molecular weight. 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 also be 100000 or less, 25000 or less, 10000 or less, 7500 or less, 5000 or less, 2500 or less, 750 or less, or 250 or less.

[0336] Examples of the anionic dispersant include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonated fatty acid salts, N-acyl amino acid type dispersants, phosphoric acid mono- or diester type dispersants, and sulfosuccinic acid esters. As an example of the anionic dispersant, carboxylate salts (for example, fatty acid salts) and the like can be mentioned.

[0337] [Amphoteric dispersant] The dispersant may contain an amphoteric dispersant. The amphoteric dispersant may be an amphoteric surfactant.

[0338] The amphoteric dispersant may be of low molecular weight or high molecular weight. 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 also be 100000 or less, 25000 or less, 10000 or less, 7500 or less, 5000 or less, 2500 or less, 750 or less, or 250 or less.

[0339] Examples of the amphoteric dispersant include alanines, imidazolinium betaines, amide betaines, betaine acetate, etc. Specifically, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetic acid betaine, fatty acid amide propyl dimethylaminoacetic acid betaine, etc. can be mentioned.

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

[0341] The average primary particle diameter 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 also 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 diameter 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 the inorganic dispersant include polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, hydroxyapatite; carbonates such as calcium carbonate, magnesium carbonate; silicates such as calcium metasilicate; sulfates such as calcium sulfate, barium sulfate; hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, etc.

[0343] [Amount of dispersant] The amount of the dispersant may be 0.01 part by weight or more, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, based on 100 parts by weight of the hydrophobic compound (A), and 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, 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 in the present disclosure may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The composition in the present disclosure may contain at least water and may be an aqueous dispersion.

[0345] Examples of the organic solvent include esters (for example, esters having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), ketones (for example, ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone), alcohols (for example, alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (for example, toluene and xylene), and petroleum solvents (for example, alkanes having 5 to 10 carbon atoms, specifically, naphtha, kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxy group (for example, polyols such as alcohols, glycol solvents, ether forms of polyols (for example, monoether forms), 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, or 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, based on 1 part by weight of the hydrophobic compound (A), and may also 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.

[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, based on 1 part by weight of the hydrophobic compound (A), and may also 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.

[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, based on 1 part by weight of the hydrophobic compound (A), and may also 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.

[0349] [Organic acid] The composition of the present disclosure may contain an organic acid. Known organic acids can be used. Preferred examples of the organic acid include carboxylic acids, sulfonic acids, sulfinic acids, etc., and carboxylic acids are 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, citric acid, etc., and formic acid or acetic acid is particularly preferred. In the present disclosure, one kind of organic acid may be used, or two or more kinds 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 the organic acid may be 0.1 part by weight or more, 1 part by weight or more, 3 part by weight or more, 5 part by weight or more, 10 part by weight or more, 15 part by weight or more, 20 part by weight or more, 50 part by weight or more, 75 part by weight or more, or 100 part by weight or more, based on 100 parts by weight of the hydrophobic compound (A). Also, it 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. The amount of the 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] [Hardening agent] The composition of the present disclosure may contain a hardening agent (active hydrogen-reactive compound or active hydrogen-containing compound).

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

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

[0354] Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanates such as 2,6-diisocyanatomethyl caproate, and lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane and other aliphatic triisocyanates. 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 are 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 are araliphatic diisocyanates and araliphatic triisocyanates. Specific examples of araliphatic polyisocyanates are 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used alone or in combination of two or more.

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

[0358] Derivatives of polyisocyanates include, for example, various derivatives such as dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, uretoimines, isocyanurates, iminooxadiazinediones, etc. of the above-mentioned polyisocyanate compounds. 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 obtained by blocking the isocyanate groups of the polyisocyanate compound with a blocking agent. It is preferable to use a blocked polyisocyanate compound because it is relatively stable even in solution.

[0360] The blocking agent blocks free isocyanate groups. The blocked polyisocyanate compound can, for example, regenerate the isocyanate groups and react easily with hydroxy groups by heating to 100 °C or higher, for example 130 °C or higher. Examples of the blocking agent are phenolic compounds, lactam compounds, aliphatic alcohol compounds, oxime compounds, etc. The polyisocyanate compound can be used alone or in combination of two or more.

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

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

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

[0364] [Other components] The composition may contain other components in addition to the above components. Examples of other components include polysaccharides, paper strength enhancers, flocculants, yield improvers, coagulants, binder resins, anti-slip agents, sizing agents, paper strength enhancers, fillers, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, fragrances, and the like. These may be used alone or in combination of two or more. In addition to the above-mentioned components, as other components, other water-repellent and / or oil-repellent agents, dispersants, texture modifiers, softeners, flame retardants, paint fixatives, anti-wrinkle agents, drying rate adjusters, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity adjusters, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage preventers, washing wrinkle preventers, shape retainers, drape retention agents, ironing property improvers, brightening agents, whitening agents, fabric softening clay, migration inhibitors such as polyvinylpyrrolidone, polymer dispersants, soil release agents, scum dispersants, fluorescent brightening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Tinopal CBS-X manufactured by Ciba Specialty Chemicals), dye fixatives, anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine, stain removers, enzymes such as cellulase, amylase, protease, lipase, keratinase as fiber surface modifiers, anti-foaming agents, silk powder, surface-modified products thereof or emulsion dispersions (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical Co., Ltd.), hydrolyzed silk solution (Jomo), Silkgen G Soluble S (Ichimaru Pharcos)) that can impart silk-like texture and functions such as moisture absorption and release, anti-pollution agents (e.g., nonionic polymer compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by Gohou Chemical Industry Co., Ltd.), SRC-1 manufactured by Clariant Japan, etc.) can be blended. These may be used alone or in combination of two or more.

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

[0366] <Additive kit for papermaking> In the above description, a composition containing the hydrophobic compound (A) has been described. However, 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 in the present disclosure includes a first agent and a second agent. The first agent contains the hydrophobic compound (A1). The second agent contains the hydrophobic compound (A2), which is a compound different from the hydrophobic compound (A1). The first agent and the second agent may be separately added and mixed for use with respect to the pulp substrate. The first agent may be first added and mixed with the pulp substrate, and then the second agent may be added and mixed, or vice versa.

[0367] The components in the first agent and the second agent may include the components in the composition described above, and the embodiments in the description of the above composition are incorporated by reference into the first agent and the second agent.

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

[0369] 〔Pulp〕 The pulp composition contains pulp, and the pulp is 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, a pulp slurry, a pulp product, etc. Examples of the pulp base material include bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp, groundwood pulp, bleached or unbleached high-yield pulps such as mechanical pulp or thermomechanical pulp, etc.; pulp slurries containing the pulp; papers made of waste paper pulps such as waste newsprint, waste magazines, corrugated cardboard waste paper or deinked waste paper, etc., pulp products such as paper containers and paper molded articles. Specific examples of the pulp products include food packaging materials, food containers, base paper for gypsum boards, base paper for coatings, medium-weight paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-proof liners and metal laminated papers, kraft paper, neutral printing and writing paper, neutral base paper for coatings, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc. Examples of preferred pulp products include food packaging materials and food containers, and particularly pulp molded articles for food contact applications.

[0370] The amount of pulp 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 in the pulp composition, and may also 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 is 30% by weight or less in the pulp composition, and when the pulp composition is prepared by external addition, the amount of pulp may be 75% by weight or more in the pulp composition.

[0371] 〔Liquid medium〕 The pulp composition may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent, and is typically an aqueous medium, particularly water. The liquid medium may also contain a liquid medium derived from the treatment agent.

[0372] [Amount of liquid medium] The amount of the liquid medium 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 in the pulp composition, and may also 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 is 50% by weight or more, particularly 90% by weight or more in the pulp composition, and when the pulp composition is prepared by external addition, the amount of the liquid medium may be 30% by weight or less, particularly 10% by weight or less in the pulp composition.

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

[0374] [Amount of hydrophobic compound (A)] The addition amount of the treatment agent added to the pulp base material may be adjusted so that the hydrophobic compound (A) reaches a desired amount. The amount of the 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 based on the pulp, and may also 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.

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

[0376] [[Paper strength agent]] The pulp composition may contain a paper strength agent. Examples of paper strength agents include Polyacrylamide-based paper strength agents such as cationic polyacrylamide, anionic polyacrylamide, and amphoteric polyacrylamide; Starch, enzyme-modified starch, thermo-chemically modified starch, oxidized starch, esterified starch, etherified starch (e.g., hydroxyethylated starch, etc.), aldehyde-modified 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 nanofibers, cellulose nanofibers, and pullulan, and polysaccharide-based paper strength agents such as these modified polysaccharides (e.g., modified polysaccharides with introduced hydroxyl groups or cationic groups); Polyamide-based paper strength agents such as polyamide resin, polyamine resin, polyamide-polyamine resin, polyamide-epichlorohydrin resin, polyamide-polyamine-epichlorohydrin resin, polyamide-polyurea-formaldehyde resin, and epoxidized polyamide resin; Urea / melamine-based paper strength agents such as urea resin, melamine resin, urea-formaldehyde resin, and melamine-formaldehyde resin; Polyvinyl alcohol-based paper strengthening 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 include styrene-butadiene copolymers, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, polyvinyl chloride, polyvinylidene chloride, polyacrylate esters, fatty acid diamides, polyethyleneimine resins, ketone aldehyde resins, etc. As the paper strengthening agent in the present disclosure, polyacrylamide-based paper strengthening agents, polysaccharide-based paper strengthening agents, or polyamide-based paper strengthening agents are preferred.

[0377] [Amount of paper strengthening agent] The amount of the paper strengthening 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 with respect to the pulp, and may also 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.

[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, neutral rosin-based sizing agents), alkyl ketene dimers, alkenyl succinic anhydrides, etc.

[0379] [Amount of sizing agent] The amount of the sizing agent may be 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more with respect to the pulp, and may also 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.

[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 (such as aluminum sulfate), organic acids (such as formic acid and acetic acid), flocculants, yield improvers, dyes, fluorescent dyes, slime control agents, and defoaming agents. The pulp composition contains components of the composition (treatment agent) containing the hydrophobic compound (A), but each component that can be contained in the composition containing the hydrophobic compound (A) described above may be separately 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 with respect to the pulp, and may also be 30% by weight or less, 20% by weight or less, 10% by weight or less, or 5% by weight or less.

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

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

[0384] Examples of the fibrous substrate include animal and plant natural fibers 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 mixed fibers thereof. The fiber products include woven fabrics, knitted fabrics, non-woven fabrics, fabrics in the form of clothing (e.g., water-repellent clothing such as raincoats), and carpets. However, the fibers, yarns, and intermediate fiber products (e.g., sliver or roving, etc.) in the state before being made into fabrics may also be treated.

[0385] The substrates to be treated with the treatment agent of the present disclosure are not limited to fibrous substrates, and other examples include stone, filters (e.g., electrostatic filters), dust masks, parts of fuel cells (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster, etc.

[0386] When the base material is glass, the manufactured glass product may be an optical member. Some layer (or film), such as a hard coat layer or an antireflection layer, etc., may be formed on the surface (outermost layer) of the glass base material. Either a single-layer antireflection layer or a multilayer antireflection layer may be used for the antireflection layer. Examples of inorganic substances that can be used for the antireflection layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, WO3, etc. These inorganic substances may be used alone or in combination of two or more of them (for example, as a mixture). When forming a multilayer antireflection layer, it is preferable to use SiO2 and / or SiO for its outermost layer. When the article to be manufactured is an optical glass component for a touch panel, it may have a thin film using a transparent electrode, such as indium tin oxide (ITO) or indium zinc oxide, etc., on a part of the surface of the base material (glass). Also, depending on its specific specifications, etc., the base material may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), a fogging film layer, a hard coating film layer, a polarizing film, a retardation film, and a liquid crystal display module, etc.

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

[0388] Regarding the pulp base material, the type and composition of the water-repellent agent, the aspects described in the above description of the "pulp composition" are incorporated by reference. The composition of the present disclosure can be applied to the base material by a conventionally known method as a treatment agent (particularly a water-repellent agent). As a treatment method, the water-repellent agent in the present disclosure can be dispersed and diluted in an organic solvent or water as necessary, and then adhered to the inside and / or surface of the pulp base material by a known method such as dip coating, spray coating, or foam coating, and then dried. After drying, a pulp product with the solid component of the water-repellent agent adhered thereto can be obtained. If necessary, it may be applied together with a suitable cross-linking agent and cured. The concentration of the water-repellent agent in the treatment agent brought into contact with the pulp base material may be appropriately changed depending on the application, but may be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0389] The water-repellent agent can be applied to the pulp base material by any of the methods known for treating the pulp base material with a liquid. The pulp base material may be immersed in the water-repellent agent, the pulp base material and the water-repellent agent may be mixed, or a solution may be adhered or sprayed onto the pulp base material. The treated pulp base material is preferably dried and cured by heating in order to exhibit water-repellent properties. 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] As a method for treating the pulp base material, an internal addition treatment method in which a water-repellent agent is added to the pulp before papermaking (for example, pulp slurry), or an external addition treatment method in which a water-repellent agent is applied to the pulp after papermaking (for example, pulp product) can be used. Examples of the internal addition treatment method include mixing, dipping, etc., and may include a step of adding a water-repellent agent to the pulp slurry and stirring and mixing. Examples of the external addition treatment method include spraying, coating, etc., and specifically include a pond-type two-roll size press, a gate roll type, and a rod metering size press, etc. The treatment may be an external addition treatment or an internal addition treatment. For example, when the pulp base material is paper, it may be coated on the paper, or a solution may be adhered or sprayed onto the paper, or it may be treated by mixing with the pulp slurry before papermaking.

[0391] The treatment method may be an internal addition treatment in which a sizing agent is added to the pulp slurry before papermaking. As the internal addition treatment, it may include one or more of the steps of adding a sizing agent to the pulp slurry and stirring and mixing it, sucking and dewatering the pulp composition prepared in the step through a reticular body of a predetermined shape to deposit the pulp composition to form an intermediate of a pulp molded product, and molding and drying the intermediate of the pulp molded product with a heated mold to obtain a pulp molded product, but it is not limited to this. The treated paper may optionally be heat-treated depending on the properties of the paper after simple drying at room temperature or high temperature. The temperature of the heat treatment may be 150 °C or higher, 180 °C or higher, or 210 °C or higher, and may be 300 °C or lower, 250 °C or lower, or 200 °C or lower, and particularly may be 80 °C to 180 °C. By performing the heat treatment within such a temperature range, excellent oil resistance, water resistance, etc. can be exhibited. An external addition treatment may be performed on the internally added pulp base material to treat it with a sizing agent, and further wax and further paper strengthening agent may be adhered to the surface.

[0392] The treatment method may be an external addition treatment in which a sizing agent is applied to the pulp base material after papermaking. The size press for the external addition treatment can also be classified as follows according to the coating method. One coating method is a so-called pond-type two-roll size press in which a coating liquid (sizing liquid) is supplied to a nip portion formed by passing paper between two rubber rolls to create a coating liquid reservoir called a pond, and the sizing liquid is applied to both sides of the paper by passing the paper through this coating liquid reservoir. Another coating method is a gate roll type in which the sizing liquid is applied by a surface transfer type, and a rod metering size press. In the pond-type two-roll size press, the sizing liquid easily penetrates into the paper, and in the surface transfer type, the sizing liquid components tend to remain on the surface of the paper. The surface transfer type has a coating layer that tends to remain on the surface of the paper and has more coating layers formed on the surface than the pond-type two-roll size press. In the present disclosure, even when the former pond-type two-roll size press is used, performance can be imparted to the paper. The paper treated in this way, after simple drying at room temperature or high temperature, may optionally be subjected to a heat treatment with a temperature range up to 300 °C, for example up to 200 °C, particularly 80 °C to 180 °C depending on the properties of the paper, and can exhibit excellent oil resistance and / or water resistance, etc.

[0393] As described above, the embodiments have been explained, but it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims.

Examples

[0394] Hereinafter, the present disclosure will be described in detail 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 melting and mixing a hydrophobic compound (A1) and a hydrophobic compound (A2) above the melting point and cooling to room temperature was used.

[0397] [Fabrication of Mold] Using an automatic mold forming machine, the mold was formed. A net-like body was placed on top of a metal pulp mold forming die with a number of suction holes provided at the bottom. A metal tank was placed at the top, and pulp slurry was put into the upper metal tank. From the side opposite to the side where the net-like body of the pulp mold forming die was placed, the pulp-containing aqueous composition was suctioned and dehydrated at 0.1 - 1 MPa through the pulp mold forming die and the net-like body by a vacuum pump, and the solid content (such as pulp) contained in the pulp-containing aqueous composition was deposited on the net-like body to obtain a pulp mold intermediate. Next, the obtained pulp mold intermediate was dried under a pressure of 0.1 - 1 MPa from above and below with a metal osmosis forming die heated to 60 - 200 °C. Thereby, a pulp mold product formed into the shape of a container was manufactured.

[0398] [Practical Oil Resistance Test (25 °C)] Pretreatment was carried out by storing the mold under the conditions of 23 °C and 50% humidity for 12 hours. 100 ml of corn oil at 25 °C was poured into the mold, left at room temperature for 45 minutes, then the corn oil was taken out from the mold, and the degree of oil stain on the mold was evaluated. According to the degree of penetration, the evaluation values were set as follows. 5: No stain on the inside 4: There is stain on the inside. No stain on the back side. 3: There is stain on the inside. Slight stain oozes out on the back side. 2: There is stain on the inside. The stain oozing to the back is less than 50% of the area. 1: There is stain on the inside. The stain oozing to the back is 50% or more and less than 100% of the area. 0: Stain oozes out over the entire back side.

[0399] [Practical Oil Resistance Test (65 °C)] Pretreatment was carried out by storing the mold under the conditions of 23 °C and 50% humidity for 12 hours. 100 ml of corn oil at 65 °C was poured into the mold, left at room temperature for 45 minutes, then the corn oil was taken out from the mold, and the degree of oil stain on the mold was evaluated. According to the degree of penetration, the evaluation values were set as follows. 5: No stain on the inside 4: There is stain on the inside. No stain on the back side. 3: There is penetration on the inner side. There is slight penetration on the back side. 2: There is penetration on the inner side. The penetration to the back side is less than 50% of the area. 1: There is penetration on the inner side. The penetration to the back side is 50% or more and less than 100% of the area. 0: The entire back side is penetrated.

[0400] [Practical water resistance test (100 °C)] The mold was pretreated by storing it for 12 hours under the conditions of 23 °C and 50% humidity. 100 ml of water at 100 °C was poured into the mold, and after leaving it at room temperature for 30 minutes, the water was taken out from the mold, and the degree of penetration of the mold was evaluated. Evaluation values were set as follows according to the degree of penetration. 5: There is no penetration on the inner side 4: There is penetration on the inner side. There is no penetration on the back side. 3: There is penetration on the inner side. There is slight penetration on the back side. 2: There is penetration on the inner side. The penetration to the back side is less than 50% of the area. 1: There is penetration on the inner side. The penetration to the back side is 50% or more and less than 100% of the area. 0: The entire back side is penetrated.

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

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

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

[0404] [Method for measuring the melting point] The melting point was calculated by differential scanning calorimetry (DSC). For the DSC measurement, under a nitrogen atmosphere (nitrogen flow rate 50 mL / min), it was cooled to -20 °C at a rate of 10 °C / 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. Thereafter, the endothermic peak observed during the temperature increase process in the second step of heating to 180 °C at a rate of 10 °C / min was measured.

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

[0406] [Penetration test of the compound] The hydrophobic compound (A) was placed in an iron container with a width of 30 mm, a length of 30 mm, and a depth of 20 mm, heated at 180 °C for 30 minutes until melted, and then allowed to cool to 25 °C by allowing it to cool naturally, thereby preparing a test piece, which was measured according to JIS K 2235 6.4.

[0407] [Penetration test of residue] The aqueous dispersion of the hydrophobic compound (A) was heated at 100 °C for 2 days to obtain a residue from which the liquid medium was removed from the aqueous dispersion of the hydrophobic compound (A). The obtained residue was placed in an iron container with a width of 30 mm, a length of 30 mm, and a depth of 20 mm, heated at 180 °C for 30 minutes until melted, and then allowed to cool to 25 °C by allowing it to cool naturally, thereby preparing a test piece, which was measured according to JIS K 2235 6.4.

[0408] [Method for measuring Shore A hardness of compound] Each of the hydrophobic compound (A) and the hydrophobic compound (A1) was placed in an iron container with a width of 30 mm, a length of 30 mm, and a depth of 20 mm, heated at 180 °C for 30 minutes until melted, and then allowed to cool to 25 °C by allowing it to cool naturally, thereby preparing a test piece. Using a polymer instrument automatic rubber hardness tester P2-A type, the Shore A hardness [1s] after 1 second, the Shore A hardness [3s] after 3 seconds, and the Shore A hardness [PEAK] of the peak strength were calculated. Also, from the obtained results, the difference in Shore A hardness ([Shore A hardness of hydrophobic compound (A1)] - [Shore A hardness of hydrophobic compound (A)]) was also calculated.

[0409] [Method for measuring Shore A hardness of residue] The aqueous dispersion of the hydrophobic compound (A) was heated at 100 °C for 2 days to obtain a residue from which the liquid medium was removed from the aqueous dispersion of the hydrophobic compound (A). The obtained residue was placed in an iron container with a width of 30 mm, a length of 30 mm, and a depth of 20 mm, heated at 180 °C for 30 minutes until melted, and then allowed to cool to 25 °C by allowing it to cool naturally, thereby preparing a test piece. Using a polymer instrument automatic rubber hardness tester P2-A type, the Shore A hardness [1s] after 1 second, the Shore A hardness [3s] after 3 seconds, and the Shore A hardness [PEAK] of the peak strength were calculated.

[0410] <Example 1> As the hydrophobic compound (A1), 2 g of N,N'-ethylenebis(octadecanamide) (bio-based content: 97%, melting point: 143 °C, hexadecane contact angle: 36.1°, Fedors SP value: 9.6), as the hydrophobic compound (A2), 1.4 g of corn oil (Nippon Corn Starch, liquid state at 25 °C), 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 solid by melt mixing. To this solid, 10 g of water was added and pulverized with a spatula. Then, 6.6 g of water was added and treated with a homogenizer at 10000 rpm for 20 minutes to obtain an aqueous dispersion composition of the composition containing the hydrophobic compound (A) (volume abundance ratio of particles of 100 μm or more: 21%, volume median diameter: 53.3 μm). The aqueous dispersion composition was added to a pulp slurry with a concentration of 0.5 wt% so that the hydrophobic compound (A1) was in a ratio of 3 wt% to the pulp in terms of solid content, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When 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), all evaluations were 4 points.

[0411] Using a mixture obtained by mixing 70 parts by mass of corn oil (Nippon Corn Starch, liquid state at 25 °C) as the hydrophobic compound (A2) with respect to 100 parts by mass of N,N'-ethylenebis(octadecanamide) (bio-based content: 97%, melting point: 143 °C, hexadecane contact angle: 36.1°, Fedors SP value: 9.6) as the hydrophobic compound (A1), Shore A hardness -1 was measured.

[0412] <Example 2> An aqueous dispersion composition of the composition containing the hydrophobic compound (A) was obtained (volume abundance ratio of particles of 100 μm or more: 19%, volume median diameter: 47.9 μm) in the same procedure as in Example 1 except that the amount of corn oil as the hydrophobic compound (A2) was changed to 0.70 g. A water-dispersed composition was added to a 0.5 wt% pulp slurry so that the hydrophobic compound (A1) was at a ratio of 3 wt% based on the pulp in terms of solid content, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When 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), all evaluations were 4 points.

[0413] Using a mixture obtained by mixing 35 parts by mass of corn oil (Nippon Corn Starch, liquid state at 25 °C) as the hydrophobic compound (A2) with respect to 100 parts by mass of N,N'-ethylenebis octadecanamide (bio-based degree: 97%, melting point: 143 °C, hexadecane contact angle: 36.1°, Fedors SP value: 9.6) as the hydrophobic compound (A1), Shore A hardness -1 was measured.

[0414] <Example 3> A water-dispersed composition containing a hydrophobic compound (A) was obtained (volume abundance ratio of particles of 100 μm or more: 23%, volume median diameter: 47.9 μm) in the same procedure as in Example 1 except that corn oil was changed to triolein (liquid state at 25 °C, Fedors SP value: 8.93) as the hydrophobic compound (A2). A water-dispersed composition was added to a 0.5 wt% pulp slurry so that the hydrophobic compound (A1) was at a ratio of 3 wt% based on the pulp in terms of solid content, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When 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), all evaluations were 4 points.

[0415] <Example 4> As the hydrophobic compound (A2), corn oil was changed to triolein (state at 25°C: liquid, Fedors SP value: 8.93), and the usage amount was changed to 0.70 g. Otherwise, in the same procedure as in Example 1, an aqueous dispersion composition of the composition containing the hydrophobic compound (A) was obtained (volume occupancy ratio of particles of 100 μm or more: 24%, volume median diameter: 49.3 μm). The aqueous dispersion composition was added to a pulp slurry with a concentration of 0.5 wt% so that the hydrophobic compound (A1) was in a ratio of 3 wt% to the pulp in terms of solid content, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When 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), all evaluations were 4 points.

[0416] <Example 5> As the hydrophobic compound (A2), corn oil was changed to trilinolein (state at 25°C: liquid, Fedors SP value: 8.951). Otherwise, in the same procedure as in Example 1, an aqueous dispersion composition of the composition containing the hydrophobic compound (A) was obtained (volume occupancy ratio of particles of 100 μm or more: 22%, volume median diameter: 52.3 μm). The aqueous dispersion composition was added to a pulp slurry with a concentration of 0.5 wt% so that the hydrophobic compound (A1) was in a ratio of 3 wt% to the pulp in terms of solid content, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When 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), all evaluations were 4 points.

[0417] <Example 6> As the hydrophobic compound (A2), corn oil was changed to trilinolein (state at 25°C: liquid, Fedors SP value: 8.951), and the usage amount was changed to 0.70 g. Otherwise, in the same procedure as in Example 1, an aqueous dispersion composition of the composition containing the hydrophobic compound (A) was obtained (volume occupancy ratio of particles of 100 μm or more: 19%, volume median diameter: 47.9 μm). A pulp slurry with a concentration of 0.5 wt% was added with a hydrophobic compound (A1) so that the ratio of the hydrophobic compound (A1) to the pulp was 3 wt% in terms of solid content, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When 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), all evaluations were 4 points.

[0418] <Example 7> 2 g of N,N'-ethylenebisoleic acid amide (bio-based degree: 97%, melting point: 116 °C, hexadecane contact angle: 42.7°) as the hydrophobic compound (A1), 1.4 g of corn oil (Japanese corn starch, liquid state at 25 °C) as the hydrophobic compound (A2), and further 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 melted and mixed by heating at 180 °C for 30 minutes to obtain a solid. To this solid, 10 g of water was added and pulverized with a spatula. Then, 6.6 g of water was added and treated with a homogenizer at 10000 rpm for 20 minutes to obtain a water-dispersed composition of the composition containing the hydrophobic compound (A) (volume occupancy ratio of particles of 100 μm or more: 18%, volume median diameter: 47.3 μm). A pulp slurry with a concentration of 0.5 wt% was added with a hydrophobic compound (A1) so that the ratio of the hydrophobic compound (A1) to the pulp was 7 wt% in terms of solid content, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When the mold was subjected to a practical oil resistance test (25 °C) and a practical oil resistance test (65 °C), all evaluations were 4 points.

[0419] <Example 8> A water-dispersed composition of the composition containing the hydrophobic compound (A) was obtained in the same procedure as in Example 7 except that the amount of corn oil as the hydrophobic compound (A2) was changed to 0.70 g (volume occupancy ratio of particles of 100 μm or more: 19%, volume median diameter: 46.2 μm). A water-dispersion composition was added to a 0.5 wt% pulp slurry such that the hydrophobic compound (A1) was at a ratio of 7 wt% based on the pulp on a solids basis to prepare an aqueous composition containing pulp. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When 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, all evaluations were 4 points.

[0420] <Example 9> A water-dispersion composition of the composition containing the hydrophobic compound (A) was obtained in the same procedure as in Example 1 except that the amount of corn oil as the hydrophobic compound (A2) was changed to 2.2 g (volume abundance ratio of particles of 100 μm or more: 17%, volume median diameter: 45.6 μm). A water-dispersion composition was added to a 0.5 wt% pulp slurry such that the hydrophobic compound (A1) was at a ratio of 3 wt% based on the pulp on a solids basis to prepare an aqueous composition containing pulp. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When 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, all evaluations were 4 points.

[0421] <Example 10> 2 g of N,N'-ethylenebis(octadecanamide) (biobased degree: 97%, melting point: 143 °C, hexadecane contact angle: 36.1°) as the hydrophobic compound (A1), 1.4 g of glyceryl tripalmitoleate (state at 25 °C: liquid, Fedors SP value: 8.971) 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 melted and mixed by heating at 180 °C for 30 minutes to obtain a solid. To this solid, 10 g of water was added and pulverized with a spatula. Then, 6.6 g of water was added and treated with a homogenizer at 7500 rpm for 20 minutes to obtain an aqueous dispersion composition of the composition containing the hydrophobic compound (A) (volume occupancy ratio of particles of 100 μm or more: 18%, volume median diameter: 47.98 μm). The aqueous dispersion composition was added to a pulp slurry with a concentration of 0.5 wt% so that the hydrophobic compound (A1) was 5 wt% based on the pulp in terms of solid content, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When 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), all evaluations were 4 points.

[0422] <Example 11> 2 g of N,N'-ethylenebis(octadecanamide) (biobased degree: 97%, melting point: 143 °C, hexadecane contact angle: 36.1°) as the hydrophobic compound (A1), 1.4 g of glyceryl tridecanoate (state at 25 °C: liquid, Fedors SP value: 9.138) 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 melt-mixed by heating at 180 °C for 30 minutes to obtain a solid. To this solid, 10 g of water was added and pulverized with a spatula. Then, 6.6 g of water was added and treated with a homogenizer at 7500 rpm for 20 minutes to obtain an aqueous dispersion composition of the composition containing the hydrophobic compound (A) (volume occupancy ratio of particles of 100 μm or more: 23%, volume median diameter: 40.35 μm). The aqueous dispersion composition was added to a pulp slurry with a concentration of 0.5 wt% so that the hydrophobic compound (A1) was 5 wt% based on the pulp in terms of solid content, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When the mold was subjected to a practical oil resistance test (65 °C), the result was 4 points.

[0423] <Example 12> As the hydrophobic compound (A1), 2 g of N,N'-ethylenebis(octadecanamide) (bio-based degree: 97%, melting point: 143°C, hexadecane contact angle: 36.1°), as the hydrophobic compound (A2), 1.4 g of glyceryl trioctanoate (state at 25°C: liquid, Fedors SP value: 9.251), 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 solid obtained by melt mixing. To this solid, 10 g of water was added and pulverized with a spatula. Then, 6.6 g of water was added and treated with a homogenizer at 7500 rpm for 20 minutes to obtain an aqueous dispersion composition of the composition containing the hydrophobic compound (A) (volume abundance ratio of particles of 100 μm or more: 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 hydrophobic compound (A1) was in a ratio of 5 wt% with respect to the pulp in terms of solid content, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When the mold was subjected to a practical oil resistance test (65°C), the result was 4 points.

[0424] <Example 13> As the hydrophobic compound (A1), 2 g of N,N'-ethylenebis(octadecanamide) (bio-based degree: 97%, melting point: 143°C, hexadecane contact angle: 36.1°), as the hydrophobic compound (A2), 1.4 g of tributyl trimellitate (state at 25°C: liquid, Fedors SP value: 10.185), 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 solid obtained by melt mixing. To this solid, 10 g of water was added and pulverized with a spatula. Then, 6.6 g of water was added and treated with a homogenizer at 7500 rpm for 20 minutes to obtain an aqueous dispersion composition of the composition containing the hydrophobic compound (A) (volume ratio of particles of 100 μm or more: 17%, volume median diameter: 44.58 μm). The aqueous dispersion composition was added to a pulp slurry with a concentration of 0.5 wt% so that the hydrophobic compound (A1) was in a ratio of 5 wt% to the pulp on a solid content basis, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When 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), all evaluations were 4 points.

[0425] <Example 14> 2 g of N,N'-ethylenebis(octadecanamide) (biobased degree: 97%, melting point: 143 °C, hexadecane contact angle: 36.1°) as the hydrophobic compound (A1), 0.7 g of sucrose oleate (liquid state at 25 °C, HLB: 1) 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 molten and mixed solid. To this solid, 10 g of water was added and pulverized with a spatula. Then, 6.6 g of water was added and treated with a homogenizer at 7500 rpm for 20 minutes to obtain an aqueous dispersion composition of the composition containing the hydrophobic compound (A) (volume ratio of particles of 100 μm or more: 17%, volume median diameter: 44.58 μm). The aqueous dispersion composition was added to a pulp slurry with a concentration of 0.5 wt% so that the hydrophobic compound (A1) was in a ratio of 5 wt% to the pulp on a solid content basis, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When the mold was subjected to a practical oil resistance test (25 °C) and a practical oil resistance test (65 °C), all evaluations were 4 points.

[0426] <Example 15> As the hydrophobic compound (A1), 2 g of N,N'-ethylenebis(octadecanamide) (bio-based degree: 97%, melting point: 143°C, hexadecane contact angle: 36.1°), as the hydrophobic compound (A2), 0.7 g of sucrose erucate (state at 40°C: liquid, HLB: 2), 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 solid obtained by melt mixing. To this solid, 10 g of water was added and pulverized with a spatula. Then, 6.6 g of water was added and treated with a homogenizer at 7500 rpm for 20 minutes to obtain an aqueous dispersion composition of the composition containing the hydrophobic compound (A) (volume ratio of particles of 100 μm or more: 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 hydrophobic compound (A1) was in a ratio of 5 wt% with respect to the pulp in terms of solid content, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When the mold was subjected to a practical oil resistance test (25°C) and a practical oil resistance test (65°C), the evaluation in each case was 4 points.

[0427] <Example 16> As the hydrophobic compound (A1), 2 g of N,N'-ethylenebis(octadecanamide) (bio-based degree: 97%, melting point: 143°C, hexadecane contact angle: 36.1°), as the hydrophobic compound (A2), 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), 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 solid obtained by melt mixing. To this solid, 10 g of water was added and pulverized with a spatula. Then, 6.6 g of water was added and treated with a homogenizer at 7500 rpm for 20 minutes to obtain an aqueous dispersion composition of a composition containing a hydrophobic compound (A) (volume ratio of particles of 100 μm or more: 17%, volume median diameter: 44.58 μm). The aqueous dispersion composition was added to a pulp slurry with a concentration of 0.5 wt% so that the hydrophobic compound (A1) was in a ratio of 5 wt% based on the pulp in terms of solid content, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When the mold was subjected to a practical oil resistance test (25 °C) and a practical oil resistance test (65 °C), the evaluation in both cases was 4 points.

[0428] <Example 17> 2 g of N,N'-ethylenebis(octadecanamide) (bio-based degree: 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 melted and mixed by heating at 180 °C for 30 minutes to obtain a solid. To this solid, 10 g of water was added and pulverized with a spatula. Then, 6.6 g of water was added and treated with a homogenizer at 7500 rpm for 20 minutes to obtain an aqueous dispersion composition of a composition containing a hydrophobic compound (A) (volume ratio of particles of 100 μm or more: 17%, volume median diameter: 44.58 μm). The aqueous dispersion composition was added to a pulp slurry with a concentration of 0.5 wt% so that the hydrophobic compound (A1) was in a ratio of 5 wt% based on the pulp in terms of solid content, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When the mold was subjected to the practical oil resistance test (25 °C) and the practical oil resistance test (65 °C), both evaluations were 4 points.

[0429] <Example 18> As the hydrophobic compound (A1), 2 g of N,N'-ethylenebis(octadecanamide) (biobased degree: 97%, melting point: 143 °C, hexadecane contact angle: 36.1°), as the hydrophobic compound (A2), 0.7 g of decaglycerin octaoleate (degree of polymerization 10, hydroxy substitution rate: 8 / 12 * 100 [66.7%], state at 25 °C: liquid, HLB: 3.7), 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 melted and mixed by heating at 180 °C for 30 minutes to obtain a solid. To this solid, 10 g of water was added and pulverized with a spatula. Then, 6.6 g of water was added and treated with a homogenizer at 7500 rpm for 20 minutes to obtain an aqueous dispersion composition of the composition containing the hydrophobic compound (A) (volume occupancy ratio of particles of 100 μm or more: 17%, volume median diameter: 44.58 μm). The aqueous dispersion composition was added to a pulp slurry with a concentration of 0.5 wt% so that the hydrophobic compound (A1) was in a ratio of 5 wt% with respect to the pulp in terms of solid content, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold molding machine to produce a mold. When the mold was subjected to the practical oil resistance test (25 °C) and the practical oil resistance test (65 °C), both evaluations were 4 points.

[0430] <Example 19> As the hydrophobic compound (A1), 2 g of N,N'-ethylenebis(octadecanamide) (bio-based degree: 97%, melting point: 143 °C, hexadecane contact angle: 36.1°), as the hydrophobic compound (A2), 1.4 g of castor oil fatty acid ester (Ricksaizer C101 manufactured by Ito Oil Co., Ltd., state at 25 °C: liquid), 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 solid obtained by melt mixing. To this solid, 10 g of water was added and pulverized with a spatula. Then, 6.6 g of water was added and treated at 7500 rpm for 20 minutes using a homogenizer to obtain an aqueous dispersion composition of the composition containing the hydrophobic compound (A) (volume occupancy ratio of particles of 100 μm or more: 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 hydrophobic compound (A1) was in a ratio of 5 wt% with respect to the pulp in terms of solid content, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold molding machine to produce a mold. When the mold was subjected to a practical oil resistance test (25 °C) and a practical oil resistance test (65 °C), the evaluation in both cases was 4 points.

[0431] <Example 20> As the hydrophobic compound (A1), 2 g of N,N'-ethylenebis(octadecanamide) (bio-based degree: 97%, melting point: 143 °C, hexadecane contact angle: 36.1°), as the hydrophobic compound (A2), 1.4 g of refined castor oil (LAV manufactured by Ito Oil Co., Ltd., state at 25 °C: liquid, Fedors SP value: 10.17), 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 solid obtained by melt mixing. To this solid, 10 g of water was added and pulverized with a spatula. Then, 6.6 g of water was added and treated with a homogenizer at 7500 rpm for 20 minutes to obtain an aqueous dispersion composition of the composition containing the hydrophobic compound (A) (volume occupancy ratio of particles of 100 μm or more: 17%, volume median diameter: 44.58 μm). The aqueous dispersion composition was added to a pulp slurry with a concentration of 0.5 wt% so that the hydrophobic compound (A1) was in a ratio of 5 wt% based on the pulp in terms of solid content, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When the mold was subjected to a practical oil resistance test (25 °C) and a practical oil resistance test (65 °C), the evaluation in both cases was 4 points.

[0432] <Example 21> 2 g of N,N'-ethylenebis(octadecanamide) (bio-based degree: 97%, melting point: 143 °C, hexadecane contact angle: 36.1°) as the hydrophobic compound (A1), 1.4 g of diheptylnonyl adipate (state at 25 °C: liquid, Fedors SP value: 9.00 - 9.08) 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 melted and mixed by heating at 180 °C for 30 minutes to obtain a solid. To this solid, 10 g of water was added and pulverized with a spatula. Then, 6.6 g of water was added and treated with a homogenizer at 7500 rpm for 20 minutes to obtain an aqueous dispersion composition of the composition containing the hydrophobic compound (A) (volume occupancy ratio of particles of 100 μm or more: 17%, volume median diameter: 44.58 μm). The aqueous dispersion composition was added to a pulp slurry with a concentration of 0.5 wt% so that the hydrophobic compound (A1) was in a ratio of 5 wt% based on the pulp in terms of solid content, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When the mold was subjected to a practical oil resistance test (25 °C) and a practical oil resistance test (65 °C), the evaluation in both cases was 4 points.

[0433] <Example 22> As the hydrophobic compound (A1), 2 g of N,N'-ethylenebis(octadecanamide) (bio-based degree: 97%, melting point: 143 °C, hexadecane contact angle: 36.1°), as the hydrophobic compound (A2), 1.4 g of diisononyl adipate (state at 25 °C: liquid, Fedors SP value: 9.00), 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 solid obtained by melt mixing. To this solid, 10 g of water was added and pulverized with a spatula. Then, 6.6 g of water was added and treated with a homogenizer at 7500 rpm for 20 minutes to obtain an aqueous dispersion composition of the composition containing the hydrophobic compound (A) (volume occupancy ratio of particles of 100 μm or more: 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 hydrophobic compound (A1) was in a ratio of 5 wt% with respect to the pulp in terms of solid content, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold molding machine to produce a mold. When the mold was subjected to a practical oil resistance test (25 °C) and a practical oil resistance test (65 °C), the evaluation in both cases was 4 points.

[0434] <Example 23> As the hydrophobic compound (A1), 2 g of N,N'-ethylenebis(octadecanamide) (bio-based degree: 97%, melting point: 143 °C, hexadecane contact angle: 36.1°), as the hydrophobic compound (A2), 1.4 g of tris(2-ethylhexyl) trimellitate (state at 25 °C: liquid, Fedors SP value: 9.489), 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 solid obtained by melt mixing. To this solid, 10 g of water was added and pulverized with a spatula. Then, 6.6 g of water was added and treated with a homogenizer at 7500 rpm for 20 minutes to obtain an aqueous dispersion composition of the composition containing the hydrophobic compound (A) (volume ratio of particles of 100 μm or more: 17%, volume median diameter: 44.58 μm). The aqueous dispersion composition was added to a pulp slurry with a concentration of 0.5 wt% so that the hydrophobic compound (A1) was 5 wt% based on the pulp in terms of solid content, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When the mold was subjected to a practical oil resistance test (25 °C) and a practical oil resistance test (65 °C), the evaluation in both cases was 4 points.

[0435] <Example 24> 2 g of N,N'-ethylenebis octadecanamide (bio-based degree: 97%, melting point: 143 °C, hexadecane contact angle: 36.1°) as the hydrophobic compound (A1), 1.4 g of pyromellitic acid (2-ethylhexyl) (liquid at 25 °C, Fedors SP value: 9.502) 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 melted and mixed by heating at 180 °C for 30 minutes to obtain a solid. To this solid, 10 g of water was added and pulverized with a spatula. Then, 6.6 g of water was added and treated with a homogenizer at 7500 rpm for 20 minutes to obtain an aqueous dispersion composition of the composition containing the hydrophobic compound (A) (volume ratio of particles of 100 μm or more: 17%, volume median diameter: 44.58 μm). The aqueous dispersion composition was added to a pulp slurry with a concentration of 0.5 wt% so that the hydrophobic compound (A1) was 5 wt% based on the pulp in terms of solid content, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When the mold was subjected to a practical oil resistance test (25 °C) and a practical oil resistance test (65 °C), the evaluation in both cases was 4 points.

[0436] <Example 25> As the hydrophobic compound (A1), 2 g of N,N'-ethylenebis(octadecanamide) (bio-based degree: 97%, melting point: 143°C, hexadecane contact angle: 36.1°), as the hydrophobic compound (A2), 1.4 g of pentaerythritol ester (state at 25°C: liquid), 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 melt-mixed by heating at 180°C for 30 minutes to obtain a solid. To this solid, 10 g of water was added and pulverized with a spatula. Then, 6.6 g of water was added and treated with a homogenizer at 7500 rpm for 20 minutes to obtain an aqueous dispersion composition of the hydrophobic compound (A) (volume occupancy ratio of particles of 100 μm or more: 17%, volume median diameter: 44.58 μm). The aqueous dispersion composition was added to a pulp slurry with a concentration of 0.5 wt% so that the hydrophobic compound (A1) was in a ratio of 5 wt% to the pulp in terms of solid content, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When the mold was subjected to a practical oil resistance test (25°C) and a practical oil resistance test (65°C), the evaluation in both cases was 4 points.

[0437] <Example 26> As the hydrophobic compound (A1), 2 g of N,N'-ethylenebis(octadecanamide) (bio-based degree: 97%, melting point: 143°C, hexadecane contact angle: 36.1°) pulverized to an average particle diameter of 18 μm by dry pulverization, 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 of the hydrophobic compound (A1) (volume occupancy ratio of particles of 100 μm or more: 4.3%, volume median diameter: 18 μm). As the hydrophobic compound (A2), 2 g of decaglycerin decaoleate (state at 25°C: liquid, HLB: 3.3), 0.16 g of polyethylene glycol trimethylnonyl ether (HLB 13.1), 0.04 g of polyethylene glycol trimethylnonyl ether (HLB 8.1), and 17.8 g of water were added and stirred to obtain an aqueous dispersion composition of the hydrophobic compound (A2). To a pulp slurry with a concentration of 0.5 wt%, an aqueous dispersion composition of the hydrophobic compound (A1) was added so that the hydrophobic compound (A1) was in a ratio of 5 wt% to the pulp on a solid content basis. Subsequently, an aqueous dispersion composition of the hydrophobic compound (A2) was added so that the hydrophobic compound (A2) was in a ratio of 10 wt% to the pulp on a solid content basis, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When the mold was subjected to a practical oil resistance test (25°C) and a practical oil resistance test (65°C), the evaluation in both cases was 4 points.

[0438] <Example 27> As the hydrophobic compound (A1), 2 g of paraffin wax (melting point 69.8°C), 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 - 16, HLB: 7), as the hydrophobic compound (A2), 1 g of corn oil, and 17.8 g of water were mixed to obtain an aqueous dispersion. After heating this aqueous dispersion to 85°C, it was treated with an ultrasonic homogenizer for 20 minutes to obtain an aqueous dispersion composition agent. The obtained aqueous dispersion composition showed the following characteristics. Median diameter D50: 3.2 μm Volume presence ratio of particles of 100 μm or more: 0% Volume presence ratio of particles of 10 μm or more: 34% The aqueous dispersion composition was added to a pulp slurry with a concentration of 0.5 wt% so that the hydrophobic compound (A1) was in a ratio of 10 wt% to the pulp on a solid content basis, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When the mold was subjected to a practical oil resistance test (25°C), the result was 4 points.

[0439] <Example 28> As the hydrophobic compound (A1), 2 g of paraffin wax (melting point 69.8 °C), 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 - 16, HLB: 7), and 17.8 g of water were mixed to obtain an aqueous dispersion. After heating this aqueous dispersion to 85 °C, it was treated with an ultrasonic homogenizer for 20 minutes to obtain an aqueous dispersion composition. The obtained aqueous dispersion composition showed the following properties. Median diameter D50: 0.8 μm Volume occupancy ratio of particles of 100 μm or more: 0% Volume occupancy ratio of particles of 10 μm or more: 12% As the hydrophobic compound (A2), 2 g of decaglycerin decaoleate (state at 25 °C: liquid, HLB: 3.3), 0.16 g of polyethylene glycol trimethylnonyl ether (HLB 13.1), 0.04 g of polyethylene glycol trimethylnonyl ether (HLB 8.1), and 17.8 g of water were added and stirred to obtain an aqueous dispersion composition of the hydrophobic compound (A2). To a pulp slurry with a concentration of 0.5 wt%, the aqueous dispersion composition of the hydrophobic compound (A1) was added so that the hydrophobic compound (A1) was in a ratio of 10 wt% to the pulp on a solid content basis. Subsequently, the aqueous dispersion composition of the hydrophobic compound (A2) was added so that the hydrophobic compound (A2) was in a ratio of 10 wt% to the pulp on a solid content basis to prepare a pulp-containing aqueous composition. The pulp-containing aqueous composition was put into an automatic mold forming machine to produce a mold. When the mold was subjected to a practical oil resistance test (25 °C), the result was 4 points.

[0440] <Comparative Example 1> As the hydrophobic compound (A1), 2 g of N,N'-ethylenebis(octadecanamide) (bio-based degree: 97%, melting point: 143 °C, hexadecane contact angle: 36.1°) pulverized to an average particle diameter of 18 μm by dry pulverization, 0.16 g of polyethylene glycol trimethylnonyl ether (HLB 13.1), 0.04 g of polyethylene glycol trimethylnonyl ether (HLB 8.1), and 17.8 g of water were added and stirred to obtain an aqueous dispersion composition (volume occupancy ratio of particles of 100 μm or more: 4.3%, volume median diameter: 18 μm). The aqueous dispersion composition was added to a 0.5 wt% pulp slurry so that the hydrophobic compound (A1) was at a ratio of 3 wt% based on the pulp on a solids basis, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When 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.

[0441] The aqueous dispersion composition was added to a 0.5 wt% pulp slurry so that the hydrophobic compound (A1) was at a ratio of 5 wt% based on the pulp on a solids basis, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When 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.

[0442] <Comparative Example 2> 2 g of N,N'-ethylenebisoleic acid amide (bio-based degree: 97%, melting point: 116 °C, hexadecane contact angle: 42.7°) ground to an average particle size of 7.4 μm by dry grinding 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 0.5 wt% pulp slurry so that the hydrophobic compound (A1) was at a ratio of 3 wt% based on the pulp on a solids basis, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When 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.

[0443] <Comparative Example 3> A water-dispersible composition was obtained in the same procedure as in Example 1, except that tripropylene glycol (state at 25°C: liquid, octanol / water partition coefficient: -0.50, Fedors SP value: 12.385), a non-hydrophobic compound of a water-miscible liquid, was used instead of the hydrophobic compound (A2). The water-dispersible composition was added to a 0.5 wt% pulp slurry so that the hydrophobic compound (A1) was in a ratio of 3 wt% to the pulp on a solid content basis, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When the mold was subjected to a practical oil resistance test (25°C), the result was 1 point.

[0444] <Comparative Example 4> A water-dispersible composition was obtained in the same procedure as in Example 1, except that tripropylene glycol (state at 25°C: liquid, octanol / water partition coefficient: -0.50, Fedors SP value: 12.385), a non-hydrophobic compound of a water-miscible liquid, was used instead of the hydrophobic compound (A2), and the amount used was changed to 0.70 g. The water-dispersible composition was added to a 0.5 wt% pulp slurry so that the hydrophobic compound (A1) was in a ratio of 3 wt% to the pulp on a solid content basis, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When the mold was subjected to a practical oil resistance test (25°C), the result was 1 point.

[0445] <Comparative Example 5> A water-dispersible composition was obtained in the same procedure as in Example 1, except that 3-methoxy-3-methyl-1-butanol (state at 25°C: liquid, octanol / water partition coefficient: 1.07, Fedors SP value: 10.489), a non-hydrophobic compound of a water-miscible liquid, was used instead of the hydrophobic compound (A2). A water-dispersed composition was added to a 0.5 wt% pulp slurry such that the hydrophobic compound (A1) was at a ratio of 3 wt% based on the pulp on a solids basis to prepare an aqueous composition containing pulp. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When the mold was subjected to a practical oil resistance test (25 °C), the result was 1 point.

[0446] <Comparative Example 6> Instead of the hydrophobic compound (A2), 3-methoxy-3-methyl-1-butanol, a water-miscible liquid and non-hydrophobic compound (liquid state at 25 °C, octanol / water partition coefficient: 1.07, Fedors SP value: 10.489), was used. A water-dispersed composition was obtained in the same procedure as in Example 1 except that the amount used was changed to 0.70 g. A water-dispersed composition was added to a 0.5 wt% pulp slurry such that the hydrophobic compound (A1) was at a ratio of 3 wt% based on the pulp on a solids basis to prepare an aqueous composition containing pulp. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When the mold was subjected to a practical oil resistance test (25 °C), the result was 1 point.

[0447] <Comparative Example 7> 2 g of paraffin wax (melting point 69.8 °C), 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 - 16, HLB: 7), and 17.8 g of water were mixed as the hydrophobic compound (A1) to obtain a water dispersion. After heating this water dispersion to 85 °C, it was treated with an ultrasonic homogenizer for 20 minutes to obtain a water-dispersed composition. The obtained water-dispersed composition showed the following properties. Median diameter D50: 0.8 μm Volume presence ratio of particles of 100 μm or more: 0% Volume presence ratio of particles of 10 μm or more: 12% To a pulp slurry with a concentration of 0.5 wt%, an aqueous dispersion composition of a hydrophobic compound (A1) was added such that the hydrophobic compound (A1) was in a ratio of 10 wt% with respect to the pulp on a solid content basis, and an aqueous composition containing pulp was prepared. The aqueous composition containing pulp was put into an automatic mold forming machine to produce a mold. When the mold was subjected to a practical oil resistance test (25°C), it was at one point.

[0448] <Examples 29 - 34 / Comparative Example 8> Tests were conducted in the same manner as in Example 1, except that the hydrophobic compound (A) was prepared and tested with the composition shown in Table 3.

[0449] The results are summarized in the following table. [Table 1] TIFF2025094940000011.tif255162

[0450] [Table 2] TIFF2025094940000012.tif233166

[0451] [Table 3] TIFF2025094940000013.tif253158

[0452] The properties of the compounds are summarized below. [Table 4] TIFF2025094940000014.tif133169

Claims

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), the hydrophobic compound (A1) is a compound selected from the group consisting of an amine-modified compound, a polycarboxylic acid-modified compound, a paraffin wax, and a microcrystalline wax; The composition, wherein the hydrophobic compound (A2) is a liquid or solid oil not falling under the category of compounds selected from the group consisting of amine-modified compounds, polycarboxylic acid-modified compounds, paraffin waxes, and microcrystalline waxes.

2. The composition of claim 1 which is a water-dispersed composition.

3. The composition according to claim 1 or 2, which is a repellent.

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

5. The composition according to claim 1 or 2, wherein the hydrophobic compound (A1) and the hydrophobic compound (A2) are each independently a compound having a hydrocarbon group having 3 to 40 carbon atoms.

6. The composition according to claim 1 or 2, wherein the hydrophobic compound (A1) is a compound selected from the group consisting of amine-modified compounds, paraffin waxes, and microcrystalline waxes.

7. The composition according to claim 1 or 2, wherein the hydrophobic compound (A1) is an amine-modified compound.

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

9. The hydrophobic compound (A1) is a compound selected from the group consisting of amine-modified compounds, polycarboxylic acid-modified compounds, paraffin wax, and microcrystalline wax; The amine-modified an amine backbone, 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 selected from the group consisting of Y Ｎ１ is 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 at 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 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 aromatic hydrocarbon 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 of 1 to 3. has 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 polycarboxylic acid modification product is a product in which the hydroxy group of one or more carboxyl groups of the polycarboxylic acid is substituted with a hydroxy group of 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 selected from the group consisting of Y Ｃ１ is 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 at 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 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 aromatic hydrocarbon 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 of 1 to 3. A compound substituted with a group represented by the formula: The composition according to claim 1 or 2.

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

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

12. The composition 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 composition according to claim 1 or 2, wherein the amount of the hydrophobic compound (A1) is from 15% by weight to 95% by weight, based on the amount of the hydrophobic compound (A).

14. The composition 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 based on 100 parts by weight of the hydrophobic compound (A1).

15. the composition comprises a dispersant; The composition 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 based on 100 parts by weight of the hydrophobic compound (A).

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 first agent and the second agent are added separately to the pulp base material and mixed for use, the hydrophobic compound (A1) is a compound selected from the group consisting of an amine-modified compound, a polycarboxylic acid-modified compound, a paraffin wax, and a microcrystalline wax; The papermaking additive kit, wherein the hydrophobic compound (A2) is a liquid or solid oil not falling under the category of compounds selected from the group consisting of amine-modified compounds, polycarboxylic acid-modified compounds, paraffin wax, and microcrystalline wax.

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: the hydrophobic compound (A1) is a compound selected from the group consisting of an amine-modified compound, a polycarboxylic acid-modified compound, a paraffin wax, and a microcrystalline wax; The product, wherein the hydrophobic compound (A2) is a liquid or solid oil not falling under the category of compounds selected from the group consisting of amine-modified compounds, polycarboxylic acid-modified compounds, paraffin wax, and microcrystalline wax.

18. The substrate is a pulp substrate, 20. The product of claim 17, wherein the product is a pulp product.

19. A method for producing an article, comprising treating a substrate with the composition of claim 1 or 2.

Images