composition

Abstract

The present invention provides a novel composition containing a hydrophobic compound (A) including a hydrophobic compound (A1) and a hydrophobic compound (A2) different from the hydrophobic compound (A1), the Shore A hardness [peak] of the hydrophobic compound (A) being 10 or more and 100 or less less than the Shore A hardness [peak] of the hydrophobic compound (A1). With this composition, liquid repellency can be imparted to a substrate.

Description

Technical Field

[0001] This invention relates to compositions, particularly compositions capable of imparting liquid-repellent properties to a substrate. Background Technology

[0002] Patent Document 1 discloses a powdered papermaking composition that can improve paper properties such as bulkiness and sizing properties and improve workability.

[0003] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2005-60921 Summary of the Invention

[0004] The technical problem that the invention aims to solve Patent Document 1 does not disclose or imply the use of a combination of multiple hydrophobic compounds. Furthermore, Patent Document 1 does not investigate imparting liquid-repellent properties to the substrate.

[0005] The technical problem of the present invention is to provide a novel composition capable of imparting liquid-repellent properties to a substrate.

[0006] Technical means for solving technical problems The present invention includes the following methods.

[0007] [Item 1] A composition containing a hydrophobic compound (A), wherein the hydrophobic compound (A) comprises a hydrophobic compound (A1) and a hydrophobic compound (A2) different from the hydrophobic compound (A1). The Shore A hardness [peak value] of the above hydrophobic compound (A) is 10 to 100 less than the Shore A hardness [peak value] of the above hydrophobic compound (A1).

[0008] [Item 2] The composition as described in Item 1 is an aqueous dispersion composition.

[0009] [Item 3] The composition as described in Item 1 or 2 is a dispensing agent.

[0010] [Item 4] The composition according to any one of items 1 to 3, wherein the hexadecane contact angle of the above-mentioned hydrophobic compound (A1) is 30° or more.

[0011] [Item 5] The composition according to any one of items 1 to 4, wherein the Shore A hardness [peak value] of the above-mentioned hydrophobic compound (A) is 4.0 or more and 70 or less.

[0012] [Item 6] The composition according to any one of items 1 to 5, wherein the hydrophobic compound (A1) and the hydrophobic compound (A2) are each independently a compound having a hydrocarbon group having 6 or more but less than 40 carbon atoms.

[0013] [Item 7] The composition according to any one of items 1 to 6, wherein the hydrophobic compound (A1) and the hydrophobic compound (A2) are each independently selected from amine modifiers, polyol modifiers, polycarboxylic acid modifiers, and other liquid or solid oils.

[0014] [Item 8] The composition of any one of items 1 to 7, wherein the hydrophobic compound (A1) has an amide structure and the hydrophobic compound (A2) does not have an amide structure.

[0015] [Item 9] The composition as described in any one of items 1 to 8, wherein, The aforementioned hydrophobic compound (A1) is selected from amine modifiers, polyol modifiers, polycarboxylic acid modifiers, paraffin wax, and microcrystalline wax. The above-mentioned amine modified form has an amine skeleton and one or more of the following formula: -Y N -Z N n The indicated group, and at least one -Y N -Z N n Compounds bonded to the nitrogen atoms in the aforementioned amine skeleton, [In the formula,] Y N The reason for selecting Y N1 and Y N2 One or more of the following groups constitute a 1+n valence group: Y N1 It is a directly bonded group composed of one or more groups selected from -O-, -C(=O)-, -C(=NR')-, -C(=S)-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2 and -N(-)2 (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms each time it appears). Y N2 It is a group composed of one or more aliphatic hydrocarbon groups with 1 to 40 carbon atoms that may have substituents, aromatic hydrocarbon rings with 2 to 4 valences that may have substituents, and heterocycles with 2 to 4 valences that may have substituents. Z N It can be a monovalent hydrocarbon group with 1 to 40 carbon atoms or a monovalent polysiloxane group that can have substituents. n is an integer greater than 1 and less than 3. The above-mentioned polyol modifiers are polyols with one or more hydroxyl groups modified by the following formula: -Y O -Z O n The compound shown has substituent groups. [In the formula,] Y O The reason for selecting Y O1 and Y O2 One or more of the following groups constitute a 1+n valence group: Y O1 It is a directly bonded group composed of one or more groups selected from -O-, -C(=O)-, -C(=NR')-, -C(=S)-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2 and -N(-)2 (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms each time it appears). Y O2 It is a group composed of one or more aliphatic hydrocarbon groups with 1 to 40 carbon atoms that may have substituents, aromatic hydrocarbon rings with 2 to 4 valences that may have substituents, and heterocycles with 2 to 4 valences that may have substituents. Z O It can be a monovalent hydrocarbon group with 1 to 40 carbon atoms or a monovalent polysiloxane group that can have substituents. n is an integer greater than 1 and less than 3. The above-mentioned polycarboxylic acid modifiers are polycarboxylic acids in which one or more carboxyl groups are modified by the following formula: -Y C -Z C n The compound shown has substituent groups. [In the formula,] Y C The reason for selecting Y C1 and Y C2 One or more of the following groups constitute a 1+n valence group: Y C1 It is a directly bonded group composed of one or more groups selected from -O-, -C(=O)-, -C(=NR')-, -C(=S)-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2 and -N(-)2 (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms each time it appears). Y C2 It is a group composed of one or more aliphatic hydrocarbon groups with 1 to 40 carbon atoms that may have substituents, aromatic hydrocarbon rings with 2 to 4 valences that may have substituents, and heterocycles with 2 to 4 valences that may have substituents. Z C It can be a monovalent hydrocarbon group with 1 to 40 carbon atoms or a monovalent polysiloxane group that can have substituents. n is an integer greater than 1 and less than 3.

[0016] [Item 10] The composition as described in any one of items 1 to 9, wherein, The aforementioned hydrophobic compound (A2) has a hydrocarbon group with 3 or more carbon atoms. The melting point of the above hydrophobic compound (A2) is below 40°C.

[0017] [Item 11] The composition as described in any one of items 1 to 10, wherein, The amount of the hydrophobic compound (A1) is 15% by weight or more and 95% by weight or less, relative to the hydrophobic compound (A) mentioned above.

[0018] [Item 12] The composition as described in any one of items 1 to 11, wherein, The amount of the hydrophobic compound (A2) is 5 to 500 parts by weight relative to 100 parts by weight of the hydrophobic compound (A1).

[0019] [Item 13] The composition as described in any one of items 1 to 12, wherein, The above-mentioned hydrophobic compound (A1) has a melting point above 50°C. The melting point of the above hydrophobic compound (A2) is below 40°C.

[0020] [Item 14] The composition as described in any one of items 1 to 13, wherein, The melting point of the above hydrophobic compound (A1) is more than 30°C higher than that of the above hydrophobic compound (A2).

[0021] [Item 15] The composition as described in any one of items 1 to 14, wherein, The above composition contains a dispersant. The amount of the above dispersant is 0.1 parts by weight or more and 100 parts by weight relative to 100 parts by weight of the hydrophobic compound (A).

[0022] [Item 16] A papermaking additive kit, comprising a first agent and a second agent, The first agent mentioned above contains a hydrophobic compound (A1). The second agent mentioned above contains a hydrophobic compound (A2), which is different from the hydrophobic compound (A1). The Shore A hardness [peak value] of the aforementioned hydrophobic compound (A) is 10 to 100 lower than that of the aforementioned hydrophobic compound (A1). The first agent and the second agent mentioned above are added and mixed into the pulp substrate for use.

[0023] [Item 17] An article comprising a substrate and a hydrophobic compound (A), wherein the hydrophobic compound (A) comprises a hydrophobic compound (A1) and a hydrophobic compound (A2) different from the hydrophobic compound (A1). The Shore A hardness [peak value] of the above hydrophobic compound (A) is 10 to 100 less than the Shore A hardness [peak value] of the above hydrophobic compound (A1).

[0024] [Item 18] The article as described in Item 17, wherein the substrate is a pulp substrate and the article is a pulp article.

[0025] [Item 19] A method of manufacturing an article, comprising a step of treating a substrate with the composition of any one of items 1 to 15, or the papermaking additive kit described in item 16.

[0026] Invention Effects According to the present invention, liquid-repellent properties can be effectively imparted to the substrate. Detailed Implementation

[0027] <Definition of Terms> In this specification, "n-valent group" refers to a group having n valence bonds, that is, a group forming n bonds. Additionally, "n-valent organic group" refers to a carbon-containing n-valent group. There is no particular limitation on such organic groups; they can be hydrocarbon groups or their derivatives. Hydrocarbon derivatives refer to groups having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, or other groups at the end of the hydrocarbon group or in the molecular chain.

[0028] As used in this specification, "hydrocarbon group" is a group containing carbon and hydrogen, which is a group that has had a hydrogen atom removed from a hydrocarbon. There are no particular limitations on what constitutes such a hydrocarbon group; examples include C. 1－20 Hydrocarbon groups, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The aforementioned "aliphatic hydrocarbon group" can be straight-chain, branched, or cyclic, and can be saturated or unsaturated. Furthermore, the hydrocarbon group can contain one or more ring structures. Where explicitly stated, the hydrocarbon group can be substituted by one or more substituents.

[0029] In this specification, whether or not the terms "independent each time it appears", "independent of each other", "independent of each other" or the same expression are explicitly stated, unless otherwise stated, when defining terms (symbols) that may appear multiple times in a chemical structure, the definition shall be applied independently each time it appears.

[0030] It should be understood that the chemical structures described in this specification do not include chemical structures that are considered chemically impossible or extremely unstable by those skilled in the art.

[0031] <Composition> The compositions of the present invention contain a hydrophobic compound (A) comprising a hydrophobic compound (A1) and a hydrophobic compound (A2) different from the aforementioned hydrophobic compound (A1). The compositions of the present invention can be used as treatment agents (e.g., barrier coating agents, surface treatment agents, repellents (liquid repellents), particularly repellents), adhering to a substrate (particularly pulp substrate), and can impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the substrate. They can also function as water-resistant agents, oil-resistant agents, water-repellent agents, oil repellents, and / or stain-resistant agents. For example, the repellents of the present invention exhibit excellent oil resistance (e.g., room temperature oil resistance, high temperature oil resistance, stain resistance), etc., which can reduce the necessary amount to be added.

[0032] The composition of the present invention may be the hydrophobic compound (A) itself, or may be used as a treatment agent (especially a peeling agent), or may be combined with other components described below.

[0033] The compositions of the present invention may be free from any one of the following compounds: fluoroalkyl compounds having 8 or more carbon atoms, perfluoroalkyl compounds having 8 or more carbon atoms, fluoroalkyl compounds having 4 or more carbon atoms, perfluoroalkyl compounds having 4 or more carbon atoms, perfluoroalkyl compounds, fluoroalkyl compounds, and compounds having fluorine atoms. Even without these fluorine compounds, the compositions of the present invention can impart liquid-repellent properties to the substrate.

[0034] The volume fraction of particles larger than 100 μm, as measured by laser diffraction scattering, in the composition of the present invention can be 0.1% or more, 0.3% or more, 0.5% or more, 1% or more, 1.5% or more, 3% or more, 4% or more, 5% or more, or 10% or more, and can be less than 50%, less than 30%, less than 20%, less than 15%, less than 10%, less than 5%, less than 3%, or less than 1.5%. The method for setting the volume fraction of particles larger than 100 μm, as measured by laser diffraction scattering, within the above range is not limited; for example, a pulverizer or homogenizer can be used to refine the particles in the raw materials and / or dispersion.

[0035] The volume median particle size in the composition of the present invention, measured by laser diffraction scattering, can 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 can be less than 300 μm, less than 200 μm, less than 100 μm, less than 50 μm, less than 30 μm, less than 20 μm, less than 10 μm, less than 5 μm, or less than 1 μm. In the present invention, the volume median particle size refers to the median particle size (D50) in the particle size distribution of the volume reference obtained by laser diffraction scattering.

[0036] When the composition contains a liquid medium (e.g., the composition is an aqueous dispersion), the penetration at 25°C of the residue after the liquid medium has been removed from the composition can 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 can be 200 or less, 150 or less, 125 or less, or 100 or less.

[0037] The conditions for determining penetration can be in accordance with the description in JIS K 2235 6.4.

[0038] When the composition contains a liquid medium (e.g., the composition is an aqueous dispersion), the hardness of the residue after the liquid medium has been removed from the composition can be as follows.

[0039] The peak strength of the Shore A hardness [peak value] during the test can be above 0.5, above 1.0, above 1.5, above 2.0, above 2.5, above 3.0, above 4.0, above 5.0, above 7.5 or above 10.0, and can be below 80, below 75, below 70, below 65 or below 60.

[0040] The Shore A hardness after 1 second from the start of the test, i.e., the Shore A hardness [1s], can be above 0.5, above 1.0, above 1.5, above 2.0, above 2.5, above 3.0, above 4.0, above 5.0, above 7.5, or above 10.0, and can be below 80, below 75, below 70, below 65, or below 60.

[0041] The Shore A hardness after 3 seconds from the start of the test, i.e., the Shore A hardness [3s], can be 0.5 or higher, 1.0 or higher, 1.5 or higher, 2.0 or higher, 2.5 or higher, 3.0 or higher, 4.0 or higher, 5.0 or higher, 7.5 or higher, or 10.0 or higher, and can be below 80, below 75, below 70, below 65, or below 60.

[0042] [Hydrophobic compound (A)] The hydrophobic compound (A) of the present invention is a mixture comprising a hydrophobic compound (A1) and a hydrophobic compound (A2) different from the above-described hydrophobic compound (A1). The hydrophobic compound (A) of the present invention is the effective component when the composition of the present invention is used as a repellent, adhering to a substrate (particularly pulp substrate) and imparting liquid-repellent properties, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the substrate.

[0043] [Characteristics, etc.] The properties that hydrophobic compound (A), hydrophobic compound (A1), and hydrophobic compound (A2) can possess are described below. In the following text, when referring to the properties of hydrophobic compound (A) itself, hydrophobic compound (A) refers to a mixture obtained by melting and mixing hydrophobic compound (A1) and hydrophobic compound (A2) above their melting points and then cooling it at room temperature.

[0044] (Solubility properties) Hydrophobic compounds (A1) and (A2) are hydrophobic and have low water solubility. The water solubility of hydrophobic compounds (A1) and (A2) at 25°C can be independently less than 3.0 g / L, less than 1.0 g / L, less than 0.5 g / L, less than 0.1 g / L, or less than 0.01 g, for example, less than 1.0 g / L. Water solubility can be calculated by adding small amounts of the compound to a specified amount of water (25°C) and calculating the amount dissolved at the point when no further dissolution is observed (visible floating or precipitation, crystallization, turbidity, etc.). Compounds with high water solubility (e.g., compounds that are water-mixable liquids) cannot be called hydrophobic compounds.

[0045] The solubility parameters (SP values) of hydrophobic compounds (A1) and (A2) can be independently 3.0 or higher, 4.0 or higher, 5.0 or higher, 6.0 or higher, 7.0 or higher, 8.0 or higher, 9.0 or higher, 10.0 or higher, or 11.0 or higher; and can be independently 15.0 or lower, 14.0 or lower, 13.0 or lower, 12.0 or lower, 10.0 or lower, 9.0 or lower, or 8.0 or lower, preferably 10.5 or lower, and particularly 10.0 or lower. The SP values ​​can be determined according to Fedors' formula (Polym. Eng. Sci., 14 [2], 147 (1974)). Only hydrophobic compound (A1), only hydrophobic compound (A2), or both can satisfy the above ranges, preferably both.

[0046] The difference in SP values ​​between hydrophobic compound (A1) and hydrophobic compound (A2) can exceed 0, be 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 can 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. It is permissible for either hydrophobic compound (A1) or hydrophobic compound (A2) to have a larger value. When multiple compounds of each of hydrophobic compounds (A1) and (A2) are present, the values ​​can be calculated using a weighted average based on weight ratio. In this specification, unless otherwise specified, the difference is an absolute difference.

[0047] The octanol / water partition coefficients (logPow) of hydrophobic compounds (A1) and (A2) can be independently 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 can 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 hydrophobic compound (A1), only hydrophobic compound (A2), or both may satisfy the above ranges, preferably both.

[0048] The difference in octanol / water partition coefficient (logPow) between hydrophobic compound (A1) and hydrophobic compound (A2) can be greater than 0, greater than 0.1, greater than 0.3, greater than 0.5, greater than 1.0, greater than 1.5, or greater than 2.0; and can be less than 5.0, less than 4.5, less than 4.0, less than 3.0, less than 2.5, less than 2.0, less than 1.5, less than 1.0, less than 0.5, less than 0.3, or less than 0.1, preferably less than 2.5, more preferably less than 1.0. It is permissible for either hydrophobic compound (A1) or hydrophobic compound (A2) to have a larger value. When multiple compounds of each of hydrophobic compounds (A1) and (A2) are present, the values ​​can be calculated using a weighted average based on weight ratio.

[0049] The HLB value (hydrophile-lipophile balance) of the hydrophobic compound (A2) can be 0.5 or higher or 1.0 or higher, and can be 11.5 or lower, 11.0 or lower, 10.5 or lower, 10.0 or lower, 9.5 or lower, 9.0 or lower, 8.5 or lower, 8.0 or lower, 7.5 or lower, or 7.0 or lower. The effects of the present invention can be well obtained by setting the value below the above upper limit.

[0050] The HLB (hydrophile-lipophile balance) value, proposed by WG Griffin, is a numerical value assigned to nonionic surfactants. It represents the balance between the strength of the lipophilic group (alkyl group, etc.) and the hydrophilic group (polyoxyalkylene chain, etc.) of a nonionic surfactant. In this invention, the HLB value is the calculated value obtained by the Griffin method (references: WG Griffin, J. Soc. Cosmetic Chemists, 1, 311 (1949) and WG Griffin, J. Soc. Cosmetic Chemists, 5, 249 (1954)). For substances with catalog values, the catalog value can be used as a simple method of judgment; however, if the catalog value and the calculated value differ, the calculated value should be used.

[0051] The HLB value of hydrophobic compound (A1) can be larger than that of hydrophobic compound (A2), or hydrophobic compound (A2) can have a larger value. When multiple hydrophobic compounds (A1) and (A2) are present, the values ​​can be calculated using a weighted average based on the weight ratio.

[0052] (Thermal properties) When hydrophobic compound (A1) and hydrophobic compound (A2) are mixed to form hydrophobic compound (A) (mixture), the endothermic peak in the DSC of hydrophobic compound (A1) (monomer) can shift to a lower temperature. The endothermic peak temperature in the differential scanning calorimetry (DSC) of the aforementioned hydrophobic compound (A1) shifts to a lower temperature by 2°C to 80°C. The endothermic peak that causes the lower temperature shift can be any peak of the hydrophobic compound (A1) (e.g., the maximum peak, any endothermic peak with a peak intensity in the top 30%), and at least one peak (e.g., more than 50%, more than 70%, or 100%) in the range of -50°C to 300°C (e.g., -30°C to 240°C, especially -20°C to 180°C, especially 0°C to 180°C) can shift to a lower temperature. The temperature shift can be above 0.5°C, above 1°C, above 1.5°C, above 2°C, above 2.5°C, above 3°C, above 4°C, above 6°C, above 8°C, above 10°C, above 12°C, above 15°C, above 20°C, or above 30°C; and can also be below 80°C, below 75°C, below 65°C, below 55°C, below 45°C, below 35°C, below 25°C, below 20°C, below 15°C, below 12°C, below 11°C, or below 10°C, for example, below 20°C; in one embodiment, it can be above 0.5°C and below 80°C, particularly above 0.5°C and below 20°C, above 3°C and below 12°C, or above 3°C and below 11°C. It can be considered that by combining two hydrophobic compounds, the thermal properties change, and the endothermic peak in the DSC shifts to a lower temperature. The aforementioned hydrophobic compound (A1) can have more than one endothermic peak above 45°C, which can shift to a lower temperature. The endothermic peak that causes a low-temperature shift in the preferred hydrophobic compound (A1) is the endothermic peak at the highest temperature side of the measurement range, such as a peak accompanied by melting (melting point peak). This endothermic peak excludes endothermic peaks resulting from compound decomposition, but rather refers to endothermic peaks within the range where the compound does not decompose. In the case of compounds that decompose without melting, it can be understood that the melting point of the compound is at least above the decomposition temperature.

[0053] The DSC measurement conditions are as follows. DSC is performed by cooling to below -20°C in a nitrogen atmosphere, followed by heating to above 180°C at a rate of 10°C / min, and measuring the endothermic peak observed during this heating process. The amount of heat absorbed is calculated by measuring the heat generated within ±10°C of the endothermic peak temperature.

[0054] The melting points of hydrophobic compounds (A1) and (A2) may be independently -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 be independently below 250°C, below 225°C, below 200°C, below 150°C, below 130°C, below 120°C, below 110°C, below 100°C, below 80°C, below 50°C, below 40°C, below 30°C, below 20°C, below 10°C, below 0°C, or below -10°C. Only hydrophobic compound (A1), only hydrophobic compound (A2), or both may satisfy the above ranges, preferably both. The hydrophobic compound (A1) is a solid at room temperature (melting point above 30°C), for example, above 50°C, while the hydrophobic compound (A2) can have a melting point below 40°C, for example, below 30°C (less than 30°C), and particularly is a liquid at room temperature (melting point below 20°C). Specifically, the hydrophobic compound (A1) can have a melting point above 50°C, while the hydrophobic compound (A2) can have a melting point below 40°C.

[0055] The difference in melting points between the hydrophobic compound (A1) and the hydrophobic compound (A2) can exceed 0°C, be 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, it can be 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, and even more preferably 90°C or more. It can also be below 300°C, below 250°C, below 200°C, below 150°C, below 100°C, below 80°C, below 60°C, below 50°C, below 40°C, below 30°C, below 20°C, or below 10°C. The value can be larger for either the hydrophobic compound (A1) or the hydrophobic compound (A2), with a particularly preferred value for the hydrophobic compound (A1). When multiple hydrophobic compounds (A1) and (A2) are present, the values ​​can be calculated using a weighted average based on the weight ratio. For example, the hydrophobic compound (A1) can have a larger melting point than the hydrophobic compound (A2); for instance, the melting point of the hydrophobic compound (A1) can be at least 30°C higher than that of the hydrophobic compound (A2).

[0056] (Mechanical properties) The penetration at 25°C of the hydrophobic compound (A) can 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 can be less than 200, less than 150, less than 125, or less than 100.

[0057] The conditions for determining penetration can be in accordance with JIS K 2235 6.4.

[0058] The 25°C penetration of hydrophobic compound (A) can be less than the larger of the 25°C penetration values ​​of hydrophobic compounds (A1) or (A2), and the difference ([(the larger of the 25°C penetration values ​​of hydrophobic compounds (A1) or (A2)]-[25°C penetration values ​​of hydrophobic compound (A)]) can be greater than 0, greater than 2, greater than 5, greater than 10, greater than 15, greater than 20, greater than 30, greater than 40, or greater than 50, and can be less than 100, less than 80, less than 70, less than 60, less than 50, less than 40, less than 30, less than 20, or less than 10.

[0059] The Shore A hardness of hydrophobic compound (A) can be shown below.

[0060] The Shore A hardness [peak value] during the test can be above 0.5, above 1.0, above 1.5, above 2.0, above 2.5, above 3.0, above 4.0, above 5.0, above 7.5, or above 10.0, for example, above 5.0; and can be below 80, below 75, below 70, below 65, or below 60, for example, below 60.

[0061] The Shore A hardness after 1 second from the start of the test, i.e., the Shore A hardness [1s], can be 0.5 or higher, 1.0 or higher, 1.5 or higher, 2.0 or higher, 2.5 or higher, 3.0 or higher, 4.0 or higher, 5.0 or higher, 7.5 or higher, or 10.0 or higher, for example, 10 or higher; and can also be below 80, below 75, below 70, below 65, or below 60, for example, below 60.

[0062] The Shore A hardness after 3 seconds from the start of the test, i.e., the Shore A hardness [3s], can be 0.5 or higher, 1.0 or higher, 1.5 or higher, 2.0 or higher, 2.5 or higher, 3.0 or higher, 4.0 or higher, 5.0 or higher, 7.5 or higher, or 10.0 or higher, for example, 10 or higher; and can also be below 80, below 75, below 70, below 65, or below 60, for example, below 60.

[0063] The preferred hydrophobic compound (A) has a Shore A hardness that is less than the larger Shore A hardness of either hydrophobic compound (A1) or (A2), and the difference can be as follows.

[0064] [The larger of the peak values ​​of the Shore A hardness of the hydrophobic compound (A1) or (A2)] - [The peak value of the Shore A hardness of the hydrophobic compound (A)] can be greater than 0, greater than 2, greater than 5, greater than 10, greater than 15, greater than 20, greater than 25, greater than 30, greater than 35, greater than 40, greater than 45, or greater than 50, for example, greater than 10, especially greater than 20, greater than 25, greater than 30, greater than 35, greater than 40, greater than 50, or greater than 55. 60 or above, 65 or above, or 70 or above, for example, 56 or above; and can be below 100, below 90, below 80, below 70, below 60, below 50, below 40, below 30, below 20, or below 10, preferably below 90, especially below 80; in one mode, it is 10 or above 100, 30 or above 90, 35 or above 90, 40 or above 90, 56 or above 90, especially 56 or above 80.

[0065] [The larger of the Shore A hardness values ​​[1s] of the hydrophobic compound (A1) or (A2)] - [The Shore A hardness [1s] of the hydrophobic compound (A) can be greater than 0, greater than 2, greater than 5, greater than 10, greater than 15, greater than 20, greater than 25, greater than 30, greater than 35, greater than 40, greater than 45, or greater than 50, for example greater than 10, especially greater than 20, greater than 25, greater than 30, greater than 35, greater than 40, greater than 50, or greater than 55. 60 or above, 65 or above, or 70 or above, for example, 56 or above; and can be below 100, below 90, below 80, below 70, below 60, below 50, below 40, below 30, below 20, or below 10, preferably below 90, especially below 80; in one mode, it is 10 or above 100, 30 or above 90, 35 or above 90, 40 or above 90, 56 or above 90, especially 56 or above 80.

[0066] [The larger of the Shore A hardness values ​​[3s] of the hydrophobic compound (A1) or (A2)] - [The Shore A hardness [3s] of the hydrophobic compound (A) can be greater than 0, greater than 2, greater than 5, greater than 10, greater than 15, greater than 20, greater than 25, greater than 30, greater than 35, greater than 40, greater than 45, or greater than 50, for example greater than 10, especially greater than 20, greater than 25, greater than 30, greater than 35, greater than 40, greater than 50, greater than 55. 60 or above, 65 or above, or 70 or above, for example, 56 or above; and can be below 100, below 90, below 80, below 70, below 60, below 50, below 40, below 30, below 20, or below 10, preferably below 90, especially below 80; in one mode, it is 10 or above 100, 30 or above 90, 35 or above 90, 40 or above 90, 56 or above 90, especially 56 or above 80.

[0067] The Shore A hardness of hydrophobic compound (A1) can be greater than that of hydrophobic compound (A2).

[0068] (Liquid-repelling properties) The HD (n-hexadecane) contact angles of the hydrophobic compounds (A1) and (A2) can be independently 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, and more preferably 30° or more; and can be independently 100° or less, 90° or less, or 75° or less. By having the hydrophobic compounds (A1) and (A2) independently possessing HD contact angles of the lower limit or above as described above, good liquid repellency (especially oil repellency) can be imparted to the substrate. The HD contact angle is the static contact angle of the spin-coated film of the hydrophobic compound (A), and is the value obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle after 1 second. Only the hydrophobic compound (A1), only the hydrophobic compound (A2), or both can satisfy the above ranges, preferably both of them satisfy the above ranges.

[0069] The difference in HD contact angle between hydrophobic compound (A1) and hydrophobic compound (A2) can be greater than 0°, greater than 5°, greater than 10°, greater than 15°, greater than 20°, greater than 25°, or greater than 30°, and can be less than 60°, less than 50°, less than 40°, less than 30°, less than 20°, or less than 10°. It can be that hydrophobic compound (A1) or hydrophobic compound (A2) has a larger value. When multiple hydrophobic compounds (A1) and (A2) are present, the values ​​can be calculated using a weighted average based on the weight ratio.

[0070] The water contact angles of hydrophobic compounds (A1) and (A2) can be independently 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more, and can be independently 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. By having the hydrophobic compounds (A1) and (A2) independently possess water contact angles above the lower limit mentioned above, good liquid repellency (especially water repellency) can be imparted to the substrate. The water contact angle is the static contact angle of the spin-coated film of hydrophobic compound (A), and is the value obtained by adding 2 μL of water to the spin-coated film and measuring the contact angle after 1 second. Only hydrophobic compound (A1), only hydrophobic compound (A2), or both can satisfy the above ranges, preferably both satisfy the above ranges.

[0071] The difference in water contact angle between hydrophobic compound (A1) and hydrophobic compound (A2) can be greater than 0°, greater than 5°, greater than 10°, greater than 15°, greater than 20°, greater than 25°, or greater than 30°, and can be less than 60°, less than 50°, less than 40°, less than 30°, less than 20°, or less than 10°. The hydrophobic compound (A1) or hydrophobic compound (A2) can have a larger value. When multiple hydrophobic compounds (A1) and (A2) are present, the values ​​can be calculated using a weighted average based on the weight ratio.

[0072] (Other characteristics) Hydrophobic compounds (A1) and (A2) are preferably bio-based compounds containing bio-based carbon. The bio-based content is determined based on ASTM D6866. The bio-based content of hydrophobic compounds (A1) and (A2) can each independently be 20% or more, preferably 30% or more, more preferably 50% or more, further preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example, 100%. A high bio-based content means less use of fossil resources such as petroleum; from this perspective, it can be said that the higher the bio-based content of hydrophobic compound (A), the better. Only hydrophobic compound (A1), only hydrophobic compound (A2), or both may satisfy the above ranges, preferably both.

[0073] The hydrophobic compounds (A1) and (A2) each independently exhibit a biodegradability of preferably 5% or more after 180 days. Higher biodegradability is preferable from the perspective of reducing environmental impact. The biodegradability of the hydrophobic compounds (A1) and (A2) after 180 days can, for example, be independently 10% or more, 20% or more, 30% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, preferably 30% or more, more preferably 50% or more, further preferably 70% or more, and most preferably 80% or more. The biodegradability of the hydrophobic compounds (A1) and (A2) after 60 days each independently preferably exhibits a biodegradability of preferably 5% or more. Higher biodegradability is preferable from the perspective of reducing environmental impact. The biodegradability of hydrophobic compounds (A1) and (A2) at 60 days can, for example, be independently 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, or 45% or more, preferably 10% or more, more preferably 30% or more. This biodegradability can be as specified in JIS K 6953-1 or ASTM D6400. Only hydrophobic compound (A1), only hydrophobic compound (A2), or both may satisfy the above ranges, preferably both.

[0074] The hydrophobic compound (A) exhibits a biodegradability of at least 5% after 180 days. Higher biodegradability is preferred from the perspective of reducing environmental impact. The biodegradability of the hydrophobic compound (A) after 180 days can be, for example, 10% or more, 20% or more, 30% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, preferably 30% or more, more preferably 50% or more, further preferably 70% or more, and most preferably 80% or more. The hydrophobic compound (A) also exhibits a biodegradability of at least 5% after 60 days. Higher biodegradability is preferred from the perspective of reducing environmental impact. The biodegradability of the hydrophobic compound (A) after 60 days can be, for example, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, or 45% or more, preferably 10% or more, more preferably 30% or more. The hydrophobic compound (A) is particularly preferred to have higher biodegradability than the hydrophobic compounds (A1) and (A2) with lower biodegradability. The difference can be greater than 0%, 5% or more, 10% or more, 15% or more, 20% or more, 25% or more, or 30% or more, and can be less than 60%, 50% or less, 40% or less, 30% or less, 20% or less, or 10% or less.

[0075] The biodegradability of hydrophobic compound (A) at 180 days can be higher than that of hydrophobic compound (A1) at 180 days, and it can also be higher than that of hydrophobic compound (A2) at 180 days. The difference between the biodegradability of hydrophobic compound (A) and that of hydrophobic compound (A1) at 180 days can be greater than 1%, greater than 2.5%, greater than 5%, greater than 7.5%, greater than 10%, greater than 15%, greater than 25%, greater than 30%, or greater than 40%, and can be less than 90%, less than 80%, less than 70%, less than 60%, less than 50%, less than 40%, less than 30%, or less than 20%. The difference between the biodegradability of hydrophobic compound (A) and that of hydrophobic compound (A2) at 180 days can be greater than 1%, greater than 2.5%, greater than 5%, greater than 7.5%, greater than 10%, greater than 15%, greater than 25%, greater than 30%, or greater than 40%, and can be less than 90%, less than 80%, less than 70%, less than 60%, less than 50%, less than 40%, less than 30%, or less than 20%.

[0076] [Structure, etc.] The structure of the hydrophobic compound (A) will be described below. In each description, the structure of either hydrophobic compound (A) (A1 or A2) or both of them may be described, and it is preferred that both of them satisfy the characteristics.

[0077] The hydrophobic compounds (A1) and (A2) of the present invention may each independently lack any one of the following groups: fluoroalkyl groups with 8 or more carbon atoms, perfluoroalkyl groups with 8 or more carbon atoms, fluoroalkyl groups with 4 or more carbon atoms, perfluoroalkyl groups with 4 or more carbon atoms, perfluoroalkyl groups, fluoroalkyl groups, and fluorine atoms. Even if the hydrophobic compounds (A1) and (A2) independently lack these fluorine-containing groups, they can still impart liquid-repellent properties to the substrate.

[0078] Hydrophobic compounds (A1) and (A2) can each independently be compounds containing a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group that may have substituents. From the viewpoint of improving liquid repellency, hydrophobic compounds (A1) and (A2) can each independently have a hydrocarbon group having 3 to 40 carbon atoms (e.g., an aliphatic hydrocarbon group), or hydrophobic compound (A1) can have a hydrocarbon group having 6 to 40 carbon atoms and hydrophobic compound (A2) can have a hydrocarbon group having 3 to 40 carbon atoms.

[0079] (Can be a monovalent hydrocarbon group with substituents) Hydrophobic compounds (A1) and (A2) may each independently contain a monovalent hydrocarbon group that may have substituents.

[0080] The hydrocarbon group can be a monovalent hydrocarbon group with 1 to 40 carbon atoms. The hydrocarbon group can be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, such as a saturated or unsaturated aliphatic hydrocarbon group. Examples of aliphatic hydrocarbon groups include alkyl groups and groups having 1 to 4 (e.g., 1 to 2) unsaturated carbon bonds. The hydrocarbon group can be branched, cyclic, or linear, more preferably linear. It is preferred that either or both of the hydrophobic compounds (A1) and (A2) have unsaturated hydrocarbon groups.

[0081] The number of carbon atoms in the hydrocarbon group can be 1 or more, 3 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 3 or more, 6 or more, 10 or more, 12 or more, or 16 or more, for example, 10 or more; and can be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, 25 or less, or 20 or less.

[0082] The hydrocarbon group may have substituents, preferably 4 or less, more preferably 1 or no substituents. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms each time it appears). The substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon group with substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more; and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, a hydrocarbon group may have 1 to 3 (e.g., 1) -OR' (especially -OH) as substituents (e.g., at positions other than the terminal).

[0083] (Monovalent polysiloxane) The hydrophobic compounds (A1) and (A2) can each independently have a monovalent polysiloxane group. Similar to the (monovalent) hydrocarbon group, the (monovalent) polysiloxane group can impart liquid-repellent properties to the substrate.

[0084] Polysiloxane can be derived from the following formula: -[-Si(R s )2-O-] a -express, [In the formula,] R sEach time it appears, it is independently a hydrocarbon group or reactive group with 1 to 40 carbon atoms. a is an integer greater than 5 and less than 10,000.

[0085] R s It is a hydrocarbon group or reactive group with 1 to 40 carbon atoms.

[0086] Examples of hydrocarbon groups with 1 to 40 carbon atoms include hydrocarbon groups with 1 to 5 carbon atoms and hydrocarbon groups with 6 to 40 carbon atoms.

[0087] Examples of hydrocarbon groups with 1 to 5 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and other hydrocarbon groups with 1 to 5 carbon atoms (especially aliphatic hydrocarbon groups, particularly alkyl groups, such as methyl or ethyl, especially methyl).

[0088] The hydrocarbon group having 6 to 40 carbon atoms can be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, and particularly preferably a saturated aliphatic hydrocarbon group (alkyl). The hydrocarbon group can be cyclic, linear, or branched, preferably linear. The number of carbon atoms in the hydrocarbon group can be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, preferably 10 or more, more preferably 12 or more; and can be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, more preferably 25 or less.

[0089] Examples of reactive groups include groups having functional groups (e.g., hydroxyl, amino, mercapto, epoxy, carboxyl, haloalkyl, vinyl, (meth)acrylate, (meth)acryloyloxy, and (meth)acrylamido, hydrogen atoms directly bonded to silicon atoms, etc.). These functional groups can be directly bonded to silicon atoms or to organic groups directly bonded to silicon atoms. The organic group can be a hydrocarbon group, such as an alkylene group or a divalent aromatic group. The hydrocarbon group can have 2 to 12 carbon atoms, and as an alkylene group, it is preferred that it has 2 to 10 carbon atoms. As a divalent aromatic group, it is preferred that it has 6 to 12 carbon atoms. The reactive group can be a group selected from hydroxyl, epoxy, carboxyl, (meth)acrylate, and amino, for example, it can be at least one selected from epoxy, hydroxyl, (meth)acrylate, and carboxyl.

[0090] a can 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 can be less than 10000, less than 7500, less than 5000, less than 3000, less than 1500, less than 1000, less than 500, less than 300, less than 200, less than 100, or less than 50, preferably less than 500.

[0091] In polysiloxane, relative to R s The total is the R of hydrocarbon groups with 1 to 5 carbon atoms. s The amount can be 20 mol% or more, 40 mol% or more, 60 mol% or more, or 80 mol% or more, preferably 50 mol% or more; and can be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less. For example, relative to R s The total amount of the radicals can be 50 mol% or more of methyl or ethyl (especially methyl).

[0092] In polysiloxane, relative to R s The total is the R of hydrocarbon groups with 6 to 40 carbon atoms. s The amount can be 3 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more, and can be less than 100 mol%, less than 90 mol%, less than 80 mol% or less than 70 mol%.

[0093] In polysiloxane, relative to R s The sum of these is the R of the reactive groups. s The amount can be 5 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more, and can be less than 50 mol%, less than 40 mol%, less than 30 mol% or less than 20 mol%.

[0094] R s Bases can be imported in random or block form, with random being preferred.

[0095] The terminal structure of the aforementioned polysiloxane alkyl group is not limited and can be -OR s 、-Si(R s )3, etc. R of the end structure s It may have more than one reactive group. Examples of reactive groups are as shown above, such as at least one selected from epoxy ring, hydroxyl, (meth)acrylate and carboxyl groups.

[0096] The polysiloxane may have a linking group, and the raw material compound and the polysiloxane may be bonded via the linking group. There is no limitation on such a linking group, which may be a hydrocarbon group with 1 to 40 (e.g., 1 to 20) carbon atoms that can be separated by oxygen atoms, or a (poly)oxyalkylene group with 1 to 40 (e.g., 1 to 20) carbon atoms.

[0097] Examples of polysiloxanes 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 , [In the formula,] R s Each time it appears, it is independently a hydrocarbon group or reactive group with 1 to 40 carbon atoms, and the terminal R s It can have more than one reactive group. Relative to R s Of the total amount of groups, 50 mol% or more are methyl groups. L s1 It consists of hydrocarbon groups with 1 to 20 carbon atoms. [a is between 5 and 10,000] wait, [In the formula, a represents an integer from 0 to 150, b represents an integer from 1 to 150, (a + b) is from 5 to 200, and n is an integer from 0 to 36.]

[0098] [Example of hydrophobic compound (A)] As an example of a hydrophobic compound (A), hydrocarbon compounds or compounds having a hydrocarbon group can be listed. Examples and preferred ranges of hydrocarbon groups are as described above.

[0099] As an example of a hydrophobic compound (A), compounds selected from amine modifiers, polyol modifiers, and polycarboxylic acid modifiers, as well as other liquid or solid oils, can be listed (described in detail below). For example, a hydrophobic compound (A1) can be a compound selected from amine modifiers, polyol modifiers, polycarboxylic acid modifiers, paraffin wax, and microcrystalline wax (e.g., compounds selected from amine modifiers, polycarboxylic acid modifiers, paraffin wax, and microcrystalline wax, especially amine modifiers), and a hydrophobic compound (A2) can be a liquid or solid oil that does not belong to the above-mentioned compound (A1) (e.g., liquid or solid oil other than amine modifiers, especially liquid or solid oils of compounds not selected from amine modifiers, polycarboxylic acid modifiers, paraffin wax, and microcrystalline wax, in one embodiment being liquid or solid oils of compounds not selected from amine modifiers, polyol modifiers, polycarboxylic acid modifiers, paraffin wax, and microcrystalline wax).

[0100] The hydrophobic compound (A) can be a hydrocarbon, but it can also be a non-hydrocarbon compound with functional groups such as ester, ether, or amide (amide structure). For example, the hydrophobic compound (A) can include compounds with an amide structure. Here, the amide structure can be a broad amide structure, selected from amides (carboxylic amides), ureas, urethanes, imides, thioamides, thioureas, thiourethanes, thioimides, sulfonamides, sulfonamides, sulfonamides, sulfonamides, sulfonamides, etc. The amide structure can be selected from -(C=O)N(-)2, -(C=S)N(-)2, and -S(=O)2N(-)2 (the orientation of each group can be reversed). Here, at least one of the valence bonds of N in the amide structure can be bonded to a hydrogen atom. The amide structure is preferably -(C=O)N(-)2, which can be an amide structure selected from amide, urea, urethane, and imide groups.

[0101] For example, a hydrophobic compound (A1) may have an amide structure, while a hydrophobic compound (A2) may not have an amide structure.

[0102] [Composition of hydrophobic compound (A)] Relative to the above-mentioned hydrophobic compound (A), the amount of the above-mentioned hydrophobic compound (A1) may be 15% or more by weight, 25% or more by weight, 35% or more by weight, 45% or more by weight, 55% or more by weight, 65% or more by weight, 75% or more by weight, 85% or more by weight, or 95% or more by weight, and may be 97.5% or less by weight, 95% or less by weight, 90% or less by weight, 80% or less by weight, 70% or less by weight, 60% or less by weight, 50% or less by weight, 40% or less by weight, 30% or less by weight, 20% or less by weight, or 10% or less by weight.

[0103] Relative to 100 parts by weight of the hydrophobic compound (A2), 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, and may be less than 2000 parts by weight, less than 1750 parts by weight, less than 1500 parts by weight, less than 1250 parts by weight, less than 1000 parts by weight, less than 750 parts by weight, less than 500 parts by weight, less than 250 parts by weight, less than 100 parts by weight, less than 75 parts by weight, less than 50 parts by weight, less than 30 parts by weight, or less than 10 parts by weight.

[0104] The amount of the hydrophobic compound (A2) relative to the hydrophobic compound (A) can be 15% or more by weight, 25% or more by weight, 35% or more by weight, 45% or more by weight, 55% or more by weight, 65% or more by weight, 75% or more by weight, 85% or more by weight, or 95% or more by weight, and can be 97.5% or less by weight, 95% or less by weight, 90% or less by weight, 80% or less by weight, 70% or less by weight, 60% or less by weight, 50% or less by weight, 40% or less by weight, 30% or less by weight, 20% or less by weight, or 10% or less by weight.

[0105] Relative to 100 parts by weight of the hydrophobic compound (A1), 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, and may be less than 2000 parts by weight, less than 1750 parts by weight, less than 1500 parts by weight, less than 1250 parts by weight, less than 1000 parts by weight, less than 750 parts by weight, less than 500 parts by weight, less than 250 parts by weight, less than 100 parts by weight, less than 75 parts by weight, less than 50 parts by weight, less than 30 parts by weight, or less than 10 parts by weight.

[0106] [Amount of hydrophobic compound (A)] In the composition, the amount of hydrophobic compound (A) can be 0.01% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, or 30% by weight or less, and can be 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight or less. Hydrophobic compound (A) can also be used alone in the composition.

[0107] [Amine-modified form] As examples of hydrophobic compounds (A1) and (A2), amine-modified compounds will be described. An amine-modified compound is a compound that has been chemically modified to exhibit liquid-repellent properties.

[0108] The amine-modified forms of the present invention exhibit excellent dispersibility in liquid media, and the compositions of the present invention demonstrate stable performance. In compositions using polymeric compounds as active ingredients, the molecular weight distribution is broad, tending to contain a high proportion of impurities. Amine-modified forms, however, can achieve lower molecular weight distribution, narrowing the molecular weight distribution (simplification) and improving performance.

[0109] The melting point of the amine modifier can be above 30°C, above 40°C, above 60°C, above 80°C, above 100°C, or above 120°C, preferably above 40°C, above 50°C, above 60°C, above 70°C, or above 80°C; and can be below 250°C, below 225°C, below 200°C, below 150°C, below 130°C, below 120°C, below 110°C, below 100°C, below 80°C, or below 50°C, for example, below 150°C or below 100°C. The melting point of the amine modifier can be determined according to JIS K2235-1991.

[0110] [Structure, etc.] The molecular weight of the amine modifier can be above 200, above 300, above 350, above 400, above 500, above 550, or above 750, and can be below 3000, below 2500, below 2000, below 1500, below 1000, below 900, below 800, below 750, or below 500.

[0111] The amine-modified forms of the present invention may not have groups containing active hydrogen. Examples of groups containing active hydrogen include amino groups (amino groups not adjacent to carbonyl groups, such as primary or secondary amino groups), hydroxyl groups, and carboxyl groups. In particular, the amine-modified forms of the present invention may not have primary or secondary amino groups not adjacent to carbonyl groups.

[0112] The amine-modified body of the present invention can be a polyamide having multiple amide groups, for example, it can be an amine (raw material amine compound, such as a polyamine) modified by amide groups with multiple modifying groups (e.g., Z described below). N The polyamide. Here, the amide may include amide moieties such as urethane, urea, and imide.

[0113] Amine modifiers can be compounds formed by modifying an amine (raw amine compound) with a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group that can have substituents.

[0114] In the amine modifier, one or more amino groups of the amine are replaced by a modifying group. The modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group that can have a substituent. From the viewpoint of improving liquid repellency, the amine modifier can be a structure in which an aliphatic hydrocarbon group with 3 to 40 carbon atoms (e.g., 6 to 40 carbon atoms) is modified onto the amine.

[0115] Details regarding monovalent hydrocarbon groups and monovalent polysiloxane groups that may have substituents are as described above in (monovalent hydrocarbon groups that may have substituents) and (monovalent polysiloxane groups).

[0116] (amine skeleton) The amine-modified body of the present invention has an amine skeleton. The amine skeleton has one or more amino groups having a predetermined number of valence bonds (valences) obtained by removing a predetermined number of atoms or groups of atoms (e.g., hydrogen) from an amine compound. The amino group in the amine skeleton refers to a group selected from -NH₂, -NH⁻, and -N(-)₂, and also includes amino groups adjacent to carbonyl groups contained in amide groups, urethane groups, urea groups, imides, etc. The amine skeleton can be an aliphatic or aromatic group having one or more amino groups, but the presence of heteroatoms other than nitrogen is not excluded.

[0117] The molecular weight of the amine skeleton can be above 30, above 50, above 100, above 200, above 300, above 400 or above 500, and can be below 2800, below 2500, below 2000, below 1500, below 1000, below 750, below 600, below 450, below 300 or below 250.

[0118] The number of carbon atoms in the amine skeleton can be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more; and can be less than 100, less than 80, less than 60, less than 40, less than 30, less than 20, less than 10, or less than 5, preferably less than 50, and especially less than 30.

[0119] The amine skeleton has one or more amino groups. The amino groups are 1 to 3 valent amino groups, and are selected from one or more of -NH2, -NH- and -N(-)2. The number of amino groups in the amine skeleton can be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, preferably 2 or more; and can be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0120] The amine skeleton has a hydrocarbon group (aliphatic or aromatic). The hydrocarbon group can be cyclic, branched, or linear. The hydrocarbon group can be saturated or unsaturated (e.g., saturated). Here, the hydrocarbon group can be separated by oxygen and / or sulfur atoms, or it can consist only of carbon, nitrogen, and hydrogen atoms. The hydrocarbon group can be a hydrocarbon group separated by oxygen and / or sulfur atoms (e.g., a chain-like saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 aromatic hydrocarbon rings), or it can be a general hydrocarbon group (e.g., a chain-like saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 aromatic hydrocarbon rings). When the hydrocarbon group is separated by oxygen and / or sulfur atoms, it has an ether, thioether, polyether, or polysulfide structure. The number of hydrocarbon groups in the amine skeleton can be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and can be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0121] The amine skeleton can be composed of 1- to 3-valent amino groups, and chain-like saturated aliphatic or aromatic hydrocarbon groups that can be separated by oxygen atoms and / or sulfur atoms.

[0122] The molar ratio (C / N ratio) of carbon atoms to nitrogen atoms in the amine skeleton can be 1 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, or 4 or more; and can be 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, or 2 or less, preferably 6 or less or 4 or less.

[0123] (-Y) N -Z N n ) The amine-modified form of the present invention has one or more of the following formula: -Y N -Z N n The indicated group, and at least one -Y N -Z N n It bonds with the nitrogen atoms in the aforementioned amine skeleton.

[0124] [In the formula,] Y N For groups that are directly bonded or have a 1+n valence, Z N It can be a monovalent hydrocarbon group with 1 to 40 carbon atoms or a monovalent polysiloxane group that can have substituents. n is an integer greater than 1 and less than 3. The -Y of the amine-modified form N -Z N nThe number can 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 can also be less than 12, less than 10, less than 8, less than 6, less than 4, less than 3, less than 2, or 1.

[0125] At least one -Y in the amine modifier N -Z N n It bonds to the nitrogen atoms in the amine skeleton. All -Y atoms in the amine modifier... N -Z N n In the number, the -Y atoms bonded to the nitrogen atoms of the amine skeleton N -Z N n The percentage can be 10% or more, 30% or more, 60% or more, 80% or more, or 100%, and can be less than 75%, less than 50%, or less than 25%. -Y atoms that are not bonded to the nitrogen atoms in the amine skeleton. N -Z N n It bonds with other groups (such as hydrocarbon groups) present in the amine skeleton.

[0126] (Y) N ) Y N It can be a directly bonded group or a group with a 1+n valence, preferably a group with a 1+n valence. N It serves to connect the amine skeleton with n Z groups N The role of the connecting base.

[0127] n is related to Y N Bonded Z N The number of elements can be an integer between 1 and 3. n can be 1 or more, 2 or more, or 3 or more, and can also be less than 3, less than 2, or less than 1, for example, less than 2.

[0128] Y N It can be an aliphatic group (unsaturated aliphatic group or saturated aliphatic group) or an aromatic group.

[0129] Y N The molecular weight can be above 10, above 50, above 100, above 200, above 300, above 500 or above 750, and can be below 2000, below 1500, below 1000, below 750, below 500 or below 300.

[0130] Y N It can have a carbonyl group. Y N It may have one or more groups selected from amide, urea, urethane, and imide, or Y NIt can form one or more groups selected from amide, urea, urethane, and imide together with the amino group in the amine skeleton. Examples of such amide, urea, urethane, and imide groups can be listed as follows: -O-C(=O)-NR'-、 -NR'-C(=O)-、 -NR'-C(=O)-O-、 -NR'-C(=O)-NR'- -C(=O)-NR'- -C(=O)-NR'-C(=O)-.

[0131] [In the formula, R' is a hydrocarbon group with 1 to 30 hydrogen atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).] Y N Preferably, the nitrogen atom in the amine skeleton is bonded to the -(C=O)- group.

[0132] Y N It can be a 1+n valence group composed of one or more of the following: directly bonded, consisting of an aliphatic hydrocarbon group with 1 to 20 carbon atoms selected from -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2, 2 to 4 valence aliphatic hydrocarbon rings with 1 to 20 carbon atoms, 2 to 4 valence aromatic hydrocarbon rings, and 2 to 4 valence heterocycles [where R' is a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)].

[0133] Y N The reason for selecting Y N1 and Y N2 One or more of the following groups constitute a 1+n valence group: Y N1 It is a directly bonded group composed of one or more groups selected from -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2 and -N(-)2 (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10 or 1 to 4 carbon atoms) in each occurrence). Y N2 It is a group composed of one or more aliphatic hydrocarbon groups with 1 to 20 carbon atoms selected from 2 to 4 valence, aromatic hydrocarbon rings with 2 to 4 valence, and heterocycles with 2 to 4 valence. It can be a 1+n valence group composed of one or more groups selected from the above groups. In this specification, it is denoted as Y. NThe left side of the group is bonded to the amine skeleton, and the right side is bonded to Z. N Bonding.

[0134] 〇Y N1 Y N1 It is a non-hydrocarbon linker.

[0135] Y N1 It is a directly bonded group or a group with a divalent or higher valence. Y N1 The valence can be 2–4, 2–3, or 2. Y is preferred. N1 It is not only a direct bond.

[0136] Y N1 The molecular weight can be above 10, above 50, above 100, above 200, above 300 or above 500, and can be below 2000, below 1500, below 1000, below 750 or below 500.

[0137] Y N1 It can be composed of one or more groups selected from direct bonding, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2 and -N(-)2 (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10 or 1 to 4 carbon atoms) each time it appears). As Y N1 Examples can be listed as follows: 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.

[0138] [In the formula, R' is independently a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears.] Among them, in Y N1 When bonded to a nitrogen atom in the amine skeleton, the nitrogen atom can be considered as part of the amine skeleton (amino group).

[0139] 〇Y N2 Y N2 It is a linker composed of one or more of a hydrocarbon group that may have substituents, an aromatic hydrocarbon ring that may have substituents, and a heterocycle that may have substituents.

[0140] Y N2 It can be a hydrocarbon group or a non-hydrocarbon group (containing heteroatoms). Y N2 It can be aliphatic or aromatic. N2 It can be linear, branched, or cyclic.

[0141] Y N2 It is a divalent or higher group. Y N2 The valence can be, for example, 2-4, 2-3, or 2.

[0142] Y N2 The number of carbon atoms can be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and can be less than 40, less than 35, less than 30, less than 25, less than 20, less than 15, less than 10, or less than 5.

[0143] Y N2 It is composed of one or more aliphatic hydrocarbon groups with 1 to 40 carbon atoms that may have substituents, aromatic hydrocarbon rings with 2 to 4 valences that may have substituents, and heterocycles with 2 to 4 valences that may have substituents.

[0144] Aliphatic hydrocarbon groups with 1 to 40 carbon atoms and a valence of 2 to 4 can be cyclic, branched, or straight-chain hydrocarbon groups. These groups can be saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon groups. The number of carbon atoms in these groups can be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and can be less than 35, less than 30, less than 25, less than 20, less than 15, less than 10, or less than 5. The valence of the aliphatic hydrocarbon group can be 2 or more, 3 or more, or 4, and can be less than 4, less than 3, or 2.

[0145] Aliphatic hydrocarbon groups may have substituents. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms each time it appears). 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 aliphatic hydrocarbon groups with substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more; and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0146] Examples of aromatic hydrocarbon rings with 2 to 4 valences include groups formed by removing 2 to 4 hydrogen atoms from aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, benzo[a]tetraphenyl (naphthene), pentabenzene, pyrene, and phenanthrene. The number of ring atoms in the aromatic hydrocarbon ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the aromatic hydrocarbon ring can be 2 or more, 3 or more, or 4, and can be 4 or less, 3 or less, or 2.

[0147] Aromatic hydrocarbon rings may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms each time it appears). Substituents may or may not have active hydrogen atoms. 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 aromatic hydrocarbon rings with substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more; and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0148] The 2- to 4-valent heterocycle can be an aliphatic or aromatic group. Examples of 2- to 4-valent heterocycles include groups from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cyclophosphine, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benziisothiazole, pyrrolidine, piperidine, piperazine, imidazole, thiazoline, etc., which have had 2 to 4 hydrogen atoms removed. The number of cyclic atoms in the heterocycle is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the heterocycle can be 2 or more, 3 or more, or 4, and can be 4 or less, 3 or less, or 2.

[0149] Heterocyclic rings may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms each time it appears). Substituents may or may not have active hydrogen atoms. 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 heterocyclic rings with 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 be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0150] As Y N2 Examples can be listed as follows: -Ali- -Cy- -Ali (-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali (-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- etc.

[0151] [In the formula, Ali is an aliphatic hydrocarbon group with 1 to 20 carbon atoms, and Cy is an aromatic hydrocarbon ring or heterocycle.] As Y N2 Specific examples can be listed as follows: - (CH2)p - (p is 1-40, 1-20, or 1-10) A straight-chain hydrocarbon group with unsaturated bonds, having 1–40, 1–20, or 1–10 carbon atoms. Hydrocarbon groups with branched structures having 1–40, 1–20, or 1–10 carbon atoms - (CH2) q -Cy- (CH2) r - (q and r are independently 0 to 20, for example 1 to 10, and Cy is an aromatic hydrocarbon ring or a heterocyclic ring) etc.

[0152] •Y N Examples For Y N Examples will be used to illustrate this. In the following text, R' is independently a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears.

[0153] As Y N For example, in Y N When it is divalent, we can list -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 -wait.

[0154] As Y N For example, in Y N When it is trivalent, the following can be listed: -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 -Y N1 -) 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.

[0155] As Y N For example, when Y N is tetravalent, the following can be listed: -Y N1 (-) 3, -Y N1 -Y N2 (-) 3, -Y N1 -(Y N2-) 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.

[0156] As Y N For a preferred example of, -Y can be listed N1 -, -YN1 -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 form, one or more Y N Preferably, the amine skeleton side end is -(C=O)- and is bonded to the nitrogen atom on the amine skeleton.

[0157] Y N Preferred is -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 shows the group.

[0158] [In the formula,] Y N1 It is independent each time it appears: 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 a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears.) Y N2 It is an aliphatic hydrocarbon group with 1 to 10 carbon atoms and a 2 to 4 valence, or a divalent aromatic group (e.g., a divalent phenyl group or a divalent triazole group). This allows the substrate to be endowed with good liquid repellency.

[0159] As Y N Further specific examples can be listed as follows: *-(C=O)- -O-(C=O)-NR'- etc. [In the formula, * indicates bonding with the nitrogen atom of the amine skeleton,] R' is a hydrocarbon group with 1 to 30 hydrogen atoms or carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[0160] (Z) N ) Z N The form can be a monovalent hydrocarbon group with 1 to 40 carbon atoms or a monovalent polysiloxane group that may have substituents, and the method described above for (monovalent hydrocarbon groups that may have substituents) and (monovalent polysiloxane groups) is followed.

[0161] [Examples of amine-modified forms] (Amine modification example 1) As an example of an amine-modified form, the following formula can be cited: 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 The compound shown is an amine-modified example 1.

[0162] [In the formula,] Y N Each time it appears, it is independently either a directly bonded group or a group with a 1+n valence. Z NEach time it appears, it is independently a straight-chain or branched monovalent hydrocarbon group with 3 to 40 carbon atoms that can have substituents. L 1 Each time it appears, it is independently a divalent aliphatic or aromatic hydrocarbon group with 2 to 20 carbon atoms that can be separated by oxygen and / or sulfur atoms. Each time n appears, it is an integer between 1 and 3. p is an integer between 0 and 2, which is independent of p in each occurrence. Each occurrence of q is an integer between 0 and 2. p + q in each N(-Y) N -Z N n ) p (-H) q The middle is 2. r is independently 0 or 1 each time it appears. s is independently 0 or 1 each time it appears. r+s in each N(-Y) N -Z N n ) r (-H) s The middle value is 1. The sum of all p and all r is greater than 1. t is an integer greater than 0 and less than 10. In amine modification example 1, regarding Y N Z N For details regarding n, the same approach described above will be used.

[0163] In amine-modified example 1, L 1 It is a divalent aliphatic or aromatic hydrocarbon group with 2 to 20 carbon atoms that can be separated by oxygen and / or sulfur atoms. It can be cyclic, branched, or linear, preferably a chain-like or aromatic hydrocarbon group. As L 1 The hydrocarbon group described above in the [amine skeleton] description can be used. The hydrocarbon group can be separated by oxygen atoms and / or sulfur atoms, or it can be composed of only carbon atoms, nitrogen atoms, and hydrogen atoms. L 1 For example, it can also be an aliphatic hydrocarbon group with saturated or unsaturated (e.g., saturated) or an aromatic hydrocarbon group with 1 to 2 aromatic hydrocarbon rings. 1 Preferably, it is a cyclic group that simultaneously has a ring (e.g., an aromatic ring) and a chain structure (e.g., a straight chain structure, an ether oxygen, a thioether sulfur). Specific examples include 1,3-phenylene diene, 1,4-phenylene diene, diphenyl ether diene, diphenyl thioether diene, etc. 1The number of carbon atoms can be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and can be less than 20, less than 18, less than 16, less than 14, less than 12, less than 10, less than 8, less than 6, less than 4, or less than 3.

[0164] In amine modification example 1, p is an integer greater than or equal to 0 and less than 2 each time it appears, q is an integer greater than or equal to 0 and less than 2 each time it appears, and p + q in each N(-Y N -Z N n ) p (-H) q The value of p is 2. It is preferable that p is independently greater than or equal to 1 each time it occurs, for example, 2.

[0165] In amine-modified example 1, r is independently 0 or 1 each time it appears, s is independently 0 or 1 each time it appears, and r + s in each N(-Y) N -Z N n ) r (-H) s The value of p is 1. It is preferable that p is 1 or higher each time it appears, for example, 2.

[0166] The sum of all p and all r is 1 or more, that is, amine-modified example 1 has more than one -Y. N -Z N n The sum of all p and all r can be 1 or more, 3 or more, 5 or more, 7 or more, 9 or more, or 12 or more (the sum of all q and all s can also be 0), and can be less than 14, less than 12, less than 10, less than 8, less than 6, or less than 4.

[0167] In amine modification example 1, t is an integer from 0 to 10. t can 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 can 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.

[0168] (Amine modification example 2) Examples of other amine modifiers can be listed as follows: N(-Y N -Z N n ) p (-H) q -L 2 (-Y N -Z N n ) u The compound shown is an amine-modified example 2.

[0169] [In the formula,] Y N Each time it appears, it is independently either a directly bonded group or a group with a 1+n valence. Z N Each time it appears, it is independently a straight-chain or branched monovalent hydrocarbon group with 3 to 40 carbon atoms that can have substituents. L 2 It is an aliphatic or aromatic hydrocarbon group with 2 to 20 carbon atoms and a +u valence that can be separated by oxygen and / or sulfur atoms. Each time n appears, it is an integer between 1 and 3. p is an integer greater than 0 and less than 2. q is an integer greater than 0 and less than 2. p + q = 2 u is an integer greater than 1 and less than 3. The sum of p and u is 1 or more. In amine modification example 2, regarding Y N Z N For details regarding n, the same approach described above will be used.

[0170] In amine-modified example 2, L 2 It is an aliphatic or aromatic hydrocarbon group with 2 to 20 carbon atoms and a +u valence that can be separated by oxygen and / or sulfur atoms. It can be a cyclic, branched, or linear hydrocarbon group, preferably a chain hydrocarbon group or an aromatic hydrocarbon group. As L 2 The hydrocarbon group described above in the [amine skeleton] description can be used. The hydrocarbon group can be separated by oxygen atoms and / or sulfur atoms, or it can be composed of only carbon atoms, nitrogen atoms, and hydrogen atoms. L 2 For example, it can also be an aliphatic hydrocarbon group with saturated or unsaturated (e.g., saturated) or an aromatic hydrocarbon group with 1 to 2 aromatic hydrocarbon rings. 2 Preferably, it is a cyclic group that simultaneously has a ring (e.g., an aromatic ring) and a chain structure (e.g., a straight chain structure, an ether oxygen, a thioether sulfur). Specific examples include 1,3-phenylene diene, 1,4-phenylene diene, diphenyl ether diene, diphenyl thioether diene, etc. 2 The number of carbon atoms can be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and can be less than 20, less than 18, less than 16, less than 14, less than 12, less than 10, less than 8, less than 6, less than 4, or less than 3.

[0171] In amine modification example 2, p is an integer greater than or equal to 0 and less than or equal to 2, q is an integer greater than or equal to 0 and less than or equal to 2, and p + q equals 2. Preferably, p can be greater than or equal to 1, for example, 2.

[0172] In amine modification example 2, u is an integer greater than or equal to 1 and less than or equal to 3. u is 1, 2, or 3, for example, 2 or 3.

[0173] In amine-modified embodiment 2, the sum of p and u is 1 or more, that is, amine-modified embodiment 2 has one or more -Y N -Z N n The sum of all p and u can be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more (the sum of all q can also be 0), and can be less than 5, less than 4, less than 3, or less than 2.

[0174] (Specific example) Specific examples of amine-modified compounds include compounds represented by the following formulas. In the following formulas, details regarding Z follow the same pattern as described above. N The method described in the instructions. Amine modifiers can be synthetic waxes derived from animal or vegetable oils. Synthetic waxes are obtained by condensing fatty acids from animal or vegetable oils with aliphatic or aromatic amines. Examples of synthetic waxes include fatty acid amide compounds such as hydroxy fatty acid amides, palmitamides, octadecanoic acid amides, stearamides, eicosanoic acid amides, betaine compounds, tetracosanoic acid amides, oleamides, linoleamides, α-linolenic acid amides, γ-linolenic acid amides, eicosapentaenoic acid amides, and docosahexaenoic acid amides.

[0175] [Manufacturing Method] There are no limitations on the manufacturing method of the amine modifier; examples include: making a Z-containing... N A method for synthesizing Z-containing carboxylic acids by reacting them with various amines (starting amines) in the presence of a desired condensing agent; N Methods for synthesizing amines include the reaction of acyl chlorides, anhydrides, isocyanates, etc., of carboxylic acids with various amines. The condensing agent can be a well-known condensing agent, such as DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA, Py-Bop, etc.

[0176] (Amine (raw material amine))Examples of amines (raw material amines) that serve as precursors to the amine skeleton include amines capable of forming the amine skeleton, such as: alkylamines like methylamine, ethylamine, propylamine, butylamine, and dibutylamine; alkylene diamines like ethylenediamine, propylenediamine, butylamine, pentanediamine, hexamethylenediamine, cyclohexanediamine, and methylenedicyclohexylamine; and diethylenetriamine, triethylenetetramine, tri(2-aminoethyl)amine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tri(2-aminopropyl)amine, tetrapropylenepentamine, pentapropylenehexamine, iminodipropylamine, dibutyltriamine, bis(2-aminoethoxy)ethane, bis(2-aminoethyl) ether, and bis[2-(2-aminoethoxy)]ethane. Polyalkylene polyamines such as 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, polyoxypropylene diamine, polyoxyethylene diamine, etc.; aromatic monoamines such as aniline, 1-naphthylamine or 2-naphthylamine, 1-aminoanthracene, 2-aminoanthracene or 9-aminoanthracene, 9-aminophenanthrene, 2-aminobiphenyl, 3-aminobiphenyl or 4-aminobiphenyl, etc.; o-phenylenediamine, m-phenylenediamine or p-phenylenediamine, o-phenylenediamine, m-phenylenediamine or p-phenylenediamine, diaminotoluene, 2,3-toluenediamine, 2,4-toluenediamine or 2,5-toluenediamine. Monocyclic aromatic polyamines, etc.; diaminobiphenyl, bisaminophenoxyphenylpropane, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl sulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenylphenylethane, bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, aminophenoxybiphenyl, aminophenoxyphenyl ketone, bisaminodi(trifluoromethyl)benzylbenzene, aminophenoxyphenyl sulfone, aminophenoxyphenyl ether, aminophenoxyphenylpropane, bis(aminophenoxybenzoyl)benzene, bis(aminophenoxy-α,α-dimethylbenzyl)benzene, bis[(aminoaryloxy)benzoyl]di Polycyclic aromatic polyamines including phenyl ether, bis(amino-α,α-dimethylbenzylphenoxy)benzophenone, aminophenoxyphenyl sulfide, bis[amino-α,α-dimethylbenzylphenoxy]diphenyl sulfone, 4,4'-bis[aminophenoxyphenoxy]diphenyl sulfone, diaminodiaryloxybenzophenone, diaminoaryloxybenzophenone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminotriphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenebisphenylamine, 4,4'-oxodiphenylamine, 1,3-bis(4-aminophenoxy)benzene, 4,4'-diaminodiphenyl ether, 4,4'-bis(aminophenyl)amine, etc.Polyamines containing oxygen or sulfur, such as 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 3,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl sulfide; and hydroxyl-containing polyamines, such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropanediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropanediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine. Polyamines can be formed by polymerizing polymerizable compounds such as allylamine.

[0177] [Polyol Modified Forms] As examples of hydrophobic compounds (A1) and (A2), polyol modifiers will be described. A polyol modifier is a compound that has been chemically modified to make a polyol exhibit hydrophobic properties.

[0178] The melting point of the polyol modifier can be above 30°C, above 40°C, above 60°C, above 80°C, above 100°C, or above 120°C, preferably above 40°C, above 50°C, above 60°C, above 70°C, or above 80°C; and can also be below 250°C, below 225°C, below 200°C, below 150°C, below 130°C, below 120°C, below 110°C, below 100°C, below 80°C, or below 50°C, for example, below 150°C or below 100°C. The melting point of the polyol modifier can be determined according to JIS K2235-1991.

[0179] [Structure, etc.] The polyol modifier can be a polymer with a degree of polymerization of 1 or higher. From the viewpoint of improving liquid repellency, the degree of polymerization of the polyol modifier can be 2 or higher, 3 or higher, 5 or higher, 6 or higher, preferably 7 or higher, more preferably 8 or higher, and even more preferably 9 or higher; and from the viewpoint of improving the workability of the composition, it can be 100 or lower, preferably 50 or lower, more preferably 30 or lower, and even more preferably 15 or lower. Here, the degree of polymerization refers to the number of repetitions of the monomer units constituting the polymer.

[0180] The degree of polymerization in this invention refers to the average degree of polymerization. The average degree of polymerization in this invention refers to the degree of polymerization measured under the following conditions.

[0181] In the case where the polyol modified body of the present invention is a polyglycerol modified body obtained by modifying polyglycerol, the degree of polymerization of the polyol modified body refers to the average degree of polymerization of the polyglycerol. The average degree of polymerization of polyglycerol is the average degree of polymerization (n) calculated from the hydroxyl value using end-group analysis. Specifically, the average degree of polymerization and the average molecular weight are calculated using the following formulas (Formula 1) and (Formula 2).

[0182] (Equation 1) Average molecular weight = 74n + 18 (Equation 2) Hydroxyl value = 56110(n+2) / average molecular weight The hydroxyl value in Equation 2 above is a numerical value indicating the number of hydroxyl groups in polyglycerol. The hydroxyl value is calculated based on the amount of potassium hydroxide required to neutralize the acetic acid needed to acetylate 1g of free hydroxyl groups in polyglycerol. This can be calculated according to the "Standard Oil Analysis Test Method (I), 2003 Edition" compiled by the Japan Oil Chemical Society. The hydroxyl value of the polyglycerol used as raw material can be measured according to the aforementioned Standard Oil Analysis Test Method, and then the average degree of polymerization and average molecular weight of the polyglycerol can be calculated using the above formula.

[0183] In the case where the polyol modified body of the present invention is a polyvinyl alcohol modified body obtained by modifying polyvinyl alcohol, the degree of polymerization of the polyol modified body refers to the average degree of polymerization of the polyvinyl alcohol. The average degree of polymerization of polyvinyl alcohol can be determined according to JIS K 6726, the test method for polyvinyl alcohol.

[0184] In the case where the polyol modifier of the present invention is a polysaccharide modifier obtained by modifying polysaccharides, the degree of polymerization of the polyol modifier refers to the average degree of polymerization of the aforementioned polysaccharides. The analysis of the average degree of polymerization of the polysaccharides can be performed as follows. The degree of polymerization refers to the number of monosaccharide units (fructose and glucose units) in the polysaccharide. The average degree of polymerization can be, for example, the peak value among the peaks of each analytical result obtained by conventional analytical methods such as HPLC, GC, and HPAEC as described below. As a chromatographic column, for example, a ULTRON PS-80N (8×300mm) (solvent: water, flow rate: 0.5ml / min, temperature: 50°C) manufactured by Shin-Ho Chemical or a TSK-GEL G30000 PWXL (7.8×300mm) manufactured by TOSOH (solvent: water, flow rate: 0.5ml / min, temperature: 50°C) can be used. As a detector, a differential refractometer can be used for measurement.

[0185] The polyol modifier can be a low molecular weight (e.g., a weight-average molecular weight of less than 1500, less than 1000, or less than 500) and / or a high molecular weight. The weight-average molecular weight of the polyol modifier can be above 100, above 200, above 300, above 400, above 500, above 1000, above 3000, above 5000, above 10000, above 30000, above 100000, above 300000, above 300000, or above 500000. It can also be below 10000000, below 3000000, below 1000000, below 750000, below 500000, below 300000, below 100000, below 75000, below 50000, below 30000, below 10000, below 9000, below 8000, below 7000, below 6000, below 5000, below 3000, below 2000, below 1000, or below 500.

[0186] The substitution rate of the hydroxyl groups in the polyol modifier can 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 can also be less than 100%, less than 95%, less than 85%, less than 75%, less than 65%, less than 55%, less than 45%, less than 35%, less than 25%, less than 15%, for example, less than 95%. Here, "substitution rate" refers to the proportion (mol%) of the hydroxyl groups from the polyol source that are modified, and refers to the proportion (mol%) modified by a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group that can have substituents.

[0187] The residual percentage of hydroxyl groups in the polyol modifier can 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 can also be less than 100%, less than 95%, less than 85%, less than 75%, less than 65%, less than 55%, less than 45%, less than 35%, less than 25%, less than 15%, or less than 5%, for example, less than 50%, less than 30%, or less than 10%. Here, "residual percentage" refers to the proportion (mol%) of unmodified hydroxyl groups from the polyol source.

[0188] The number of modifying groups in the polyol modifier can 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 can be less than 1000, less than 750, less than 500, less than 300, less than 100, less than 50, less than 30, or less than 20. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group that can have substituents.

[0189] The equivalent of the modifying group in the polyol modifier can 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 can be less than 2500, less than 2000, less than 1500, less than 1000, less than 750, less than 500, or less than 400, which is the value obtained by dividing the weight-average molecular weight of the polyol modifier by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group that can have substituents.

[0190] In the polyol modifier, one or more hydroxyl groups of the polyol are replaced by a modifying group. The modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group that can have a substituent. From the viewpoint of improving liquid repellency, the polyol modifier can be a structure in which an aliphatic hydrocarbon group with 3 to 40 carbon atoms (e.g., 6 to 40 carbon atoms) is modified on the polyol.

[0191] For details regarding monovalent hydrocarbon groups that may have substituents and monovalent polysiloxane groups, the same approach was taken in the descriptions above for (monovalent hydrocarbon groups that may have substituents) and (monovalent polysiloxane groups).

[0192] (-Y) O -Z O n ) In the polyol modifier of the present invention, one or more hydroxyl groups of the polyol can be expressed by the following formula: -Y O -Z O n The shown group substitutions, [In the formula,] Y O The reason for selecting Y O1 and Y O2 One or more of the following groups constitute a 1+n valence group: Y O1It is a directly bonded group composed of one or more groups selected from -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2 and -N(-)2 (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10 or 1 to 4 carbon atoms) in each occurrence). Y O2 It is a group composed of one or more aliphatic hydrocarbon groups with 1 to 40 carbon atoms that may have substituents, aromatic hydrocarbon rings with 2 to 4 valences that may have substituents, and heterocycles with 2 to 4 valences that may have substituents. Z O It can be a monovalent hydrocarbon group with 1 to 40 carbon atoms or a monovalent polysiloxane group that can have substituents. n is an integer greater than 1 and less than 3.

[0193] (Y) O ) Y O The reason for selecting Y O1 and Y O2 One or more of the following groups constitute a 1+n valence group: Y O1 It is a directly bonded group composed of one or more groups selected from -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2 and -N(-)2 (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10 or 1 to 4 carbon atoms) in each occurrence). Y O2 It is a group composed of one or more of an aliphatic hydrocarbon group with 1 to 40 carbon atoms that may have substituents, an aromatic hydrocarbon ring with 2 to 4 valences that may have substituents, and a heterocycle with 2 to 4 valences that may have substituents.

[0194] n is related to Y O Bonded Z O The number of elements can be an integer between 1 and 3. n can be 1 or more, 2 or more, or 3 or more, and can also be less than 3, less than 2, or less than 1, for example, less than 2.

[0195] Y OThe molecular weight can be above 10, above 50, above 100, above 200, above 300, above 500, or above 750, and can be below 3000, below 2500, below 2000, below 1500, below 1000, below 750, below 500, below 300, below 200, below 100, or below 50.

[0196] Y O It can have an amide structure. Here, the amide structure can be a broad amide structure, selected from amides (acid amides), ureas, urethanes, imides, thioamides, thioureas, thiourethanes, thioimides, sulfonamides, sulfonamides, sulfonamides, sulfonamides, sulfonamides, etc. The amide structure can be selected from -(C=O)N(-)2, -(C=S)N(-)2, and -S(=O)2N(-)2 (the orientation of each group can be reversed). Here, at least one of the valence bonds of the N group in the amide structure can be bonded to a hydrogen atom. The amide structure is preferably -(C=O)N(-)2, and can be an amide structure selected from amide groups, urethane groups, urea groups, and imide groups. By having an amide structure, the liquid repellency can be improved.

[0197] ○ Y O1 Y O1 It is a non-hydrocarbon linker.

[0198] Y O1 It is a directly bonded group or a group with a divalent or higher valence. Y O1 The valence can be 2–4, 2–3, or 2. Y is preferred. O1 It is not only a direct bond.

[0199] Y O1 The molecular weight can be above 10, above 50, above 100, above 200, above 300 or above 500, and can be below 2000, below 1500, below 1000, below 750 or below 500.

[0200] Y O1 It can be composed of one or more groups selected from direct bonding, -O-, -C(=O)-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2 (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears). As Y O1 Examples can be listed as follows: 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.

[0201] (In the formula, R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears.) Y O2 It can have at least an amide structure. Here, the amide structure can be a broad amide structure, selected from amides (acid amides), ureas, urethanes, imides, thioamides, thioureas, thiourethanes, thioimides, sulfonamides, sulfonamides, sulfonamides, sulfonamides, sulfonamides, etc. The amide structure can be selected from -(C=O)N(-)2, -(C=S)N(-)2, and -S(=O)2N(-)2 (the orientation of each group can be reversed). Here, at least one of the valence bonds of the N group in the amide structure can be bonded to a hydrogen atom. The amide structure is preferably -(C=O)N(-)2, and can be an amide structure selected from amide groups, urethane groups, urea groups, and imide groups. By having an amide structure, the liquid repellency can be improved.

[0202] ○ Y O2 Y O2 It is a linker composed of one or more of a hydrocarbon that may have substituents, an aromatic hydrocarbon ring that may have substituents, and a heterocycle that may have substituents.

[0203] Y O2 It can be a hydrocarbon group or a non-hydrocarbon group (containing heteroatoms). Y O2 It can be aliphatic or aromatic. O2 It can be linear, branched, or cyclic.

[0204] Y O2 It is a divalent or higher group. Y O2 The valence can be, for example, 2-4, 2-3, or 2.

[0205] Y O2The number of carbon atoms can be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and can be less than 40, less than 35, less than 30, less than 25, less than 20, less than 15, less than 10, or less than 5.

[0206] Y O2 It is composed of one or more aliphatic hydrocarbon groups with 1 to 40 carbon atoms that may have substituents, aromatic hydrocarbon rings with 2 to 4 valences that may have substituents, and heterocycles with 2 to 4 valences that may have substituents.

[0207] Aliphatic hydrocarbon groups with 1 to 40 carbon atoms and a valence of 2 to 4 can be cyclic, branched, or straight-chain hydrocarbon groups. These groups can be saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon groups. The number of carbon atoms in these groups can be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and can be less than 35, less than 30, less than 25, less than 20, less than 15, less than 10, or less than 5. The valence of the aliphatic hydrocarbon group can be 2 or more, 3 or more, or 4, and can be less than 4, less than 3, or 2.

[0208] Aliphatic hydrocarbon groups may have substituents. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms each time it appears). 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 aliphatic hydrocarbon groups with substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more; and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0209] Examples of aromatic hydrocarbon rings with 2 to 4 valences include groups formed by removing 2 to 4 hydrogen atoms from aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, benzo[a]tetraphenyl (naphthene), pentabenzene, pyrene, and phenanthrene. The number of ring atoms in the aromatic hydrocarbon ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the aromatic hydrocarbon ring can be 2 or more, 3 or more, or 4, and can be 4 or less, 3 or less, or 2.

[0210] Aromatic hydrocarbon rings may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms each time it appears). Substituents may or may not have active hydrogen atoms. 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 aromatic hydrocarbon rings with substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more; and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0211] The 2- to 4-valent heterocycle can be an aliphatic or aromatic group. Examples of 2- to 4-valent heterocycles include groups from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cyclophosphine, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benziisothiazole, pyrrolidine, piperidine, piperazine, imidazole, thiazoline, etc., which have had 2 to 4 hydrogen atoms removed. The number of cyclic atoms in the heterocycle is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the heterocycle can be 2 or more, 3 or more, or 4, and can be 4 or less, 3 or less, or 2.

[0212] Heterocyclic rings may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms each time it appears). Substituents may or may not have active hydrogen atoms. 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 heterocyclic rings with 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 be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0213] As Y O2 Examples can be listed as follows: -Ali- -Cy- -Ali (-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali (-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- etc. [In the formula, Ali is an aliphatic hydrocarbon group with 1 to 20 carbon atoms, and Cy is an aromatic hydrocarbon ring or heterocycle.]

[0214] As Y O2 Specific examples can be listed as follows: - (CH2) p - (p is 1-40, 1-20, or 1-10) A straight-chain hydrocarbon group with unsaturated bonds, having 1–40, 1–20, or 1–10 carbon atoms. Hydrocarbon groups with branched structures having 1–40, 1–20, or 1–10 carbon atoms - (CH2) q -Cy- (CH2) r - (q and r are independently 0 to 20, for example 1 to 10, and Cy is an aromatic hydrocarbon ring or a heterocyclic ring) etc.

[0215] (Y) O (Example) For Y O Examples will be used to illustrate this. In the following text, R' is independently a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears.

[0216] As Y O For example, in Y O When it is divalent, we can list -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 -Y O1 -Y O2 -、-Y O2 -YO1 -Y O2 -Y O1 - etc.

[0217] As Y O For example, when Y O is trivalent, the following can be listed: -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 -Y O1 (-)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, etc.

[0218] As Y O For example, when Y O is tetravalent, the following can be listed: -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, -Y O2 -Y O1 (-Y O2 -), 3, -Y O2 -(Y O1 -Y O2 -), 3, -Y O2 -YO1 -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.

[0219] As Y O Preferred examples can be listed as -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.

[0220] (Y) O (Preferred example) Y O -O-Y can be preferred. O11 - or -O-Y O11 -Y O21 -Y O12 -.

[0221] [In the formula, each symbol appears independently each time.] Y O11 For direct bonding, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-. Y O21 It consists of hydrocarbon groups with 1 to 40 carbon atoms. Y O12are -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. ] Y O11 It is a non-hydrocarbon linker, which is a directly bonded or divalent or higher group.

[0222] Y O11 The molecular weight can be above 10, above 50, above 100, above 200, above 300 or above 500, and can be below 2000, below 1500, below 1000, below 750 or below 500.

[0223] Y O11 It can be a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-.

[0224] Y O21 It is a divalent hydrocarbon linker, which can be a hydrocarbon group with 1 to 40 carbon atoms.

[0225] Y O21 The number of carbon atoms can be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and can be less than 40, less than 35, less than 30, less than 25, less than 20, less than 15, less than 10, or less than 5.

[0226] Here, the hydrocarbon group with 1 to 40 carbon atoms can be a cyclic, branched, or straight-chain hydrocarbon group, and can be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group.

[0227] As Y O21 Specific examples can be listed as follows: - (CH2) p - (p is 1-40, 1-20, or 1-10) A straight-chain hydrocarbon group with unsaturated bonds, having 1–40, 1–20, or 1–10 carbon atoms. Hydrocarbon groups with branched structures having 1–40, 1–20, or 1–10 carbon atoms - (CH2) q -Cy- (CH2) r - (q and r are independently 0 to 20, for example 1 to 10, and Cy is an aromatic hydrocarbon ring or a heterocyclic ring) etc.

[0228] Y O12 Can 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.

[0229] Y O12 It can have at least an amide structure. Here, the amide structure can be a broad amide structure, selected from amides (acid amides), ureas, urethanes, imides, thioamides, thioureas, thiourethanes, thioimides, sulfonamides, sulfonamides, sulfonamides, sulfonamides, sulfonamides, etc. The amide structure can be selected from -(C=O)N(-)2, -(C=S)N(-)2, and -S(=O)2N(-)2 (the orientation of each group can be reversed). Here, at least one of the valence bonds of the N group in the amide structure can be bonded to a hydrogen atom. The amide structure is preferably -(C=O)N(-)2, and can be an amide structure selected from amide groups, urethane groups, urea groups, and imide groups. By having an amide structure, the liquid repellency can be improved.

[0230] (Z) O ) Z O The following are examples of monovalent hydrocarbon groups or monovalent polysiloxane groups that may have substituents and have 1 to 40 carbon atoms: (monovalent hydrocarbon groups that may have substituents) and (monovalent polysiloxane groups).

[0231] [Other Modifying Groups] The hydroxyl groups of polyols can be -Y O -Z O n Other modifying groups may be substituted. Examples of modifying groups include anionic and / or cationic groups.

[0232] Monomers having carboxyl, sulfonic acid, or phosphate groups can be listed as anionic groups.

[0233] Salts that are anionic groups can be alkali metal salts, alkaline earth metal salts, or ammonium salts, such as methyl ammonium salts, ethanol ammonium salts, triethanolammonium salts, etc.

[0234] As cationic groups, there are amino, preferably tertiary amine, and quaternary ammonium groups. In the tertiary amine group, the two groups bonded to the nitrogen atom may be the same or different, preferably an aliphatic group (especially alkyl) with 1 to 5 carbon atoms, an aromatic group (aryl) with 6 to 20 carbon atoms, or an aromatic aliphatic group (especially aralkyl, for example benzyl (C6H5-CH2-)) with 7 to 25 carbon atoms. In the quaternary ammonium group, the three groups bonded to the nitrogen atom may be the same or different, preferably an aliphatic group (especially alkyl) with 1 to 5 carbon atoms, an aromatic group (aryl) with 6 to 20 carbon atoms, or an aromatic aliphatic group (especially aralkyl, for example benzyl (C6H5-CH2-)) with 7 to 25 carbon atoms. In the tertiary amine and quaternary ammonium groups, the remaining group bonded to the nitrogen atom may have a carbon-carbon double bond. The cationic group may be in the form of a salt.

[0235] The cationic group of the salt is a salt formed with an acid (organic acid or inorganic acid). Organic acids are preferred, such as carboxylic acids with 1 to 20 carbon atoms (especially monocarboxylic acids such as acetic acid, propionic acid, butyric acid, stearic acid, etc.).

[0236] [Manufacturing Method] Polyol modifiers can be manufactured by reacting a modifier having a modifier group (or a precursor structure of the modifier group) with the hydroxyl group of the polyol.

[0237] (Polyols) Polyols are compounds with two or more hydroxyl groups and are used as raw materials for polyol modifiers. A polyol is a compound with two or more hydroxyl groups within its molecule. Polyols can be aliphatic or aromatic, preferably aliphatic.

[0238] Polyols may have ether bonds. Preferably, polyols have two or more ether bonds. Specifically, polyols are preferably compounds having two or more hydroxyl groups and two or more ether bonds. In other words, polyols are preferably polyethers having two or more hydroxyl groups.

[0239] In the case of polyols as polymers, the repeating structure of monomer units can contain hydroxyl and ether bonds.

[0240] Polyols can be low molecular weight (e.g., weight average molecular weight less than 1000, below 500) and / or high molecular weight. The weight average molecular weight of polyols can be above 50, above 100, above 300, above 500, above 1000, above 3000, above 5000, above 10000, above 30000, above 100000, above 300000, or above 500000, and can be below 1000000, below 750000, below 500000, below 300000, below 100000, below 75000, below 50000, below 30000, below 10000, below 5000, below 3000, below 2000, below 1000, or below 500.

[0241] The number of hydroxyl groups in a polyol can be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more, and can be less than 3000, less than 1000, less than 750, less than 500, less than 300, less than 100, less than 50, less than 30, or less than 20.

[0242] The hydroxyl equivalent of a polyol can be 20 or higher, 40 or higher, 60 or higher, 80 or higher, 100 or higher, 120 or higher, or 150 or higher, and can also be below 1000, below 800, below 600, below 400, below 200, below 100, or below 75. The hydroxyl equivalent of a polyol is the value obtained by dividing the weight-average molecular weight of the polyol by the number of hydroxyl groups.

[0243] Polyols can be natural products. These natural products can be high-molecular-weight natural products, low-molecular-weight natural products, or their derivatives. The aforementioned natural products also include compounds transformed by microorganisms. Examples of polyols include monosaccharides, oligosaccharides, polysaccharides, sugar alcohols (reducing sugars), hydroxy acids, amino acids, vitamins, flavonols, hydroxy hydrocarbons, hydroxyl-containing polymers, polyether polyols, polymer polyols, polyester polyols, and other polyols.

[0244] Examples of monosaccharides include glucose, fructose, galactose, and xylose.

[0245] Examples of oligosaccharides include sucrose, cyclic starch, cyclodextrin, maltose, trehalose, lactose, and sucralose.

[0246] Examples of sugar alcohols (reducing sugars) include sorbitol, maltitol, erythritol, isomaltitol, lactitol, mannitol, xylitol, dehydrated sorbitol, and lactitol.

[0247] Examples of polysaccharides include starch, cellulose, gel polysaccharides, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, κ-carrageenan, ι-carrageenan, isomaltulin, gellan gum, tamarind gum, etc.

[0248] Examples of hydroxy acids include ascorbic acid, kojic acid, quinic acid, chlorogenic acid, and gluconic acid.

[0249] Examples of amino acids include glucosamine, etc.

[0250] Examples of vitamins include ascorbic acid and inositol.

[0251] Examples of flavanols include catechins, quercetin, and anthocyanins.

[0252] Examples of hydroxy hydrocarbons include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerol, trimethylolpropane, and trimethylolethane. Hydroxy hydrocarbons are hydrocarbons containing a hydroxyl group; they can be aromatic or aliphatic, preferably aliphatic. When referring to hydroxy hydrocarbons, it can also refer to hydroxy hydrocarbons other than those included in other groups such as polysaccharides (other hydroxy hydrocarbons).

[0253] Examples of polymers containing hydroxyl compounds include polyglycerol, polyvinyl alcohol, hydroxyethyl methacrylate polymers, hydroxypropyl methacrylate polymers, and hydroxybutyl methacrylate polymers.

[0254] Examples of polyether polyols include compounds obtained by adding olefin oxides to an initiator. Initiators can be compounds having two or more functional hydroxyl groups. Examples of initiators include propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, glycerol, polyglycerol, trimethylolpropane, triethanolamine, pentaerythritol, ethylenediamine, aromatic diamines, diethylenetriamine, sorbitol, and sucrose. Examples of olefin oxides include ethylene oxide and propylene oxide. Polyether polyols obtained by adding olefin oxides to the above-mentioned initiators are also called polyoxyalkylene polyols or alkylene derivatives of polyols. Representative examples of polyether polyols include polyoxypropylene triol obtained by adding propylene oxide to glycerol, and polyoxypropylene polyglycidyl ether obtained by adding propylene oxide to polyglycerol.

[0255] Examples of polymeric polyols include compounds obtained by polymerizing at least a portion of a polyether polyol with an olefinically unsaturated monomer. Examples of such olefinically unsaturated monomers include acrylonitrile and styrene.

[0256] Examples of polyester polyols include compounds obtained by dehydration condensation of compounds with two or more carboxyl groups and compounds with two or more hydroxyl groups. Examples of compounds with two or more carboxyl groups include terephthalic acid, isophthalic acid, phthalic acid, methyl phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, and their anhydrides. Examples of compounds with two or more hydroxyl groups include ethylene glycol, propylene glycol, propanediol, neopentyl glycol, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, and their polymers.

[0257] (Modifier) The modifier is a compound that is reactive with polyols, preferably a compound containing a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group that may have substituents.

[0258] Examples of modifiers are as follows: Acyl halide G(O=)C-Z O Acid anhydride O(C(=O)-Z) O )2 Carboxylic acid HO (O=) C-Z O Isocyanates O=C=N-Z O Thioisocyanates S=C=N-Z O Epoxy (CH2OCH)CH2O-Z O Halides G-Z O Amine H2N-Z O Hydroxyl HO-Z O [In the formula, Z] O As shown above, G is a halogen atom (e.g., F, Cl, Br, or I).

[0259] The Z in the structure of the above-mentioned modifiers can also be... O Replace it with any group that constitutes the modifying group; for example, Z can be made... O It can be a group containing a monovalent hydrocarbon group with 1 to 40 carbon atoms or a monovalent polysiloxane group that can have substituents, for example, it can be Z O For -Y O-Z O n .

[0260] Polyol modifiers can be synthesized by reacting polyols with modifiers. For example, polyol modifiers can be synthesized by reacting acyl halides, acid anhydrides, or carboxylic acids as modifiers with the hydroxyl groups of polyols to form ester bonds. Alternatively, polyol modifiers can be generated by reacting halides or epoxides as modifiers with the hydroxyl groups of polyols to form ether bonds. Regarding the reaction conditions between polyols and modifiers, those skilled in the art can appropriately design the conditions using catalysts (e.g., acid catalysts, base catalysts), condensing agents, etc., depending on the target product.

[0261] [Polycarboxylic acid modified forms] As examples of hydrophobic compounds (A1) and (A2), polycarboxylic acid modifiers will be described. A polycarboxylic acid modifier is a compound that has been chemically modified to exhibit liquid-repellent properties.

[0262] The melting point of the polycarboxylic acid modifier can be above 0°C, above 40°C, above 60°C, above 80°C, above 100°C, or above 120°C, preferably above 40°C, above 50°C, above 60°C, above 70°C, or above 80°C; and can be below 250°C, below 225°C, below 200°C, below 150°C, below 130°C, below 120°C, below 110°C, below 100°C, below 80°C, or below 50°C, for example, below 150°C or below 100°C. The melting point of the polycarboxylic acid modifier can be determined according to JIS K 2235-1991.

[0263] [Structure, etc.] The polycarboxylic acid modifier can be a low molecular weight (e.g., a weight-average molecular weight of less than 1500, less than 1000, or less than 500) and / or a high molecular weight. The weight-average molecular weight of the polycarboxylic acid modifier can be above 100, above 200, above 300, above 400, above 500, above 1000, above 3000, above 5000, above 10000, above 30000, above 100000, above 300000, or above 500000. It can also be below 1,000,000, below 750,000, below 500,000, below 300,000, below 100,000, below 75,000, below 50,000, below 30,000, below 10,000, below 9,000, below 8,000, below 7,000, below 6,000, below 5,000, below 3,000, below 2,000, below 1,000, or below 500.

[0264] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polycarboxylic acid modifiers can be obtained by GFC analysis using polyethylene glycol / polyoxyethylene as a standard sample under the following apparatus and conditions.

[0265] Separation column: SB-806M (8mm×30mm, Shodex) Column temperature: 40℃ Mobile phase solvent: ion-exchanged water Mobile phase flow rate: 1.0 mL / min Sample concentration: 0.5 wt% Injection volume: 50μL Detector: RI detector (Waters 2414, Waters Corporation) The weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity index (Mw / Mn) of polycarboxylic acid modified polystyrene can be determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as the eluent and Shodex KF400RL and KF400RH columns (polystyrene gel) manufactured by Showa Denko Corporation.

[0266] The substitution rate of the hydroxyl group of the carboxyl group in the polycarboxylic acid modifier can 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 can be less than 100%, less than 95%, less than 85%, less than 75%, less than 65%, less than 55%, less than 45%, less than 35%, less than 25%, less than 15%, for example, less than 95%. Here, "substitution rate" refers to the proportion (mol%) of the hydroxyl group of the carboxyl group derived from the polycarboxylic acid that is modified, and refers to the proportion (mol%) modified by a monovalent hydrocarbon group having 1 or more to 40 carbon atoms or a monovalent polysiloxane group that can have substituents.

[0267] The residual percentage of the hydroxyl groups of the carboxyl groups in the polycarboxylic acid modified body can 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 can be less than 100%, 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, less than 50%, less than 30% or less. Here, "residual percentage" refers to the proportion (mol%) of the hydroxyl groups of the carboxyl groups derived from the polycarboxylic acid that are not modified.

[0268] The number of modifying groups in the polycarboxylic acid modifier can be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, or 50 or more, and can be less than 1000, less than 750, less than 500, less than 300, less than 100, less than 50, less than 30, or less than 20. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group that can have substituents.

[0269] The equivalent of the modifying group in the polycarboxylic acid modifier can 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 can be less than 2500, less than 2000, less than 1500, less than 1000, less than 750, less than 500, or less than 400. The equivalent of the modifying group is the value obtained by dividing the weight-average molecular weight of the polycarboxylic acid modifier by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group that may have substituents.

[0270] In a polycarboxylic acid modifier, one or more hydroxyl groups of the polycarboxylic acid are replaced by a modifying group. The modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group that can have a substituent. From the viewpoint of improving liquid repellency, the polycarboxylic acid modifier can be a structure in which an aliphatic hydrocarbon group having 3 to 40 carbon atoms (e.g., 6 to 40 carbon atoms) is modified onto the polycarboxylic acid.

[0271] For details regarding monovalent hydrocarbon groups and monovalent polysiloxane groups that may have substituents, the same approach was taken in the descriptions of (monovalent hydrocarbon groups that may have substituents) and (monovalent polysiloxane groups) above.

[0272] (-Y) C -Z C n ) In the polycarboxylic acid modified body of the present invention, the hydroxyl groups of one or more carboxyl groups of the polycarboxylic acid can be represented by the following formula: -Y C -Z C nThe shown group substitutions, [In the formula,] Y C The reason for selecting Y C1 and Y C2 One or more of the following groups constitute a 1+n valence group: Y C1 It is a directly bonded group composed of one or more groups selected from -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2 and -N(-)2 (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10 or 1 to 4 carbon atoms each time it appears). Y C2 It is a group composed of one or more aliphatic hydrocarbon groups with 1 to 40 carbon atoms that may have substituents, aromatic hydrocarbon rings with 2 to 4 valences that may have substituents, and heterocycles with 2 to 4 valences that may have substituents. Z C It can be a monovalent hydrocarbon group with 1 to 40 carbon atoms or a monovalent polysiloxane group that can have substituents. n is an integer greater than 1 and less than 3.

[0273] (Y) C ) Y C The reason for selecting Y C1 and Y C2 One or more of the following groups constitute a 1+n valence group: Y C1 It is a directly bonded group composed of one or more groups selected from -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2 and -N(-)2 (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10 or 1 to 4 carbon atoms) in each occurrence). Y C2 It is a group composed of one or more of an aliphatic hydrocarbon group with 1 to 40 carbon atoms that may have substituents, an aromatic hydrocarbon ring with 2 to 4 valences that may have substituents, and a heterocycle with 2 to 4 valences that may have substituents.

[0274] n is related to Y C Bonded Z C The number of elements can be an integer between 1 and 3. n can be 1 or higher, 2 or higher, or 3 or higher, and can also be less than 3, less than 2, or less than 1, for example, less than 2.

[0275] Y C The molecular weight can be above 10, above 50, above 100, above 200, above 300, above 500, or above 750, and can be below 3000, below 2500, below 2000, below 1500, below 1000, below 750, below 500, below 300, below 200, below 100, or below 50.

[0276] Y C It can have at least an amide structure. Here, the amide structure can be a broad amide structure, selected from amides (acid amides), ureas, urethanes, imides, thioamides, thioureas, thiourethanes, thioimides, sulfonamides, sulfonamides, sulfonamides, sulfonamides, sulfonamides, etc. The amide structure can be selected from -(C=O)N(-)2, -(C=S)N(-)2, and -S(=O)2N(-)2 (the orientation of each group can be reversed). Here, at least one of the valence bonds of the N group in the amide structure can be bonded to a hydrogen atom. The amide structure is preferably -(C=O)N(-)2, and can be an amide structure selected from amide groups, urea groups, urethane groups, and imide groups. By having an amide structure, the liquid repellency can be improved.

[0277] ○ Y C1 Y C1 It is a non-hydrocarbon linker.

[0278] Y C1 It is a directly bonded group or a group with a divalent or higher valence. Y C1 The valence can be 2–4, 2–3, or 2. Y is preferred. C1 It is not only a direct bond.

[0279] Y C1 The molecular weight can be above 10, above 50, above 100, above 200, above 300 or above 500, and can be below 2000, below 1500, below 1000, below 750 or below 500.

[0280] Y C1 It can be composed of one or more groups selected from direct bonding, -O-, -C(=O)-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2 (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears). As Y C1 Examples can be listed as follows: 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.

[0281] (In the formula, R' is independently a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears.)

[0282] Y C1 It can have at least an amide structure. Here, the amide structure can be a broad amide structure, selected from amides (acid amides), ureas, urethanes, imides, thioamides, thioureas, thiourethanes, thioimides, sulfonamides, sulfonamides, sulfonamides, sulfonamides, sulfonamides, etc. The amide structure can be selected from -(C=O)N(-)2, -(C=S)N(-)2, and -S(=O)2N(-)2 (the orientation of each group can be reversed). Here, at least one of the valence bonds of the N group in the amide structure can be bonded to a hydrogen atom. The amide structure is preferably -(C=O)N(-)2, and can be an amide structure selected from amide groups, urea groups, urethane groups, and imide groups. By having an amide structure, the liquid repellency can be improved.

[0283] ○ Y C2 Y C2 It is a linker composed of one or more of a hydrocarbon group that may have substituents, an aromatic hydrocarbon ring that may have substituents, and a heterocycle that may have substituents.

[0284] Y C2 It can be a hydrocarbon group or a non-hydrocarbon group (containing heteroatoms). Y C2 It can be aliphatic or aromatic. C2 It can be linear, branched, or cyclic.

[0285] Y C2 It is a divalent or higher group. Y C2 The valence can be, for example, 2-4, 2-3, or 2.

[0286] Y C2 The number of carbon atoms can be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and can be less than 40, less than 35, less than 30, less than 25, less than 20, less than 15, less than 10, or less than 5.

[0287] Y C2 It is composed of one or more aliphatic hydrocarbon groups with 1 to 40 carbon atoms that may have substituents, aromatic hydrocarbon rings with 2 to 4 valences that may have substituents, and heterocycles with 2 to 4 valences that may have substituents.

[0288] Aliphatic hydrocarbon groups with 1 to 40 carbon atoms and a valence of 2 to 4 can be cyclic, branched, or straight-chain hydrocarbon groups. These groups can be saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon groups. The number of carbon atoms in these groups can be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and can be less than 35, less than 30, less than 25, less than 20, less than 15, less than 10, or less than 5. The valence of the aliphatic hydrocarbon group can be 2 or more, 3 or more, or 4, and can be less than 4, less than 3, or 2.

[0289] Aliphatic hydrocarbon groups may have substituents. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (where R' is a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms each time it appears). 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 aliphatic hydrocarbon groups with substituents, the amount of carbon atoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, relative to the amount of carbon atoms and heteroatoms; and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0290] Examples of aromatic hydrocarbon rings with 2 to 4 valences include groups formed by removing 2 to 4 hydrogen atoms from aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, benzo[a]tetraphenyl (naphthene), pentabenzene, pyrene, and phenanthrene. The number of ring atoms in the aromatic hydrocarbon ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the aromatic hydrocarbon ring can be 2 or more, 3 or more, or 4, and can be 4 or less, 3 or less, or 2.

[0291] Aromatic hydrocarbon rings may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms each time it appears). Substituents may or may not have active hydrogen atoms. 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 aromatic hydrocarbon rings with substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more; and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0292] The 2- to 4-valent heterocycle can be an aliphatic or aromatic group. Examples of 2- to 4-valent heterocycles include groups from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cyclophosphine, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benziisothiazole, pyrrolidine, piperidine, piperazine, imidazole, thiazoline, etc., which have had 2 to 4 hydrogen atoms removed. The number of cyclic atoms in the heterocycle is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the heterocycle can be 2 or more, 3 or more, or 4, and can be 4 or less, 3 or less, or 2.

[0293] Heterocyclic rings may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms each time it appears). Substituents may or may not have active hydrogen atoms. 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 heterocyclic rings with 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 be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0294] As Y C2 Examples can be listed as follows: -Ali- -Cy- -Ali (-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali (-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- etc. [In the formula, Ali is an aliphatic hydrocarbon group with 1 to 20 carbon atoms, and Cy is an aromatic hydrocarbon ring or heterocycle.]

[0295] As Y C2 Specific examples can be listed as follows: - (CH2) p - (p is 1-40, 1-20, or 1-10) A straight-chain hydrocarbon group with unsaturated bonds, having 1–40, 1–20, or 1–10 carbon atoms. Hydrocarbon groups with branched structures having 1–40, 1–20, or 1–10 carbon atoms - (CH2) q -Cy- (CH2) r - (q and r are independently 0 to 20, for example 1 to 10, and Cy is an aromatic hydrocarbon ring or a heterocyclic ring) etc.

[0296] (Y) C (Example) For Y C Examples will be used to illustrate this. In the following text, R' is independently a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears.

[0297] As Y C For example, in Y C When it is divalent, we can list -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 -、-Y C2 -Y C1 -Y C2 -、-Y C2 -YC1 -Y C2 -Y C1 - etc.

[0298] As Y C For example, when Y C is trivalent, the following can be listed: -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 -Y C2 -Y C1 (-)2, -Y C2 -Y C1 -Y C2 -(YC1 -)2, -Y C2 -Y C1 -(Y C2 -Y C1 -)2, -Y C2 -(Y C1 -Y C2 -Y C1 -)2 etc.

[0299] As Y C For example, when Y C is tetravalent, the following can be listed: -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 -Y C2 (-)3, -Y C2 -Y C1 (-Y C2 -)3, -Y C2 -(Y C1 -Y C2 -)3, -Y C2 -YC1 -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.

[0300] As Y C Preferred examples can be listed as -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.

[0301] (Y) C (Preferred example) Preferred Y C For -Y C11 - or -Y C11 -Y C21 -Y C12 -, [In the formula, each symbol appears independently each time.] Y C11 It is either -O- or -NR'-. Y C21 It consists of hydrocarbon groups with 1 to 40 carbon atoms. Y C12 are -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. ].

[0302] Y C11 It is a non-hydrocarbon linker, which is a directly bonded or divalent or higher group.

[0303] Y C11 The molecular weight can be above 10, above 50, above 100, above 200, above 300 or above 500, and can be below 2000, below 1500, below 1000, below 750 or below 500.

[0304] Y C11 It can be a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-.

[0305] Y C21 It is a divalent hydrocarbon linker, which can be a hydrocarbon group with 1 to 40 carbon atoms.

[0306] Y C21 The number of carbon atoms can be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and can be less than 40, less than 35, less than 30, less than 25, less than 20, less than 15, less than 10, or less than 5.

[0307] Here, the hydrocarbon group with 1 to 40 carbon atoms can be a cyclic, branched, or straight-chain hydrocarbon group, and can be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group.

[0308] As Y C21 Specific examples can be listed as follows: - (CH2) p - (p is 1-40, 1-20, or 1-10) A straight-chain hydrocarbon group with unsaturated bonds, having 1–40, 1–20, or 1–10 carbon atoms. Hydrocarbon groups with branched structures having 1–40, 1–20, or 1–10 carbon atoms - (CH2) q -Cy- (CH2) r - (q and r are independently 0 to 20, for example 1 to 10, and Cy is an aromatic hydrocarbon ring or a heterocyclic ring) etc.

[0309] Y C12Can 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.

[0310] Y C12 It can have at least an amide structure. Here, the amide structure can be a broad amide structure, selected from amides (acid amides), ureas, urethanes, imides, thioamides, thioureas, thiourethanes, thioimides, sulfonamides, sulfonamides, sulfonamides, sulfonamides, sulfonamides, etc. The amide structure can be selected from -(C=O)N(-)2, -(C=S)N(-)2, and -S(=O)2N(-)2 (the orientation of each group can be reversed). Here, at least one of the valence bonds of the N group in the amide structure can be bonded to a hydrogen atom. The amide structure is preferably -(C=O)N(-)2, and can be an amide structure selected from amide groups, urea groups, urethane groups, and imide groups. By having an amide structure, the liquid repellency can be improved.

[0311] (Z) C ) Z C The following are examples of monovalent hydrocarbon groups or monovalent polysiloxane groups that may have substituents and have 1 to 40 carbon atoms: (monovalent hydrocarbon groups that may have substituents) and (monovalent polysiloxane groups).

[0312] [Other Modifying Groups] The hydroxyl group in the carboxyl group of a polycarboxylic acid can also be replaced by -Y C -Z C n Other modifying groups may be substituted. Examples of modifying groups include anionic and / or cationic groups. As anionic and / or cationic groups, the manner in which they are described in the section on [other modifying groups] of polyols above shall be followed.

[0313] [Manufacturing Method] Polycarboxylic acid modifiers can be manufactured by reacting a modifier having a modifier group (or a precursor structure of the modifier group) with a hydroxyl group in the carboxyl group of a polycarboxylic acid.

[0314] (Polycarboxylic acids) Polycarboxylic acids are compounds with two or more carboxyl groups and are the starting materials for polycarboxylic acid modifiers. A polycarboxylic acid is a compound with two or more carboxyl groups within its molecule. Polycarboxylic acids can be aliphatic or aromatic, preferably aliphatic.

[0315] Polycarboxylic acids can be low molecular weight (e.g., weight average molecular weight less than 1000, below 500) and / or high molecular weight. The weight average molecular weight of polycarboxylic acids can be above 100, above 300, above 500, above 1000, above 3000, above 5000, above 10000, above 30000, above 100000, above 300000, or above 500000, and can be below 1000000, below 7500000, below 500000, below 300000, below 100000, below 75000, below 50000, below 30000, below 10000, below 5000, below 3000, below 2000, below 1000, or below 500.

[0316] The number of carboxyl groups in a polycarboxylic acid can be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more, and can be less than 3000, less than 1000, less than 750, less than 500, less than 300, less than 100, less than 50, less than 30, or less than 20.

[0317] The carboxyl equivalent of a polycarboxylic acid can be greater than 20, greater than 40, greater than 60, greater than 80, greater than 100, greater than 120, or greater than 150, and can also be less than 1000, less than 800, less than 600, less than 400, less than 200, less than 100, or less than 75. The carboxyl equivalent of a polycarboxylic acid is the value obtained by dividing the weight-average molecular weight of the polycarboxylic acid by the number of hydroxyl groups.

[0318] Polycarboxylic acids can be natural products. These natural products can be high-molecular-weight natural products, low-molecular-weight natural products, or their derivatives. Compounds transformed by microorganisms are also included among these natural products.

[0319] The polycarboxylic acid can be at least one selected from dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, carboxyl-containing polymers, and their salts.

[0320] Dicarboxylic acids are compounds that have two carboxyl groups, such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid, terephthalic acid, malic acid, tartaric acid, aldonic acid, and their salts.

[0321] Tricarboxylic acids are compounds with three carboxyl groups, such as citric acid, procarboxylic acid, trans-aconitic acid, trimellitic acid, and their salts.

[0322] Tetracarboxylic acids are compounds with four carboxyl groups, such as pyromellitic acid and its salts.

[0323] Carboxyl-containing polymers are compounds with 5 or more carboxyl groups, such as alginate, tragacanth gum, gum arabic, polyacrylic acid, polymethacrylic acid, polymaleic acid, polyaspartic acid, polyglutamic acid, hyaluronic acid, heparin, xanthan gum, gellan gum, alginate carboxymethyl cellulose, galacturonic acid, mannouronic acid, and their salts.

[0324] (Modifier) The modifier is a compound that is reactive with polycarboxylic acids, preferably the above-mentioned compound containing a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group that may have substituents.

[0325] Examples of modifiers are as follows: Epoxy (CH2OCH)CH2O-Z C Amine H2N-Z C Hydroxyl HO-Z C [In the formula, Z] C As above.

[0326] The Z in the structure of the above-mentioned modifiers can also be... C Replace it with any group that constitutes the modifying group; for example, Z can be made... C It can be a hydrocarbon group with 1 to 40 monovalent carbon atoms that can have substituents, for example, it can be a Z-type hydrocarbon group. C For -Y C -Z C n .

[0327] Polycarboxylic acid modifiers can be synthesized by reacting polycarboxylic acids with modifying agents. For example, reacting an epoxy compound as a modifying agent with the carboxyl group of a polycarboxylic acid to form an ester bond can generate a polycarboxylic acid modifier. Those skilled in the art can design appropriate reaction conditions for the polycarboxylic acid and the modifying agent based on the target product, using catalysts (e.g., acid catalysts, base catalysts), condensing agents, etc.

[0328] 〔Oil〕 Oils are described as examples of hydrophobic compounds (A1) and (A2), respectively. Oils can be liquid or solid (wax) at room temperature. Oils can be selected from synthetic oils, mineral oils, animal oils, and vegetable oils. Oils can be hydrocarbon oils or non-hydrocarbon oils, typically compounds with higher hydrocarbon structures (e.g., 10 or more, 20 or more, or 30 or more carbon atoms). Oils can have the hydrocarbon groups described above. Oils can be compounds different from the amine modifiers, polyol modifiers, and polycarboxylic acid modifiers described above. Furthermore, oils are non-volatile oily compounds with boiling points, for example, above 200°C, above 250°C, or above 300°C.

[0329] The melting point of the oil can be above -100℃, above -75℃, above -50℃, above 0℃, above 30℃, above 40℃, above 60℃, above 80℃, above 100℃, or above 120℃, preferably above 40℃, above 50℃, above 60℃, above 70℃, or above 80℃; and can also be below 250℃, below 225℃, below 200℃, below 150℃, below 130℃, below 120℃, below 110℃, below 100℃, below 80℃, below 50℃, below 25℃, below 0℃, below -25℃, below -50℃, below -75℃, or below -100℃, for example, below 150℃, below 100℃, below 50℃, below 0℃, or below -50℃. The melting point of the oil can be determined according to JIS K 2235-1991.

[0330] Oils can be low molecular weight (e.g., molecular weight below 1000 or 500) or high molecular weight. When oils are high molecular weight, their weight-average molecular weight can be above 1000, above 3000, above 5000, above 7500, above 10000, above 30000, above 100000, above 300000, or above 500000. Furthermore, they can be below 10000000, below 7500000, below 500000, below 300000, below 100000, below 750000, below 500000, below 300000, below 100000, below 75000, below 50000, below 30000, below 10000, below 7500, below 50000, below 30000, below 10000, below 7500, below 5000, or below 3000.

[0331] [Synthetic oil] Synthetic oils are oils (oil-like compounds) obtained through chemical synthesis. They can be liquid or solid (wax) at room temperature. Examples of synthetic oils include hydrocarbon oils, ester oils, ether oils, amide oils, and silicone oils.

[0332] [Mineral oil] Mineral oil can be liquid or solid (wax) at room temperature. Examples of mineral oils include petrolatum, liquid paraffin, paraffin wax, microcrystalline wax, lignite wax, ceresin wax, pure ceresin wax, and fine-crystalline petroleum wax.

[0333] [Vegetable oil, animal oil] Vegetable and animal oils can 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, flaxseed oil, castor oil, jojoba oil, cocoa butter, palm oil, palm kernel oil, coconut oil, hemp seed oil, rice bran oil, tea seed oil, castor oil, sesame oil, fish oil, shark liver oil, squalene oil, squalene, beef tallow, lard, mutton tallow, beef foot fat, whale oil, salmon oil, bonito oil, herring oil, cod oil, etc., as well as the hardened and hydrogenated forms of these oils; rice bran wax, carnauba wax, sunflower oil, etc. Candelilla wax, lacquer wax, beeswax, lanolin, cetearyl wax, white wax, etc.; fatty acids such as stearic acid, capric acid, hexanoic acid, linoleic acid, linolenic acid, palmitic acid, lauric acid, tung oil acid, etc.; fatty alcohols such as lauryl alcohol, cetearyl alcohol, stearyl alcohol, cetyl alcohol, myristyl alcohol, etc.; fatty acid esters such as glyceryl monostearate, glyceryl monooleate, acetylated glyceryl monostearate, tristearate, tripalmitin, and cetyl ester-based glyceryl palmitate; behenyl ester; medium-chain triglycerides, etc.

[0334] [An example of hydrophobic compounds (A1) and (A2)] The hydrophobic compound (A1) can be, for example, the amine modifier described above, especially the aliphatic amine modifier.

[0335] The hydrophobic compound (A1) can be, for example, the amine modifier or wax (e.g., hydrocarbon wax) described above, especially the amine modifier (particularly aliphatic amine modifiers). As a specific example, the following can be cited: Paraffin wax with 20 to 40 carbon atoms, etc.

[0336] Examples of hydrophobic compounds (A2) include monoester compounds, diester compounds, trimer compounds, tetraester compounds, polyester compounds, monoamide compounds, diamide compounds, triamide compounds, polyamide compounds, etc.

[0337] Examples of ester compounds include glycerides, polyglycerides, sucrose esters, sorbitol esters, pentaerythritol esters, trimellitates, phthalates, adipates, pyromellitic esters, citrates, benzoates, or CH3(CH2). n Ester compounds formed by the condensation of alcohols and fatty acids with OH (n = 0 to 30, with straight or branched structures).

[0338] Examples of amide compounds include condensates of fatty acids and monoamines, condensates of fatty acids and diamines, condensates of fatty acids and triamines, condensates of fatty acids and tetraamines, and condensates of fatty acids and pentamines.

[0339] Hydrophobic compounds (A2) can be, for example, the polycarboxylic acid modified forms, polyol modified forms, or oils described above, especially compounds having multiple (e.g., 2-10, 2-6, 2-4) monovalent aliphatic hydrocarbon structures (especially fatty acid ester structures). Examples of hydrophobic compounds (A2) include fatty acid-modified polyols (e.g., fatty acid-modified sugars), oils, and long-chain aliphatic alcohol-modified polycarboxylic acids (e.g., long-chain alcohol-modified polyvalent aromatic rings). As a specific example, the following can be listed: wait.

[0340] [Dispersant] The compositions of the present invention may contain a dispersant. The dispersant may be at least one selected from organic and inorganic dispersants. The dispersant may be at least one selected from anionic dispersants, nonionic dispersants, cationic dispersants, amphoteric dispersants, and inorganic dispersants.

[0341] Dispersants can be organic dispersants and inorganic dispersants, or a combination of organic and inorganic dispersants.

[0342] Organic dispersants can be used as dispersants. Organic dispersants can be classified into nonionic dispersants, anionic dispersants, cationic dispersants, and amphoteric dispersants. Organic dispersants are essentially surfactants.

[0343] The dispersant can be a non-fluorinated dispersant.

[0344] [Nonionic dispersant] Dispersants may include nonionic dispersants. Nonionic dispersants may be nonionic surfactants.

[0345] Nonionic dispersants can be either low molecular weight or high molecular weight. Molecular weights can be above 100, 500, 1000, 2000, 4000, or 6000, and can also be below 100,000, 25,000, 10,000, 7,500, 5,000, 2,500, 750, or 250.

[0346] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides.

[0347] Examples of ethers include compounds having oxyalkylene groups (preferably polyoxyethylene groups).

[0348] Examples of esters include esters of alcohols and fatty acids. Examples of alcohols include 1- to 30-membered (especially 2- to 10-membered) alcohols with 1 to 50 carbon atoms (especially 10 to 30 carbon atoms), such as aliphatic alcohols. Examples of fatty acids include saturated or unsaturated fatty acids with 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0349] Examples of ester ethers include compounds formed by the addition of alkyl epoxides (especially ethylene oxide) to the esters of alcohols and fatty acids. Examples of alcohols include 1- to 30-membered (especially 2- to 10-membered) alcohols (e.g., aliphatic alcohols) with 1 to 50 carbon atoms (especially 3 to 30 carbon atoms). Examples of fatty acids include saturated or unsaturated fatty acids with 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0350] Examples of alkanolamides are formed from fatty acids and alkanolamines. Alkanolamides can be monoalkanolamides or dialkanolamides. Examples of fatty acids are saturated or unsaturated fatty acids with 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. Alkanolamines can be alkanols with 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0351] Polyols can be 2 to 5-membered alcohols with 10 to 30 carbon atoms.

[0352] The amine oxide can be an oxide of an amine (secondary amine or preferably tertiary amine) (e.g., having 5 to 50 carbon atoms).

[0353] The nonionic dispersant is preferably a nonionic dispersant having an alkylene oxide (preferably polyoxyethylene). The number of carbon atoms in the alkylene oxide is preferably 2 to 10. The number of alkylene oxides in the molecule of the nonionic dispersant is generally preferably 2 to 100.

[0354] The nonionic dispersant is selected from ethers, esters, ester ethers, alkanolamides, polyols and amine oxides, and is preferably a nonionic dispersant with oxyalkylene groups.

[0355] Nonionic dispersants can 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), dehydrated sorbitol esters of linear and / or branched fatty acids (saturated and / or unsaturated), glycerides of linear and / or branched fatty acids (saturated and / or unsaturated), polyglycerol esters of linear and / or branched fatty acids (saturated and / or unsaturated), sucrose esters of linear and / or branched fatty acids (saturated and / or unsaturated), polyoxyethylene (POE) / polyoxypropylene (POP) copolymers (random copolymers or block copolymers), alkylene glycol alkylene oxide adducts, etc. Among these, the preferred structures of the alkylene oxide addition portion and the polyalkylene glycol portion are polyoxyethylene (POE), polyoxypropylene (POP), or POE / POP copolymers (which can be random copolymers or block copolymers).

[0356] In addition, nonionic dispersants may not contain aromatic groups.

[0357] Nonionic dispersants can be of the following formula: R 1 O-(CH2CH2O) p - (R) 2 O) q -R 3 The compound shown, [In the formula, R] 1 It is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an acyl group. Each R 2 Independent, can be the same or different, and is an alkylene group with 3 or more carbon atoms (e.g., 3 to 10). R 3 It consists of hydrogen atoms, alkyl groups having 1 to 22 carbon atoms, or alkenyl groups having 2 to 22 carbon atoms. p is a number greater than or equal to 2. q is a number that is 0 or greater than 1.

[0358] R 1 Preferably, the number of carbon atoms is 8–20, particularly 10–18. As R… 1 Preferred specific examples may include octyl, nonyl, trimethylnonyl, lauryl, tridecyl, oleyl, and stearyl.

[0359] R 2 Examples include propylidene and butylidene.

[0360] In nonionic dispersants, p can be a number greater than 3 (e.g., 5–200). q can be a number greater than 2 (e.g., 5–200). That is, -(R 2 O) q- It can form polyoxyalkylene chains.

[0361] The nonionic dispersant can be a polyoxyethylene alkylene ether having a central hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (especially a polyoxyalkylene chain). Examples of hydrophobic oxyalkylene chains include oxypropylene chains, oxybutylene chains, and styrene chains, with oxypropylene chains being preferred.

[0362] Specific examples of nonionic dispersants include: ethylene oxide with hexylphenol, isooctylphenol, hexadecyl alcohol, oleic acid, and alkyl groups (C... 12 -C 16 Thiols, sorbitol monofatty acids (C7-C5) 19 ) or alkyl (C 12 -C 18 Condensation products of amines, etc., dehydrated sorbitol fatty acid esters, glycerol fatty acid esters, polyglycerol fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerol fatty acid esters, polyoxyethylene dehydrated sorbitol fatty acid esters, lecithin derivatives, etc. Examples of nonionic dispersants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycol, polyoxyethylene imine ethoxylates, etc.

[0363] The proportion of polyoxyethylene blocks relative to the molecular weight of the nonionic dispersant (copolymer) can be 5 to 80% by weight, for example 30 to 75% by weight, and particularly 40 to 70% by weight.

[0364] The average molecular weight of nonionic dispersants is typically 300–5000, for example, 500–3000.

[0365] Nonionic dispersants can be a single type or a mixture of two or more. Nonionic dispersants can be mixtures of compounds with an HLB (hydrophilicity-hydrophobicity balance) of less than 15 (particularly less than 5) and compounds with an HLB of 15 or more. Specifically, preferred dispersants are polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyethylene oxide, polyoxypropylene, or dehydrated sorbitol fatty acid esters, glycerol fatty acid esters, polyglycerol fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerol fatty acid esters, and polyoxyethylene dehydrated sorbitol fatty acid esters with an HLB of 1 to 18.

[0366] [Catonic dispersant] Dispersants may include cationic dispersants. Cationic dispersants may be cationic surfactants. Cationic dispersants may be compounds without amide groups.

[0367] Cationic dispersants can be low molecular weight (e.g., molecular weight below 2000, especially below 10000) or high molecular weight (e.g., molecular weight above 2000). The molecular weight of cationic dispersants can be above 100, above 500, above 1000, above 2000, above 4000, or above 6000, and can be below 1,000,000, below 750,000, below 500,000, below 250,000, below 100,000, below 50,000, below 25,000, below 10,000, below 7,500, below 5,000, below 2,500, below 750, or below 250.

[0368] Cationic dispersants can be aliphatic or aromatic, and examples include ammonium salts (such as quaternary ammonium salts). Cationic dispersants can be addition-type ammonium salts of ethylene oxide. Specifically, examples include: amine salt dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazoline; quaternary ammonium salt dispersants such as alkyl trimethylammonium salts, dialkyl dimethylammonium salts, alkyl dimethyl benzylammonium salts, pyridinium salts, alkyl isoquinoline onion salts, benzalkonium chloride, and benzyl chloride; and high-molecular-weight cationic dispersants such as polyquaternium salts-1 to 47. Examples of cationic dispersants include alkylamine salts and quaternary ammonium salts.

[0369] Low molecular weight cationic dispersants can be R 21 -N ＋ (-R) 22 (-R) 23 (-R) 24 )X － The compound shown.

[0370] [In the formula, R] 21 R 22 R 23 and R 24 It consists of hydrogen or a hydrocarbon group having 1 to 40 carbon atoms. X is an anionic group. R 21 R 22 R 23 and -R 24 Specific examples of X include alkyl groups (e.g., methyl, butyl, stearyl, palmityl). Specific examples of X include halogens (e.g., chlorine) and acids (e.g., hydrochloric acid, acetic acid). Cationic dispersants can be monoalkyl trimethylammonium salts (alkyl groups with 4 to 40 carbon atoms).

[0371] Specifically, low-molecular-weight cationic dispersants can be of the following formula: R 1 p -N ＋ R 2q X － The ammonium salt shown.

[0372] [In the formula, R] 1 For C12 and above (e.g., C 12 ~C 50 Straight-chain and / or branched aliphatic (saturated and / or unsaturated) groups, R 2 It is an alkyl group, benzyl group, or polyoxyethylene group (with an oxyethylene number of, for example, 1 (especially 2, especially 3) to 50) of H or C1 to 4 (particularly preferred CH3, C2H5). X is a halogen atom (e.g., chlorine), a C1-C4 fatty acid salt, or a C1-C4 sulfonate. p is 1 or 2, q is 2 or 3, and p + q = 4. R 1 The number of carbon atoms can be 12 to 50, for example, 12 to 30.

[0373] Low molecular weight cationic dispersants may include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyl di(hydroxypolyoxyethylene)ammonium chloride, benzyldodecyl di(hydroxypolyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride, etc.

[0374] High molecular weight cationic dispersants can be various polymers (e.g., polyquaternium salts-1 to 47) containing cationic groups (e.g., ammonium groups, quaternary ammonium groups). Examples of high molecular weight cationic dispersants include: cationic starch, cationic cellulose (e.g., O-(2-hydroxy-3-(trimethylammonium)propylhydroxyethyl cellulose chloride), cationic guar gum, cationic xanthan gum, chitosan, and other cationic natural products (especially cationic sugars); polymers of monomers containing cationic groups such as aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, dimethylammonium quaternized ethyl methacrylate, diallyl dimethylammonium chloride, dimethylaminopropylamine, and quaternized vinylimidazole.

[0375] [Anionic dispersant] Dispersants may contain anionic dispersants. Anionic dispersants may be anionic surfactants. Dispersants may also not contain anionic dispersants.

[0376] Anionic dispersants can be either low molecular weight or high molecular weight. Molecular weights can be above 100, 500, 1000, 2000, 4000, or 6000, and can also be below 100,000, 25,000, 10,000, 7,500, 5,000, 2,500, 750, or 250.

[0377] Examples of anionic dispersants include: alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonyl fatty acid salts, N-acyl amino acid type dispersants, phosphate monoester or diester type dispersants, and sulfosuccinates. Examples of anionic dispersants include carboxylates (e.g., fatty acid salts).

[0378] [Amphoteric Dispersant] Dispersants may include amphoteric dispersants. Amphoteric dispersants may be amphoteric surfactants.

[0379] Amphoteric dispersants can be either low molecular weight or high molecular weight. Molecular weight can be above 100, above 500, above 1000, above 2000, above 4000, or above 6000, and can also be below 100000, below 25000, below 10000, below 7500, below 5000, below 2500, below 750, or below 250.

[0380] Examples of amphoteric dispersants include: alanine derivatives, imidazoline betaines, amide betaines, and acetate betaines. More specifically, examples include: lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazoline betaine, lauryl dimethyl aminoacetic acid betaine, and fatty acid amide propyl dimethyl aminoacetic acid betaine.

[0381] [Inorganic dispersant] Dispersants may include inorganic dispersants.

[0382] The average primary particle size of inorganic dispersants can be greater than 5 nm, greater than 30 nm, greater than 100 nm, greater than 1 μm, greater than 10 μm, or greater than 25 μm, and can also be less than 100 μm, less than 50 μm, less than 10 μm, less than 1 μm, less than 500 nm, or less than 300 nm. The average primary particle size can be determined, for example, by observation using a microscope (scanning electron microscope or transmission electron microscope). Inorganic dispersants can be hydrophilic particles.

[0383] Examples of inorganic dispersants include: tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, hydroxyapatite and other polyvalent metal salts of phosphate; calcium carbonate, magnesium carbonate and other carbonates; calcium metasilicate and other silicates; calcium sulfate, barium sulfate and other sulfates; calcium hydroxide, magnesium hydroxide, aluminum hydroxide and other hydroxides, etc.

[0384] [Amount of dispersant] The amount of dispersant relative to 100 parts by weight of hydrophobic compound (A) can be more than 0.01 parts by weight, more than 0.1 parts by weight, more than 1 part by weight, more than 3 parts by weight, more than 5 parts by weight, more than 10 parts by weight, more than 15 parts by weight, more than 20 parts by weight, more than 50 parts by weight, more than 75 parts by weight, or more than 100 parts by weight, and can be less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, less than 5 parts by weight, less than 3 parts by weight, or less than 1 part by weight.

[0385] [Liquid medium] The compositions of the present invention may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The compositions of the present invention may contain at least water, and may be an aqueous dispersion.

[0386] Examples of organic solvents include esters (e.g., esters with 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2 to 40 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols with 1 to 40 carbon atoms, specifically isopropanol), aromatic solvents (e.g., toluene and xylene), and petroleum-based solvents (e.g., alkanes with 5 to 10 carbon atoms, specifically naphtha and kerosene). Water-soluble organic solvents are preferred. Water-soluble organic solvents may also contain compounds having at least one hydroxyl group (e.g., alcohols, diols, polyols, ethers of polyols (e.g., monoethers)). They can be used alone or in combination of two or more.

[0387] [Amount of liquid medium] The amount of liquid medium relative to 1 part by weight of hydrophobic compound (A) can be more than 1 part by weight, more than 3 parts by weight, more than 5 parts by weight, more than 10 parts by weight, more than 20 parts by weight, more than 30 parts by weight, more than 40 parts by weight, or more than 50 parts by weight, more than 100 parts by weight, more than 200 parts by weight, more than 300 parts by weight, more than 500 parts by weight, or more than 1000 parts by weight, and can be less than 3000 parts by weight, less than 2000 parts by weight, less than 1000 parts by weight, less than 500 parts by weight, less than 200 parts by weight, less than 175 parts by weight, less than 150 parts by weight, less than 125 parts by weight, less than 100 parts by weight, less than 80 parts by weight, less than 60 parts by weight, less than 40 parts by weight, less than 20 parts by weight, or less than 10 parts by weight.

[0388] The amount of water relative to 1 part by weight of hydrophobic compound (A) can be more than 1 part by weight, more than 3 parts by weight, more than 5 parts by weight, more than 10 parts by weight, more than 20 parts by weight, more than 30 parts by weight, more than 40 parts by weight, more than 50 parts by weight, more than 100 parts by weight, more than 200 parts by weight, more than 300 parts by weight, more than 500 parts by weight, or more than 1000 parts by weight, and can be less than 3000 parts by weight, less than 2000 parts by weight, less than 1000 parts by weight, less than 500 parts by weight, less than 200 parts by weight, less than 175 parts by weight, less than 150 parts by weight, less than 125 parts by weight, less than 100 parts by weight, less than 80 parts by weight, less than 60 parts by weight, less than 40 parts by weight, less than 20 parts by weight, or less than 10 parts by weight.

[0389] The amount of organic solvent relative to 1 part by weight of hydrophobic compound (A) can be more than 1 part by weight, more than 3 parts by weight, more than 5 parts by weight, more than 10 parts by weight, more than 20 parts by weight, more than 30 parts by weight, more than 40 parts by weight, more than 50 parts by weight, more than 100 parts by weight, more than 200 parts by weight, more than 300 parts by weight, more than 500 parts by weight, or more than 1000 parts by weight, and can be less than 3000 parts by weight, less than 2000 parts by weight, less than 1000 parts by weight, less than 500 parts by weight, less than 200 parts by weight, less than 175 parts by weight, less than 150 parts by weight, less than 125 parts by weight, less than 100 parts by weight, less than 80 parts by weight, less than 60 parts by weight, less than 40 parts by weight, less than 20 parts by weight, or less than 10 parts by weight.

[0390] [Organic acids] The compositions of the present invention may contain organic acids. Known organic acids can be used as organic acids. Examples of preferred organic acids include carboxylic acids, sulfonic acids, and sulfinic acids, with carboxylic acids being particularly preferred. Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, and citric acid, with formic acid or acetic acid being particularly preferred. In the present invention, one or more organic acids may be used. For example, formic acid and acetic acid may be used in combination.

[0391] [Amount of organic acids] The amount of organic acid relative to 100 parts by weight of the hydrophobic compound (A) can be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and can be less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 40 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight. The amount of organic acid can be adjusted so that the pH of the composition reaches 3 to 10, for example 5 to 9, especially 6 to 8. The composition can be acidic (pH 7 or less, for example 6 or less).

[0392] [Curing agent] The compositions of the present invention may contain a curing agent (an active hydrogen reactive compound or a compound containing active hydrogen).

[0393] The curing agent (crosslinking agent) in the composition enables the hydrophobic compound (A) to cure well. The curing agent can be an active hydrogen reactive compound, or a compound containing active hydrogen, that reacts with the active hydrogen or active hydrogen reactive groups present in the hydrophobic compounds (A1) and (A2). Examples of active hydrogen reactive compounds include isocyanate compounds, epoxy compounds, chloromethyl compounds, carboxyl compounds, and acylhydrazine compounds. Examples of compounds containing active hydrogen include hydroxyl compounds, amino compounds, carboxyl compounds, ketone compounds, acylhydrazine compounds, and melamine compounds.

[0394] Curing agents can contain isocyanate compounds. Isocyanate compounds can be polyisocyanate compounds. Polyisocyanate compounds are compounds having two or more isocyanate groups in one molecule. Polyisocyanate compounds act as crosslinking agents. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, and their derivatives. Isocyanate compounds can also be end-capped isocyanate compounds (e.g., end-capped polyisocyanate compounds). End-capped isocyanate compounds are compounds in which the isocyanate groups of the isocyanate compound are masked by a end-capping agent, thereby inhibiting the reaction.

[0395] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate or 2,2,4-trimethylhexamethylene diisocyanate, 2,6- Aliphatic diisocyanates such as diisocyanate-methylhexanoate, as well as aliphatic triisocyanates such as lysine ester triisocyanates, 1,4,8-triisocyanate-octane, 1,6,11-triisocyanate-undecane, 1,8-diisocyanate-4-isocyanate-methyloctane, 1,3,6-triisocyanate-hexane, and 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate-methyloctane, etc. They can be used alone or in combination of two or more.

[0396] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isoflurone diisocyanate), and 1,3,5-triisocyanate cyclohexane. They can be used alone or in combination of two or more.

[0397] Examples of aromatic aliphatic polyisocyanates include aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of aromatic aliphatic polyisocyanates include 1,3-phenylenedimethyl diisocyanate or 1,4-phenylenedimethyl diisocyanate or mixtures thereof, 1,3-bis(1-isocyano-1-methylethyl)benzene or 1,4-bis(1-isocyano-1-methylethyl)benzene (tetramethylphenyldimethyl diisocyanate) or mixtures thereof, and 1,3,5-triisocyanomethylbenzene. They can be used alone or in combination of two or more.

[0398] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylene diisocyanate, terephthalene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'-diphenylmethane diisocyanate or 4,4'-diphenylmethane diisocyanate or mixtures thereof, 2,4-toluene diisocyanate or 2,6-toluene diisocyanate or mixtures thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate, etc. They can be used alone or in combination of two or more.

[0399] Derivatives of polyisocyanates include, for example, various derivatives of the aforementioned polyisocyanate compounds such as dimers, trimers, biurets, urethanes, carbodiimides, urea diketones, urea imides, isocyanurates, and iminooxadiazine diketones. They can be used alone or in combination of two or more.

[0400] These polyisocyanates can be used alone or in combination of two or more.

[0401] As a polyisocyanate compound, it is preferable to use a compound in which the isocyanate group of the polyisocyanate compound is capped by a capping agent, i.e., a capped polyisocyanate compound (capped isocyanate). Capped polyisocyanate compounds are preferred due to their greater stability in solution.

[0402] End-capping agents are substances that seal free isocyanate groups. End-capped polyisocyanate compounds, by heating to, for example, above 100°C or 130°C, regenerate the isocyanate groups and readily react with hydroxyl groups. Examples of end-capping agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. Polyisocyanate compounds can be used alone or in combination of two or more.

[0403] Epoxides are compounds that contain epoxy groups. Examples of epoxy compounds include those with polyoxyalkylene groups, such as polyglycerol polyglycidyl ether, polypropylene glycol diglycidyl ether, and sorbitol polyglycidyl ether.

[0404] Compounds containing chloromethyl groups are compounds that have a chloromethyl group present in their structure. Examples of compounds containing chloromethyl groups include chloromethyl polystyrene.

[0405] Compounds containing a carboxyl group are compounds that have a carboxyl group. Examples of compounds containing a carboxyl group include (poly)acrylic acid and (poly)methacrylic acid.

[0406] Specific examples of compounds containing ketone groups include (poly)diacetone acrylamide and diacetone alcohol.

[0407] Specific examples of acylhydrazide compounds include hydrazine, carbazide, and adipic hydrazide.

[0408] Specific examples of melamine compounds include melamine resins and methyl etherified melamine resins.

[0409] [Amount of curing agent] The amount of curing agent relative to 100 parts by weight of hydrophobic compound (A) can be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or less, and can be less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 40 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight.

[0410] [Other ingredients] The composition may contain other ingredients besides those listed above. Examples of other ingredients include polysaccharides, paper strength enhancers, coagulants, retention aids, binders, adhesive resins, antislip agents, sizing agents, paper strength enhancers, fillers, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorants, and fragrances. They may be used alone or in combination of two or more.

[0411] In addition to the above-mentioned ingredients, other components may be added as follows: water-repellent and / or oil-repellent agents, dispersants, hand feel modifiers, softeners, flame retardants, paint fixatives, anti-wrinkle agents, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, defoamers, anti-shrinkage agents, washing anti-wrinkle agents, shape-retaining agents, drape-retaining agents, ironing enhancers, whitening agents, fabric softening clays, anti-staining agents for polyvinylpyrrolidone, etc., polymeric dispersants, dirt removers, scum dispersants, and 4,4-bis(2-sulfonylstyryl)biphenyl disodium (TINOPAL, manufactured by Ciba Specialty Chemicals). Fluorescent whitening agents such as CBS-X, dye fixatives, anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine, bleaching agents, enzymes such as cellulase, amylase, protease, lipase, and keratinase used as fiber surface modifiers, antifoaming agents, silk protein powders that impart the feel / function of silk, such as moisture absorption and release properties, their surface modifiers or emulsion dispersions (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk solution (hair application), SILKGEN G Soluble S (ICHIMARU PHARCOS Co., Ltd.)), anti-fouling agents (e.g., nonionic polymers composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by Muyo Chemical Industry, SRC-1 manufactured by CLARIANT Japan), etc. They can be used individually or in combination.

[0412] [Amount of other ingredients] Relative to 100 parts by weight of the hydrophobic compound (A), the amount or total amount of each of the other components may be more than 0.1 parts by weight, more than 1 part by weight, more than 3 parts by weight, more than 5 parts by weight, more than 10 parts by weight, more than 15 parts by weight, more than 20 parts by weight, more than 50 parts by weight, more than 75 parts by weight, or more than 100 parts by weight, and may be less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 40 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight.

[0413] <Paper Making Additives Reagent Kit> The composition containing hydrophobic compound (A) has been described above, but the hydrophobic compound (A1) and hydrophobic compound (A2) can also be used as separate treatment agents (additive kit) to treat the substrate.

[0414] The papermaking additive kit of the present invention comprises a first agent and a second agent. The first agent mentioned above contains a hydrophobic compound (A1). The second agent contains a hydrophobic compound (A2) that is different from the hydrophobic compound (A1) mentioned above. The first agent and the second agent described above can be added separately to the pulp substrate and mixed together. Alternatively, the first agent can be added to the pulp substrate first and mixed, and then the second agent can be added and mixed, or they can be added in the reverse order.

[0415] Regarding the ingredients in the first and second agents, they may contain the ingredients of the composition described above, and the first and second agents shall follow the manner described in the composition description above.

[0416] <Pulp Composition> The pulp composition of the present invention may contain pulp and a hydrophobic compound (A). The pulp composition of the present invention is obtained by treating pulp with the above-described composition containing the above-described hydrophobic compound (A) as a treatment agent.

[0417] 〔pulp〕 The pulp composition contains pulp, which is treated as a pulp base material using the aforementioned composition (treatment agent) containing hydrophobic compound (A). The pulp base material can be in the form of a single pulp, pulp stock, pulp products, etc. Examples of pulp base materials include: bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp or thermomechanical pulp, etc.; pulp stock containing the aforementioned pulp; and pulp products such as paper, paper containers, and paper molded bodies containing waste paper pulp such as old newspapers, old magazines, old corrugated paper or deinked waste paper. Specific examples of pulp products include food packaging materials, food containers, gypsum board base paper, coated base paper, medium-quality paper, ordinary liner paper and core paper, neutral pure white roll paper, neutral liner paper, rust-proof liner paper and metal composite paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, and molded paper (molded containers). Preferred examples of pulp products include food packaging materials and food containers, and particularly pulp molded products for food contact applications.

[0418] [Quantity of pulp] In the pulp composition, the amount of pulp can be 0.1% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, 75% by weight or more, or 90% by weight or more, and can be 99% by weight or less, 75% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 4% by weight or less, or 3% by weight or less. Typically, when the pulp composition is prepared by internal addition, the amount of pulp in the pulp composition can be 30% by weight or less; when the pulp composition is prepared by external addition, the amount of pulp in the pulp composition can be 75% by weight or more.

[0419] [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, typically an aqueous medium, especially water. The liquid medium may contain a liquid medium derived from a treatment agent.

[0420] [Amount of liquid medium] In the pulp composition, the amount of liquid medium can be 0.1% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, 75% by weight or more, 90% by weight or more, or 95% by weight or more, and can be less than 99% by weight, less than 75% by weight, less than 50% by weight, less than 40% by weight, less than 30% by weight, less than 20% by weight, less than 10% by weight, less than 5% by weight, less than 4% by weight, or less than 3% by weight. Typically, when the pulp composition is prepared by internal addition, the amount of liquid medium in the pulp composition can be 50% by weight or more, particularly 90% by weight or more; when the pulp composition is prepared by external addition, the amount of liquid medium in the pulp composition can be less than 30% by weight, particularly less than 10% by weight.

[0421] [Hydrophobic compound (A)] The pulp composition may contain a hydrophobic compound (A) from the treatment agent.

[0422] [Amount of hydrophobic compound (A)] The amount of treatment agent added to the pulp substrate can be adjusted to achieve the desired amount of hydrophobic compound (A). The amount of hydrophobic compound (A) relative to the pulp can be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more; and can be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, preferably 5.0% by weight or less, more preferably 3.0% by weight or less.

[0423] In the external additive treatment, the amount of hydrophobic compound (A) contained in the coating layer can be 0.01 g / m. 2 Above, 0.03g / m 2 Above, 0.05g / m 2 Above, 0.1g / m 2 Above, 0.3g / m 2 Above, 0.5g / m 2 Above or 1.0g / m 2 The above, and can be 5.0 g / m 2 Below, 4.0g / m 2 Below, 3.0g / m 2 Below, 2.0g / m 2 Below, 1.0g / m 2 Below, 0.5g / m 2 Below, 0.3g / m 2 Below or 0.1g / m 2 the following.

[0424] [Paper strength enhancer] Pulp compositions may contain paper strength enhancers. Examples of paper strength enhancers include: Cationic polyacrylamide, anionic polyacrylamide, amphoteric polyacrylamide, and other polyacrylamide-based paper strength enhancers; Starch, enzyme-modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (e.g., hydroxyethylated starch), aldehyde starch, cationic starch, starch, xanthan gum, ebony gum, vinylon 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 their modified polysaccharides (e.g., modified polysaccharides with hydroxyl or cationic groups) are all polysaccharide-based paper strength reinforcing agents. Polyamide-based paper strength reinforcing agents, such as polyamide resin, polyamine resin, polyamide-polyamine resin, polyamide-epoxychlorohydrin resin, polyamide-polyamine-epoxychlorohydrin resin, polyamide-polyurea-formaldehyde resin, and epoxy polyamide resin; Urea / melamine-based paper strength enhancers, such as urea resin, melamine resin, urea-formaldehyde resin, and melamine-formaldehyde resin. Polyvinyl alcohol (PVA) is a type of paper strength reinforcing agent, including fully saponified PVA, partially saponified PVA, carboxyl-modified PVA, silanol-modified PVA, cationic-modified PVA, and terminal alkyl-modified PVA. Styrene-butadiene copolymer, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyacrylate, fatty acid diamide, polyethyleneimine resin, ketone-aldehyde resin, etc. As the paper strength reinforcing agent of the present invention, polyacrylamide-based paper strength reinforcing agents, polysaccharide-based paper strength reinforcing agents, or polyamide-based paper strength reinforcing agents are preferred.

[0425] [Amount of paper strength enhancer] The amount of paper strength enhancer relative to the pulp can be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more; and can be less than 10% by weight, less than 7.5% by weight, less than 5.0% by weight, less than 4.0% by weight, less than 3.0% by weight, less than 2.0% by weight, less than 1.0% by weight, less than 0.75% by weight, or less than 0.5% by weight, preferably less than 5.0% by weight.

[0426] [Sizing agent] The pulp composition may contain a sizing agent. Examples of sizing agents include cationic sizing agents, anionic sizing agents, neutral sizing agents, 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 anhydride, etc.

[0427] [Amount of sizing agent] The amount of sizing agent relative to pulp can be 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and can be less than 10% by weight, less than 7.5% by weight, less than 5.0% by weight, less than 4.0% by weight, less than 3.0% by weight, less than 2.0% by weight, less than 1.0% by weight, less than 0.75% by weight, or less than 0.5% by weight.

[0428] [Other additives] In addition to the components mentioned above, the pulp composition may also contain additives that can be used in the manufacture of pulp products, such as fixatives (aluminum sulfate, etc.), organic acids (formic acid, acetic acid, etc.), coagulants, retention aids, dyes, fluorescent dyes, adhesive control agents, and defoamers. The pulp composition includes components of a composition (treatment agent) containing a hydrophobic compound (A), but each component that can be contained in the above-mentioned composition containing a hydrophobic compound (A) may also be added to the pulp composition individually as an additive.

[0429] The amount of the above-mentioned additives relative to the pulp can be more than 0.1% by weight, more than 1% by weight, more than 3% by weight, more than 5% by weight, and can be less than 30% by weight, less than 20% by weight, less than 10% by weight, or less than 5% by weight.

[0430] <Manufacturing Method of the Product> The method of manufacturing the article of the present invention may include a step of treating a substrate with the composition of the present invention containing a hydrophobic compound (A) as a treatment agent (especially a stripping agent).

[0431] The substrate that can be treated with the treatment agent of the present invention is not limited, but fiber substrates are preferred. It can be a fabric substrate or a pulp substrate, especially a pulp substrate.

[0432] Examples of fiber substrates include natural plant and animal fibers such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and cellulose acetate; inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber; or blends thereof. Fiber products include woven fabrics, knitted fabrics, and nonwoven fabrics; clothing forms (such as water-repellent clothing, like raincoats) and blankets; but can also be fibers, yarns, and intermediate fiber products (such as cotton slivers or rovings) in their state before becoming cloth.

[0433] The substrates that can be treated with the treatment agent of the present invention are not limited to fiber substrates. Other examples include stone, filters (e.g., electrostatic filters), dust covers, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, brick, cement, metals and oxides, kiln products, plastics, coatings and plaster, etc.

[0434] When the substrate is glass, the manufactured glass product can be an optical component. The surface (outermost layer) of the glass substrate can have certain layers (or films), such as a hard coating or an anti-reflective layer. The anti-reflective layer can be either a single-layer or multi-layer anti-reflective layer. Examples of inorganic materials that can be used as anti-reflective layers include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, WO3, etc. These inorganic materials can be used alone or in combination of two or more (e.g., in the form of a mixture). When a multi-layer anti-reflective layer is formed, it is preferable to use SiO2 and / or SiO as the outermost layer. When the desired product is an optical glass component for a touch panel, a portion of the substrate (glass) surface can have transparent electrodes, such as thin films using indium tin oxide (ITO) or indium zinc oxide. In addition, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), a frosting film layer, a hard coating layer, a polarizing film, a phase difference film, and a liquid crystal display module, depending on its specific style.

[0435] [Methods for manufacturing pulp products] The manufacturing method of the article of the present invention is preferably a method for manufacturing pulp articles, which may include a step of treating a pulp substrate with a dispersing agent. The pulp substrate is treated with a dispersing agent to obtain a pulp composition. The obtained pulp composition may be subjected to processing steps such as drying, heating, and molding as needed to obtain a pulp article.

[0436] Regarding the pulp substrate, the type and composition of the dispersing agent, the manner described in the "Pulp Composition" section above remains the same. The composition of the present invention can be applied to the substrate as a treatment agent (particularly a dispersing agent) using existing known methods. As a treatment method, the dispersing agent of the present invention can be diluted by dispersing it as needed in an organic solvent or water, adhering it to the interior and / or surface of the pulp substrate using known methods such as dip coating, spraying, or blister coating, and then drying it. After drying, a pulp article with the solid component adhering to the dispersing agent can be obtained. Furthermore, it can also be applied together with a suitable crosslinking agent as needed for curing. The concentration of the dispersing agent in the treatment agent in contact with the pulp substrate can be appropriately varied depending on the application, and can be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0437] The repellent agent can be applied to the pulp substrate using any known method for treating the pulp substrate with a liquid. The pulp substrate can be immersed in the repellent agent, mixed with the repellent agent, or the solution can be adhered to or sprayed onto the pulp substrate. To induce the treated pulp substrate to exhibit repellency, drying and curing by heating is preferred. Heating temperatures can be, for example, 100°C–200°C, 100°C–170°C, or 100°C–120°C. In this invention, the heating time can be from 5 seconds to 60 minutes, for example, from 30 seconds to 3 minutes.

[0438] As a treatment method for pulp substrate, one can employ an internal addition treatment method, which involves adding a dispersant to the pulp before papermaking (e.g., pulp stock), or an external addition treatment method, which involves applying a dispersant to the pulp after papermaking (e.g., pulp products). Examples of internal addition treatment methods include mixing and impregnation, which may include the process of adding a dispersant to the pulp stock and then mixing it. Examples of external addition treatment methods include spraying and coating, specifically including sizing presses with glue tanks, weir rolls, and metering rods. The treatment can be either an external or internal addition treatment. For example, when the pulp substrate is paper, the solution can be coated onto the paper, applied to the paper, sprayed onto the paper, or mixed with the pulp stock before papermaking.

[0439] The treatment method can be an internal addition treatment by adding a dispersant to the pulp before papermaking. This internal addition treatment may include, but is not limited to, one or more steps: a step of adding a dispersant to the pulp and mixing it; a step of dewatering the pulp composition obtained by this step through a mesh of a predetermined shape, causing the pulp composition to accumulate and form a pulp molding intermediate; and a step of molding and drying the pulp molding intermediate using a heated molding die to obtain a pulp molding product. After the treated paper is simply dried at room temperature or high temperature, it can optionally undergo heat treatment depending on the properties of the paper. The heat treatment temperature can be above 150°C, above 180°C, or above 210°C, and can be below 300°C, below 250°C, or below 200°C, particularly 80°C to 180°C. Heat treatment within such a temperature range can exhibit excellent oil and water resistance, etc. The internally added pulp substrate can also be externally treated with a dispersant to allow more wax and more paper strength enhancers to adhere to the surface.

[0440] The treatment method can also be an external treatment of applying a sizing agent to the pulp substrate after papermaking. Sizing presses with external treatment can be classified according to the coating method as follows. One coating method is a so-called sizing press where paper passes between two rubber rollers, and a coating liquid (sizing liquid) is supplied to the resulting clamping section, forming a coating liquid accumulation section called a sizing pool. The paper passes through this accumulation section, and the sizing liquid is coated on both sides of the paper. Other coating methods include weir roll type and metering rod type sizing presses that use a surface transfer die to apply the sizing liquid. In a sizing press, the sizing liquid easily penetrates into the interior of the paper; in a surface transfer die, the sizing liquid components easily remain on the surface of the paper. Compared to a sizing press, a surface transfer die results in a coating layer that is more easily retained on the surface of the paper, and a larger coating layer is formed on the surface. In this invention, even when using a sizing press with the former method (sizing pool type), it is possible to impart properties to the paper. Paper treated in this way, after being simply dried at room temperature or high temperature, can exhibit excellent oil resistance and / or water resistance, depending on the properties of the paper, by optionally undergoing heat treatment at temperatures below 300°C, such as below 200°C, and especially in the range of 80°C to 180°C.

[0441] The implementation methods have been described above, but it should be understood that various changes in manner and details may be made without departing from the spirit and scope of the claimed protection.

[0442] Example The following examples illustrate the present invention in detail, but the present invention is not limited to these examples.

[0443] <Experimental Methods> The experimental steps are as follows.

[0444] [Preparation of hydrophobic compound (A)] As the hydrophobic compound (A), a mixture is obtained by melting and mixing hydrophobic compounds (A1) and (A2) at a temperature above their melting points and then cooling it at room temperature.

[0445] [Made of molded parts] An automatic molding machine is used to mold the product. A mesh assembly is mounted on a metal pulp molding die with multiple suction holes at the bottom, and a metal trough is located at the top. Pulp slurry is added into the upper metal trough. From the side of the pulp molding die opposite to the side with the mesh assembly, a vacuum pump is used to suction and dehydrate the aqueous composition containing pulp through the pulp molding die and the mesh assembly at 0.1–1 MPa. This causes the solid components (pulp, etc.) contained in the aqueous composition to accumulate on the mesh assembly, resulting in a pulp molding intermediate. Next, the obtained pulp molding intermediate is dried from top to bottom under a pressure of 0.1–1 MPa using metal male and female molding dies heated to 60–200°C. This produces a pulp molding product molded into a container shape.

[0446] [Practical oil resistance test (25℃)] Pretreatment was performed by storing the molded parts at 23°C and 50% humidity for 12 hours. 100 ml of corn oil at 25°C was then injected into the molded parts. After standing at room temperature for 45 minutes, the corn oil was removed from the molded parts, and the degree of oil penetration was evaluated. Evaluation values ​​were set according to the degree of penetration as described below.

[0447] 5: No seepage on the inside.

[0448] 4: The inside is impregnated, but the back side is not.

[0449] 3: There is seepage on the inside and slight seepage on the back side.

[0450] 2: There is seepage on the inside, and the seepage to the back is less than 50% of the area.

[0451] 1: The inner side has seepage, and the seepage towards the back is more than 50% but less than 100% of the area.

[0452] 0: Exudation throughout the back side.

[0453] [Practical oil resistance test (65℃)] Pretreatment was performed by storing the molded parts at 23°C and 50% humidity for 12 hours. 100 ml of corn oil at 65°C was then injected into the molded parts. After standing at room temperature for 45 minutes, the corn oil was removed from the molded parts, and the degree of oil penetration was evaluated. Evaluation values ​​were set according to the degree of penetration as described below.

[0454] 5: No seepage on the inside.

[0455] 4: The inside is impregnated, but the back side is not.

[0456] 3: There is seepage on the inside and slight seepage on the back side.

[0457] 2: There is seepage on the inside, and the seepage to the back is less than 50% of the area.

[0458] 1: The inner side has seepage, and the seepage towards the back is more than 50% but less than 100% of the area.

[0459] 0: Exudation throughout the back side.

[0460] [Practical water resistance test (100℃)] Pretreatment was performed by storing the molded product at 23°C and 50% humidity for 12 hours. 100 ml of water at 100°C was then injected into the molded product, and after standing at room temperature for 30 minutes, the water was removed from the molded product, and the degree of impregnation was evaluated. Evaluation values ​​were set according to the degree of impregnation as described below.

[0461] 5: No seepage on the inside.

[0462] 4: The inside is impregnated, but the back side is not.

[0463] 3: There is seepage on the inside and slight seepage on the back side.

[0464] 2: There is seepage on the inside, and the seepage to the back is less than 50% of the area.

[0465] 1: The inner side has seepage, and the seepage towards the back is more than 50% but less than 100% of the area.

[0466] 0: Exudation throughout the back side.

[0467] [Hexadecane contact angle (HD contact angle)] A solution (dispersion) of a hydrophobic compound (A1) or a hydrophobic compound (A2) with a solid component concentration of 1.0% was prepared. The prepared solution was then sonicated at 40°C for 60 minutes.

[0468] The solution (dispersion) was spin-coated onto a silicon wafer at 2500 rpm for 25 seconds to obtain a spin-coated film. This film was then heated at 140°C for 1 minute to produce a compound-treated silicon wafer. Chloroform was used as the solvent or dispersion medium. 2 μL of HD (hexadecane) was dropped onto the compound-treated silicon wafer, and the static contact angle after 1 second of dropping was taken as the HD contact angle of each hydrophobic compound.

[0469] [Water contact angle] A solution (dispersion) of a hydrophobic compound (A1) or a hydrophobic compound (A2) with a solid component concentration of 1.0% was prepared. The prepared solution was then sonicated at 40°C for 60 minutes.

[0470] The solution (dispersion) was spin-coated onto a silicon wafer at 2500 rpm for 25 seconds to obtain a spin-coated film. This film was then heated at 140°C for 1 minute to produce a compound-treated silicon wafer. Chloroform was used as the solvent or dispersion medium. 2 μL of water was dropped onto the compound-treated silicon wafer, and the static contact angle after 1 second was taken as the water contact angle of each hydrophobic compound.

[0471] [Low-temperature shift of the endothermic peak of hydrophobic compound (A1)] For hydrophobic compounds (A) and (A1), the temperature was increased from -20°C to 180°C at a rate of 10°C / min under a nitrogen atmosphere. The low-temperature shift (°C) of the endothermic peak at the highest temperature side within the measurement range of hydrophobic compound (A1) was determined when hydrophobic compound (A1) was used as hydrophobic compound (A).

[0472] [Methods for determining melting point] The melting point was calculated using differential scanning calorimetry (DSC). DSC measurements were performed under a nitrogen atmosphere (nitrogen flow rate 50 mL / min) with cooling to -20 °C at a rate of 10 °C / min, followed by heating to 180 °C at a rate of 10 °C / min, and then cooling back to -20 °C at a rate of 10 °C / min. The endothermic peak observed during the second heating step, with a rate of 10 °C / min to 180 °C, was then measured.

[0473] [Calculation method of solubility parameter (SP value) using Fedors method] Regarding the solubility parameter (SP value) using the Fedors method, the solubility parameter at 25°C was calculated using the Fedors method (Polym.Eng.Sci., 14(2), 147-154(1974)) by the group contribution method (addition of atomic groups) of Fedors.

[0474] [Penetrating test of the compound] Hydrophobic compound (A) was added to an iron container with a width of 30 mm, a length of 30 mm, and a depth of 20 mm. The container was heated at 180°C for 30 minutes to melt it. The container was then allowed to cool to 25°C to prepare a test piece. The test piece was then determined according to JIS K 2235 6.4.

[0475] [Penetrating test of residue] Aqueous dispersions of hydrophobic compound (A) were heated at 100°C for 2 days to obtain a residue from which the liquid medium had been removed. The obtained residue was added to an iron container with a width of 30 mm, a length of 30 mm, and a depth of 20 mm, and heated at 180°C for 30 minutes to melt it. After cooling to 25°C, test pieces were prepared and measured according to JIS K 2235 6.4.

[0476] [Method for determining the Shore A hardness of compounds] Hydrophobic compounds (A) and (A1) were added to iron containers with a width of 30 mm, a length of 30 mm, and a depth of 20 mm, respectively. The containers were heated to 180°C for 30 minutes to melt them, and then cooled to 25°C to prepare test specimens. Using a polymer comparator and an automatic rubber hardness tester (P2-A type), the Shore A hardness after 1 second [1s], the Shore A hardness after 3 seconds [3s], and the peak intensity of the Shore A hardness [peak value] were calculated. Furthermore, the difference in Shore A hardness ([Shore A hardness of hydrophobic compound (A1)] - [Shore A hardness of hydrophobic compound (A)] was calculated based on the obtained results.

[0477] [Method for determining the Shore A hardness of residues] Aqueous dispersions of hydrophobic compound (A) were heated at 100°C for 2 days to obtain a residue from which the liquid medium was removed. The obtained residue was added to an iron container with a width of 30 mm, a length of 30 mm, and a depth of 20 mm, and heated at 180°C for 30 minutes to melt it. The container was then allowed to cool to 25°C to prepare a test piece. Using a polymer comparator and an automatic rubber hardness tester P2-A, the Shore A hardness after 1 second [1s], the Shore A hardness after 3 seconds [3s], and the peak intensity of the Shore A hardness [peak value] were calculated.

[0478] <Example 1> 2 g of N,N'-ethylenebisoctadecylamide (bio-based content: 97%, melting point: 143℃, hexadecane contact angle: 36.1°, Fedors SP value: 9.6) as hydrophobic compound (A1), 1.4 g of corn oil (JAPAN CORN STARCH CO., LTD., liquid at 25℃) as hydrophobic compound (A2), 0.16 g of polyethylene glycol trimethyl nonyl ether (HLB13.1), and 0.04 g of polyethylene glycol trimethyl nonyl ether (HLB8.1) were mixed and heated at 180℃ for 30 minutes to obtain a molten solid mixture.

[0479] 10 g of water was added to the solid and pulverized using a spatula. Then, 6.6 g of water was added and the mixture was homogenized at 10,000 rpm for 20 minutes to obtain an aqueous dispersion of the composition containing the hydrophobic compound (A) (volume percentage of particles larger than 100 μm: 21%, median particle size: 53.3 μm).

[0480] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 3 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0481] The molded parts were subjected to practical oil resistance tests (25℃), practical oil resistance tests (65℃), and practical water resistance tests (100℃), and all scores were 4 points.

[0482] The Shore A hardness -1 was determined using a mixture of 100 parts by mass of N,N'-ethylenebisoctadecylamide (bio-based content: 97%, melting point: 143°C, hexadecane contact angle: 36.1°, Fedors SP value: 9.6) as hydrophobic compound (A1) and 70 parts by mass of corn oil (JAPAN CORN STARCH CO., LTD., liquid at 25°C) as hydrophobic compound (A2).

[0483] <Example 2> Except that the amount of corn oil as the hydrophobic compound (A2) was changed to 0.70 g, an aqueous dispersion composition containing the hydrophobic compound (A) was obtained by following the same steps as in Example 1 (volume percentage of particles larger than 100 μm: 19%, median particle size: 47.9 μm).

[0484] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 3 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0485] The molded parts were subjected to practical oil resistance tests (25℃), practical oil resistance tests (65℃), and practical water resistance tests (100℃), and all scores were 4 points.

[0486] The Shore A hardness -1 was determined by mixing 35 parts by mass of corn oil (JAPAN CORN STARCH CO., LTD., liquid at 25°C) as hydrophobic compound (A2) with 100 parts by mass of N,N'-ethylenebisoctadecylamide (bio-based content: 97%, melting point: 143°C, hexadecane contact angle: 36.1°, Fedors SP value: 9.6) as hydrophobic compound (A1).

[0487] <Example 3> Except that the corn oil (A2) was replaced with triolein (state at 25°C: liquid, Fedors SP value: 8.93), an aqueous dispersion of the composition containing the hydrophobic compound (A) was obtained by following the same steps as in Example 1 (volume percentage of particles larger than 100 μm: 23%, median particle size: 47.9 μm).

[0488] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 3 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0489] The molded parts were subjected to practical oil resistance tests (25℃), practical oil resistance tests (65℃), and practical water resistance tests (100℃), and all scores were 4 points.

[0490] <Example 4> Except for changing the corn oil (A2) used as the hydrophobic compound to triolein (state at 25°C: liquid, Fedors SP value: 8.93) and changing the amount used to 0.70 g, an aqueous dispersion composition containing the hydrophobic compound (A) was obtained by following the same steps as in Example 1 (volume percentage of particles larger than 100 μm: 24%, median particle size: 49.3 μm).

[0491] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 3 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0492] The molded parts were subjected to practical oil resistance tests (25℃), practical oil resistance tests (65℃), and practical water resistance tests (100℃), and all scores were 4 points.

[0493] <Example 5> Except that the corn oil (A2) used as the hydrophobic compound was replaced with Sanya oil essence (state at 25°C: liquid, Fedors SP value: 8.951), an aqueous dispersion composition containing the hydrophobic compound (A) was obtained by following the same steps as in Example 1 (volume percentage of particles larger than 100 μm: 22%, median particle size: 52.3 μm).

[0494] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 3 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0495] The molded parts were subjected to practical oil resistance tests (25℃), practical oil resistance tests (65℃), and practical water resistance tests (100℃), and all scores were 4 points.

[0496] <Example 6> Except for changing the corn oil (A2) used as the hydrophobic compound to Sanya oil essence (state at 25°C: liquid, Fedors SP value: 8.951) and changing the amount used to 0.70g, an aqueous dispersion composition containing the hydrophobic compound (A) was obtained by following the same steps as in Example 1 (volume percentage of particles larger than 100μm: 19%, median particle size: 47.9μm).

[0497] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 3 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0498] The molded parts were subjected to practical oil resistance tests (25℃), practical oil resistance tests (65℃), and practical water resistance tests (100℃), and all scores were 4 points.

[0499] <Example 7> 2 g of N,N'-ethylene dioleoamide (bio-based content: 97%, melting point: 116°C, hexadecane contact angle: 42.7°) as hydrophobic compound (A1), 1.4 g of corn oil (JAPAN CORN STARCHCO., LTD., liquid at 25°C) as hydrophobic compound (A2), 0.16 g of polyethylene glycol trimethyl nonyl ether (HLB13.1), and 0.04 g of polyethylene glycol trimethyl nonyl ether (HLB8.1) were mixed and heated at 180°C for 30 minutes to obtain a molten solid mixture.

[0500] 10 g of water was added to the solid and pulverized using a scraper. Then, 6.6 g of water was added and the mixture was homogenized at 10,000 rpm for 20 minutes to obtain an aqueous dispersion of the composition containing the hydrophobic compound (A) (volume percentage of particles larger than 100 μm: 18%, median volume particle size: 47.3 μm).

[0501] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 7 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0502] The molded parts were subjected to practical oil resistance tests (25℃) and practical oil resistance tests (65℃), and both scored 4 points in all evaluations.

[0503] <Example 8> Except that the amount of corn oil as the hydrophobic compound (A2) was changed to 0.70 g, an aqueous dispersion composition containing the hydrophobic compound (A) was obtained by following the same steps as in Example 7 (volume percentage of particles larger than 100 μm: 19%, median particle size: 46.2 μm).

[0504] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 7 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0505] The molded parts were subjected to practical oil resistance tests (25℃), practical oil resistance tests (65℃), and practical water resistance tests, and all scores were 4 points.

[0506] <Example 9> Except that the amount of corn oil as the hydrophobic compound (A2) was changed to 2.2 g, an aqueous dispersion composition containing the hydrophobic compound (A) was obtained by following the same steps as in Example 1 (volume percentage of particles larger than 100 μm: 17%, median particle size: 45.6 μm).

[0507] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 3 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0508] The molded parts were subjected to practical oil resistance tests (25℃), practical oil resistance tests (65℃), and practical water resistance tests, and all scores were 4 points.

[0509] <Example 10> 2 g of N,N'-ethylenebisoctadecylamide (bio-based content: 97%, melting point: 143℃, hexadecane contact angle: 36.1°), which is a hydrophobic compound (A1), 1.4 g of tridecanoic acid glyceride (liquid at 25℃, Fedors SP value: 9.138), 0.16 g of polyethylene glycol trimethyl nonyl ether (HLB13.1), and 0.04 g of polyethylene glycol trimethyl nonyl ether (HLB8.1) were mixed and heated at 180℃ for 30 minutes to obtain a molten solid mixture.

[0510] 10 g of water was added to the solid and the mixture was pulverized using a scraper. Then, 6.6 g of water was added and the mixture was homogenized at 7500 rpm for 20 minutes to obtain an aqueous dispersion of the composition containing the hydrophobic compound (A) (volume percentage of particles larger than 100 μm: 23%, median volume particle size: 40.35 μm).

[0511] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 5 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0512] The molded part was subjected to a practical oil resistance test (65℃) and scored 4 points.

[0513] <Example 11> 2 g of N,N'-ethylenebisoctadecylamide (bio-based content: 97%, melting point: 143℃, hexadecane contact angle: 36.1°), which is a hydrophobic compound (A1), 1.4 g of tricaprylic acid glyceride (liquid at 25℃, Fedors SP value: 9.251), 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℃ for 30 minutes to obtain a molten solid mixture.

[0514] 10 g of water was added to the solid and the mixture was pulverized using a scraper. Then, 6.6 g of water was added and the mixture was homogenized at 7500 rpm for 20 minutes to obtain an aqueous dispersion of the composition containing the hydrophobic compound (A) (volume percentage of particles larger than 100 μm: 26%, median volume particle size: 57.06 μm).

[0515] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 5 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0516] The molded part was subjected to a practical oil resistance test (65℃) and scored 4 points.

[0517] <Example 12> 2 g of N,N'-ethylidene bis(octadecylamide) (bio-based content: 97%, melting point: 143℃, hexadecane contact angle: 36.1°) as hydrophobic compound (A1), 1.4 g of tributyl trimellitate (liquid at 25℃, Fedors SP value: 10.185) as hydrophobic compound (A2), 0.16 g of polyethylene glycol trimethyl nonyl ether (HLB13.1), and 0.04 g of polyethylene glycol trimethyl nonyl ether (HLB8.1) were mixed and heated at 180℃ for 30 minutes to obtain a molten solid mixture.

[0518] 10 g of water was added to the solid and pulverized using a scraper. Then, 6.6 g of water was added and the mixture was homogenized at 7500 rpm for 20 minutes to obtain an aqueous dispersion of the composition containing the hydrophobic compound (A) (volume percentage of particles larger than 100 μm: 17%, median particle size: 44.58 μm).

[0519] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 5 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0520] The molded parts were subjected to practical oil resistance tests (25℃), practical oil resistance tests (65℃), and practical water resistance tests (100℃), and all scores were 4 points.

[0521] <Example 13> 2 g of N,N'-ethylenebisoctadecylamide (bio-based content: 97%, melting point: 143℃, hexadecane contact angle: 36.1°), which is the hydrophobic compound (A1), 0.7 g of sucrose oleate (liquid at 25℃, HLB: 1), 0.16 g of polyethylene glycol trimethyl nonyl ether (HLB13.1), and 0.04 g of polyethylene glycol trimethyl nonyl ether (HLB8.1) were mixed and heated at 180℃ for 30 minutes to obtain a molten solid mixture.

[0522] 10 g of water was added to the solid and pulverized using a scraper. Then, 6.6 g of water was added and the mixture was homogenized at 7500 rpm for 20 minutes to obtain an aqueous dispersion of the composition containing the hydrophobic compound (A) (volume percentage of particles larger than 100 μm: 17%, median particle size: 44.58 μm).

[0523] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 5 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0524] The molded parts were subjected to practical oil resistance tests (25℃) and practical oil resistance tests (65℃), and both scored 4 points in all evaluations.

[0525] <Example 14> 2 g of N,N'-ethylenebisoctadecylamide (bio-based content: 97%, melting point: 143℃, hexadecane contact angle: 36.1°) as hydrophobic compound (A1), 0.7 g of sucrose erucic acid ester (liquid at 40℃, HLB: 2) as hydrophobic compound (A2), 0.16 g of polyethylene glycol trimethyl nonyl ether (HLB13.1), and 0.04 g of polyethylene glycol trimethyl nonyl ether (HLB8.1) were mixed and heated at 180℃ for 30 minutes to obtain a molten solid mixture.

[0526] 10 g of water was added to the solid and pulverized using a scraper. Then, 6.6 g of water was added and the mixture was homogenized at 7500 rpm for 20 minutes to obtain an aqueous dispersion of the composition containing the hydrophobic compound (A) (volume percentage of particles larger than 100 μm: 17%, median particle size: 44.58 μm).

[0527] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 5 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0528] The molded parts were subjected to practical oil resistance tests (25℃) and practical oil resistance tests (65℃), and both scored 4 points in all evaluations.

[0529] <Example 15> 2 g of N,N'-ethylenebisoctadecylamide (bio-based content: 97%, melting point: 143°C, hexadecane contact angle: 36.1°) as hydrophobic compound (A1), 0.7 g of decaglycerol decaoleate (degree of polymerization 10, hydroxyl substitution rate: 10 / 12*100 [83.3%], state at 25°C: liquid, HLB: 3.3) as hydrophobic compound (A2), 0.16 g of polyethylene glycol trimethyl nonyl ether (HLB13.1), and 0.04 g of polyethylene glycol trimethyl nonyl ether (HLB8.1) were mixed and heated at 180°C for 30 minutes to obtain a molten solid mixture.

[0530] 10 g of water was added to the solid and pulverized using a scraper. Then, 6.6 g of water was added and the mixture was homogenized at 7500 rpm for 20 minutes to obtain an aqueous dispersion of the composition containing the hydrophobic compound (A) (volume percentage of particles larger than 100 μm: 17%, median particle size: 44.58 μm).

[0531] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 5 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0532] The molded parts were subjected to practical oil resistance tests (25℃) and practical oil resistance tests (65℃), and both scored 4 points in all evaluations.

[0533] <Example 16> 2 g of N,N'-ethylenebisoctadecylamide (bio-based content: 97%, melting point: 143°C, hexadecane contact angle: 36.1°) as hydrophobic compound (A1), 0.7 g of hexaglycerol pentaoleate (degree of polymerization 6, hydroxyl substitution rate: 5 / 8*100 [62.5%], state at 25°C: liquid, HLB: 4.7) as hydrophobic compound (A2), 0.16 g of polyethylene glycol trimethyl nonyl ether (HLB13.1), and 0.04 g of polyethylene glycol trimethyl nonyl ether (HLB8.1) were mixed and heated at 180°C for 30 minutes to obtain a molten solid mixture.

[0534] 10 g of water was added to the solid and pulverized using a scraper. Then, 6.6 g of water was added and the mixture was homogenized at 7500 rpm for 20 minutes to obtain an aqueous dispersion of the composition containing the hydrophobic compound (A) (volume percentage of particles larger than 100 μm: 17%, median particle size: 44.58 μm).

[0535] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 5 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0536] The molded parts were subjected to practical oil resistance tests (25℃) and practical oil resistance tests (65℃), and both scored 4 points in all evaluations.

[0537] <Example 17> 2 g of N,N'-ethylenebisoctadecylamide (bio-based content: 97%, melting point: 143°C, hexadecane contact angle: 36.1°) as hydrophobic compound (A1), 0.7 g of decaglycerol octaurinate (degree of polymerization 10, hydroxyl substitution rate: 8 / 12*100 [66.7%], state at 25°C: liquid, HLB: 3.7) as hydrophobic compound (A2), 0.16 g of polyethylene glycol trimethyl nonyl ether (HLB13.1), and 0.04 g of polyethylene glycol trimethyl nonyl ether (HLB8.1) were mixed and heated at 180°C for 30 minutes to obtain a molten solid mixture.

[0538] 10 g of water was added to the solid and pulverized using a scraper. Then, 6.6 g of water was added and the mixture was homogenized at 7500 rpm for 20 minutes to obtain an aqueous dispersion of the composition containing the hydrophobic compound (A) (volume percentage of particles larger than 100 μm: 17%, median particle size: 44.58 μm).

[0539] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 5 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0540] The molded parts were subjected to practical oil resistance tests (25℃) and practical oil resistance tests (65℃), and both scored 4 points in all evaluations.

[0541] <Example 18> 2 g of N,N'-ethylidene bis(octadecylamide) (bio-based content: 97%, melting point: 143℃, hexadecane contact angle: 36.1°) as hydrophobic compound (A1), 1.4 g of diisononyl adipate (liquid at 25℃, Fedors SP value: 9.00) as hydrophobic compound (A2), 0.16 g of polyethylene glycol trimethyl nonyl ether (HLB13.1), and 0.04 g of polyethylene glycol trimethyl nonyl ether (HLB8.1) were mixed and heated at 180℃ for 30 minutes to obtain a molten solid mixture.

[0542] 10 g of water was added to the solid and pulverized using a scraper. Then, 6.6 g of water was added and the mixture was homogenized at 7500 rpm for 20 minutes to obtain an aqueous dispersion of the composition containing the hydrophobic compound (A) (volume percentage of particles larger than 100 μm: 17%, median particle size: 44.58 μm).

[0543] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 5 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0544] The molded parts were subjected to practical oil resistance tests (25℃) and practical oil resistance tests (65℃), and both scored 4 points in all evaluations.

[0545] <Comparative Example 1> 2 g of N,N'-ethylenebisoctadecylamide (bio-based content: 97%, melting point: 143℃, hexadecane contact angle: 36.1°), 0.16 g of polyethylene glycol trimethyl nonyl ether (HLB13.1), 0.04 g of polyethylene glycol trimethyl nonyl ether (HLB8.1), and 17.8 g of water, which were dry-milled to an average particle size of 18 μm, were added as hydrophobic compound (A1), and the mixture was stirred to obtain an aqueous dispersion composition (volume percentage of particles larger than 100 μm: 4.3%, median volume particle size: 18 μm).

[0546] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 3 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0547] The molded parts were subjected to practical oil resistance tests (25℃), practical oil resistance tests (65℃), and practical water resistance tests. The oil resistance score for the practical oil resistance test (25℃) was 1 point.

[0548] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 5 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0549] The molded parts were subjected to practical oil resistance tests (25℃), practical oil resistance tests (65℃), and practical water resistance tests. The oil resistance score for the practical oil resistance test (25℃) was 1 point.

[0550] <Comparative Example 2> 2 g of N,N'-ethylene dioleoamide (bio-based content: 97%, melting point: 116℃, hexadecane contact angle: 42.7°), 0.16 g of polyethylene glycol trimethyl nonyl ether (HLB13.1), 0.04 g of polyethylene glycol trimethyl nonyl ether (HLB8.1), and 17.8 g of water, which were dry-milled to an average particle size of 7.4 μm, were added as hydrophobic compound (A1), and the mixture was stirred to obtain an aqueous dispersion composition (volume percentage of particles larger than 100 μm: 1.4%, median volume particle size: 7.8 μm).

[0551] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 3 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0552] Practical oil resistance test (25℃), practical oil resistance test (65℃) and practical water resistance test were conducted on the molded parts. The oil resistance score for the practical oil resistance test (25℃) was 1 point and the oil resistance score for the practical oil resistance test (65℃) was 4 points.

[0553] <Comparative Example 3> The aqueous dispersion composition was obtained by following the same steps 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 used as an aqueous mixture, was used instead of the hydrophobic compound (A2).

[0554] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 3 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0555] A practical oil resistance test (25℃) was conducted on the molded product, and the score was 1 point.

[0556] <Comparative Example 4> Except that tripropylene glycol (state at 25°C: liquid, octanol / water partition coefficient: -0.50, Fedors SP value: 12.385), a non-hydrophobic compound used as an aqueous mixture, was used instead of hydrophobic compound (A2), and the amount used was changed to 0.70 g, the aqueous dispersion composition was obtained by following the same steps as in Example 1.

[0557] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 3 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0558] A practical oil resistance test (25℃) was conducted on the molded product, and the score was 1 point.

[0559] <Comparative Example 5> The aqueous dispersion composition was obtained by following the same steps 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 used as an aqueous mixture, was substituted for the hydrophobic compound (A2).

[0560] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 3 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0561] A practical oil resistance test (25℃) was conducted on the molded product, and the score was 1 point.

[0562] <Comparative Example 6> The aqueous dispersion composition was obtained by following the same steps 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 used as an aqueous mixture, was replaced with the hydrophobic compound (A2), and the amount used was changed to 0.70 g.

[0563] An aqueous composition containing pulp was prepared by adding an aqueous dispersion to a pulp concentrate of 0.5 wt% such that the hydrophobic compound (A1) was at a ratio of 3 wt% relative to the pulp on a solids basis. The aqueous composition containing pulp was then fed into an automated molding machine to produce molded articles.

[0564] A practical oil resistance test (25℃) was conducted on the molded product, and the score was 1 point.

[0565] <Comparative Example 7> 2 g of paraffin (melting point 69.8 °C), acting as the hydrophobic compound (A1), 0.2 g of polyoxyethylene alkyl ether (alkyl group with 6-16 carbon atoms, HLB: 7), and 17.8 g of water were mixed to obtain an aqueous dispersion. This aqueous dispersion was heated to 85 °C and then treated with an ultrasonic homogenizer for 20 minutes to obtain an aqueous composition. The obtained aqueous dispersion exhibits the following properties.

[0566] Median particle size D50: 0.8 μm Volume ratio of particles larger than 100 μm: 0% Volume ratio of particles larger than 10 μm: 12% An aqueous dispersion of a hydrophobic compound (A1) was added to 0.5 wt% pulp, such that the hydrophobic compound (A1) was at a ratio of 10 wt% relative to the pulp (based on solids content), to prepare an aqueous pulp-containing composition. The aqueous pulp-containing composition was then fed into an automatic molding machine to produce molded articles. A practical oil resistance test (25°C) was performed on the molded articles, scoring 1 point.

[0567] <Examples 19-24 / Comparative Example 8> Except for the preparation of hydrophobic compound (A) according to the composition shown in Table 3, the experiments were conducted in the same manner as in Example 1.

[0568] The results are summarized in the table below.

[0569] [Table 1] [Table 2] [Table 3] The properties of the compounds are summarized below.

[0570] [Table 4] .

Claims

1. A composition containing hydrophobic compound A, characterized in that, The hydrophobic compound A includes hydrophobic compound A1 and hydrophobic compound A2, which is different from hydrophobic compound A1. The Shore A hardness peak value of the hydrophobic compound A is 10 to 100 smaller than that of the hydrophobic compound A1.

2. The composition according to claim 1, characterized in that, It is an aqueous dispersion composition.

3. The composition according to claim 1 or 2, characterized in that, It is a dispensing agent.

4. The composition according to any one of claims 1 to 3, characterized in that, The hexadecane contact angle of the hydrophobic compound A1 is greater than 30°.

5. The composition according to any one of claims 1 to 4, characterized in that, The peak Shore A hardness of the hydrophobic compound A is above 4.0 and below 70.

6. The composition according to any one of claims 1 to 5, characterized in that, The hydrophobic compound A1 and the hydrophobic compound A2 are each independently compounds having a hydrocarbon group having 6 to 40 carbon atoms.

7. The composition according to any one of claims 1 to 6, characterized in that, The hydrophobic compound A1 and the hydrophobic compound A2 are each independently selected from amine modifiers, polyol modifiers, polycarboxylic acid modifiers, and other liquid or solid oils.

8. The composition according to any one of claims 1 to 7, characterized in that, The hydrophobic compound A1 has an amide structure. The hydrophobic compound A2 does not have an amide structure.

9. The composition according to any one of claims 1 to 8, characterized in that, The hydrophobic compound A1 is selected from amine-modified, polyol-modified, polycarboxylic acid-modified, paraffin, and microcrystalline wax compounds. The amine modified body has an amine skeleton and one or more of the following formulas: -Y N -Z N n The indicated group, and at least one -Y N -Z N n Compounds bonded to the nitrogen atoms of the amine skeleton, Formula-Y N -Z N n middle, Y N The reason for selecting Y N1 and Y N2 One or more of the following groups constitute a 1+n valence group: Y N1 It is a directly bonded group composed of one or more groups selected from -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 a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms each time it appears. Y N2 It is a group composed of one or more aliphatic hydrocarbon groups with 1 to 40 carbon atoms that may have substituents, aromatic hydrocarbon rings with 2 to 4 valences that may have substituents, and heterocycles with 2 to 4 valences that may have substituents. Z N It can be a monovalent hydrocarbon group with 1 to 40 carbon atoms or a monovalent polysiloxane group that can have substituents. n is an integer greater than 1 and less than 3. The polyol modifier is a polyol with one or more hydroxyl groups modified by the following formula: -Y O -Z O n The compound shown has substituent groups. Formula-Y O -Z O n middle, Y O The reason for selecting Y O1 and Y O2 One or more of the following groups constitute a 1+n valence group: Y O1 It is a directly bonded group composed of one or more groups selected from -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 a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms each time it appears. Y O2 It is a group composed of one or more aliphatic hydrocarbon groups with 1 to 40 carbon atoms that may have substituents, aromatic hydrocarbon rings with 2 to 4 valences that may have substituents, and heterocycles with 2 to 4 valences that may have substituents. Z O It can be a monovalent hydrocarbon group with 1 to 40 carbon atoms or a monovalent polysiloxane group that can have substituents. n is an integer greater than 1 and less than 3. The polycarboxylic acid modifier is formed when the hydroxyl group of one or more carboxyl groups of the polycarboxylic acid is modified by the following formula: -Y C -Z C n The compound shown has substituent groups. Formula-Y C -Z C n middle, Y C The reason for selecting Y C1 and Y C2 One or more of the following groups constitute a 1+n valence group: Y C1 It is a directly bonded group composed of one or more groups selected from -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 a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms each time it appears. Y C2 It is a group composed of one or more aliphatic hydrocarbon groups with 1 to 40 carbon atoms that may have substituents, aromatic hydrocarbon rings with 2 to 4 valences that may have substituents, and heterocycles with 2 to 4 valences that may have substituents. Z C It can be a monovalent hydrocarbon group with 1 to 40 carbon atoms or a monovalent polysiloxane group that can have substituents. n is an integer between 1 and 3.

10. The composition according to any one of claims 1 to 9, characterized in that, The hydrophobic compound A2 has a hydrocarbon group with 3 or more carbon atoms. The hydrophobic compound A2 has a melting point below 40°C.

11. The composition according to any one of claims 1 to 10, characterized in that, The amount of hydrophobic compound A1 relative to hydrophobic compound A is more than 15% by weight and less than 95% by weight.

12. The composition according to any one of claims 1 to 11, characterized in that, The amount of hydrophobic compound A2 is 5 to 500 parts by weight relative to 100 parts by weight of the hydrophobic compound A1.

13. The composition according to any one of claims 1 to 12, characterized in that, The hydrophobic compound A1 has a melting point above 50°C. The hydrophobic compound A2 has a melting point below 40°C.

14. The composition according to any one of claims 1 to 13, characterized in that, The melting point of the hydrophobic compound A1 is more than 30°C higher than that of the hydrophobic compound A2.

15. The composition according to any one of claims 1 to 14, characterized in that, The composition contains a dispersant. The amount of the dispersant is 0.1 parts by weight to 100 parts by weight relative to 100 parts by weight of the hydrophobic compound A.

16. A papermaking additive reagent kit, characterized in that, It has a first agent and a second agent. The first agent contains a hydrophobic compound A1. The second agent contains a hydrophobic compound A2, which is a compound different from the hydrophobic compound A1. The Shore A hardness peak value of the hydrophobic compound A is 10 to 100 lower than that of the hydrophobic compound A1. The first agent and the second agent are added and mixed into the pulp substrate for use.

17. An article characterized in that, The material comprises a substrate and a hydrophobic compound A, wherein the hydrophobic compound A includes a hydrophobic compound A1 and a hydrophobic compound A2, which is different from the hydrophobic compound A1. The Shore A hardness peak value of the hydrophobic compound A is 10 to 100 smaller than that of the hydrophobic compound A1.

18. The article of claim 17, characterized in that, The substrate is a pulp substrate, and the product is a pulp product.

19. A method for manufacturing an article, characterized in that, The process includes treating a substrate using the composition of any one of claims 1 to 15 or the papermaking additive kit of claim 16.

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