Method for manufacturing pulp product

Abstract

To provide a novel method for manufacturing a pulp product having liquid repellency.SOLUTION: There is provided a method for manufacturing a pulp product, comprising: a first heating step for heating a pulp composition containing pulp and a liquid-repellent compound to a first heating temperature to obtain a precursor product in which the liquid-repellent compound is adhered to the pulp; a first cooling step for cooling the precursor product to a first cooling temperature to obtain a cooled precursor product; and a second heating step for heating the cooled precursor product to a second heating temperature to obtain a pulp product.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a method for producing a pulp product. [Background technology]

[0002] Patent Document 1 discloses that a method for producing a pulp molded product, which is characterized by applying a coating agent to the surface of the pulp molded body immediately after the pulp is drawn and before or while the back surface of the body is being suctioned with a vacuum, can enhance the effect of the coating agent (waterproofing, strength, etc.) and be economical. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2002-129499 A Summary of the Invention [Problem to be solved by the invention]

[0004] Patent Document 1 does not mention or suggest the provision of multiple heating steps or a cooling step in the manufacturing process. Furthermore, Patent Document 1 does not discuss the oil resistance of the product.

[0005] An object of the present disclosure is to provide a novel method for producing a pulp product to which liquid repellency has been imparted. [Means for solving the problem]

[0006] The present disclosure includes the following aspects: [Section 1] a first heating step of heating a pulp composition containing pulp and a liquid repellent compound to a first heating temperature to obtain a precursor product in which the liquid repellent compound is adhered to the pulp; a first cooling step of cooling the precursor product to a first cooling temperature to obtain a cooled precursor product; and a second heating step of heating the cooled precursor product to a second heating temperature to obtain a pulp product. A method for producing a pulp product comprising: [Section 2] The first heating temperature is 40° C. or more, The first cooling temperature is less than 40°C; Item 2. The method for producing a pulp product according to Item 1, wherein the second heating temperature is 40° C. or higher. [Section 3] the first heating temperature is equal to or higher than the melting point of the liquid repellent compound, Item 3. The method for producing a pulp product according to Item 1 or 2, wherein the first cooling temperature is lower than the melting point of the liquid repellent compound. [Section 4] Item 4. The method for producing a pulp product according to Item 3, wherein the second heating temperature is 0.7 times or more the melting point of the liquid repellent compound. [Section 5] Item 4. The method for producing a pulp product according to Item 3, wherein the second heating temperature is equal to or higher than the first cooling temperature +30°C and equal to or higher than the melting point of the liquid repellent compound -50°C. [Section 6] the first heating temperature is equal to or higher than the melting point of the liquid repellent compound, The first cooling temperature is less than 40°C; 6. The method for producing a pulp product according to any one of items 1 to 5, wherein the second heating temperature is not less than the melting point of the liquid repellent compound −50° C. and not more than the melting point of the liquid repellent compound +100° C. [Section 7] the pulp composition comprises a liquid medium; 7. The method for producing a pulp product according to any one of items 1 to 6, wherein in the first heating step, the liquid medium is removed until the amount of the liquid medium in the pulp composition becomes 10% by weight or less. [Section 8] In the first heating step, the pulp composition is shaped, Item 8. The method for producing a pulp product according to any one of items 1 to 7, wherein the precursor product is a pulp mold. [Section 9] Item 9. The method for producing a pulp product according to any one of items 1 to 8, wherein the liquid repellent compound has a bio-based content of 30% or more. [Section 10] Item 10. The method for producing a pulp product according to any one of Items 1 to 9, wherein the liquid repellent compound is a compound having a hydrocarbon group having 6 to 40 carbon atoms. [Section 11] Item 11. The method for producing a pulp product according to any one of items 1 to 10, wherein the liquid repellent compound is at least one selected from the group consisting of fatty acid esters, fatty acid amides, linear hydrocarbons, and vinyl polymers. [Section 12] The pulp composition contains at least one repellent selected from the group consisting of a water-resistant agent, an oil-resistant agent, a water-repellent agent, an oil-repellent agent, and a stain-resistant agent; Item 12. The method for producing a pulp product according to any one of items 1 to 11, wherein the repellent agent comprises the liquid repellent compound. [Section 13] Item 13. The method for producing a pulp product according to any one of items 12 to 13, wherein the repellent is at least one selected from the group consisting of a water-resistant agent and an oil-resistant agent. [Section 14] Item 14. The method for producing a pulp product according to any one of items 12 or 13, wherein the repellent comprises a dispersant and water. [Section 15] Item 15. The method for producing a pulp product according to any one of items 1 to 14, wherein the pulp product has the liquid repellent compound added thereto. [Section 16] Item 16. The method for producing a pulp product according to any one of items 1 to 15, wherein the amount of the liquid repellent compound attached to the pulp product is 3.0% by weight or less. [Section 17] the liquid repellent compound is a polyol-modified compound or an amine-modified compound, The polyol modification product is a product in which a hydroxy group possessed by a polyglycerol having a polymerization degree of 1 to 15 is converted into a hydroxy group possessed by a polyglycerol having a polymerization degree of 1 to 15 by the following formula: -OC(=O)-Z O [In the formula, Z O is an alkyl group having 14 to 24 carbon atoms. is a compound substituted with a group represented by the hydroxyl group substitution rate in the modified polyol is 50% or more; The amine modification has the following formula: N(-C(=O)-Z N ) p (-H) q -L 1 -[N(-C(=O)-Z N ) r (-H) s -L 1 -] t -N(-C(=O)-Z N ) p (-H) q [In the formula, Z N is, independently in each occurrence, an alkyl group having from 14 to 24 carbon atoms; L 1 is independently in each occurrence a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms; p, in each occurrence, is an integer greater than or equal to 1 and less than or equal to 2; q is independently in each occurrence 0 or 1; p+q is each N(-C(=O)-Z N ) p (-H) q In, 2, r is independently in each occurrence 0 or 1; s is independently in each occurrence 0 or 1; r+s is each N(-C(=O)-Z N ) r (-H) s In, t is an integer between 0 and 3. Item 17. The method for producing a pulp product according to any one of items 1 to 16, wherein the compound is represented by the formula: Effect of the Invention

[0007] According to the present disclosure, a pulp product having liquid repellency can be produced. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

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

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

[0011] It should be understood that the chemical structures illustrated herein do not encompass chemical structures that would be recognized by those of ordinary skill in the art as being chemically impossible or extremely unstable.

[0012] <Manufacturing method of pulp products> The method for producing a pulp product according to the present disclosure includes: a first heating step of heating a pulp composition containing pulp and a liquid repellent compound to a first heating temperature to obtain a precursor product in which the liquid repellent compound is adhered to the pulp; a first cooling step of cooling the precursor product to a first cooling temperature to obtain a cooled precursor product; and a second heating step of heating the cooled precursor product to a second heating temperature to obtain a pulp product. Includes.

[0013] In one embodiment of the present disclosure, a pulp product to which liquid repellency (particularly high-temperature oil resistance) is favorably imparted can be produced. In one embodiment of the present disclosure, the amount of repellent (particularly liquid repellent compound) used can be reduced. It is presumed that the arrangement and rearrangement of the molecular structure of the liquid repellent compound attached to the pulp (e.g., the hydrocarbon group of a hydrocarbon-based repellent) that occurs during heating and cooling contributes to the effects of the present disclosure.

[0014] [First heating step] In the first heating step, a pulp composition containing pulp and a liquid repellent compound is heated to a first heating temperature to obtain a precursor product in which the liquid repellent compound adheres to the pulp. The pulp composition will be described in detail below.

[0015] In the first heating step, the liquid repellent compound, which is an active ingredient of the repellent, adheres to the inside and / or surface of the pulp by heating. Here, the adhesion may be physical or chemical, and for example, the liquid repellent compound may be physically or chemically modified (by reacting) with the hydroxyl groups of the pulp.

[0016] When the pulp composition contains a liquid medium, the liquid medium contained in the pulp composition may be removed from the pulp composition in the first heating step. That is, drying may be performed in the first heating step. In the first heating step, the liquid medium may be removed until the amount of the liquid medium in the pulp composition is 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, 5% by weight or less, 2.5% by weight or less, 1.0% by weight or less, 0.5% by weight or less, or 0.3% by weight or less. The amount after removal may correspond to the liquid medium content of the precursor product.

[0017] The first heating step may be performed while pressing the pulp composition, or may be performed without pressing. The pressure during pressing may be 0.03 MPa or more, 0.05 MPa or more, 0.1 MPa or more, 0.2 MPa or more, 0.3 MPa or more, 0.5 MPa or more, or 1.0 MPa or more. The pressure during pressing may be 10 MPa or less, 7.5 MPa or less, 5.0 MPa or less, 2.5 MPa or less, 1.0 MPa or less, 0.7 MPa or less, 0.5 MPa or less, or 0.3 MPa or less. Preferably, the first heating step is performed while pressing the pulp composition to 0.1 to 1.0 MPa.

[0018] In the first heating step, the pulp composition may be molded. That is, the precursor product may be a molded body (pulp mold). An example of molding is as follows: (1) Preparation of pulp mold intermediate A mesh-like body is placed on a metal pulp mold forming die with a suction hole for the slurry, and the pulp slurry is poured in. A liquid-repellent compound may be added to the pulp slurry. The pulp slurry is sucked and dehydrated through the pulp mold forming die and mesh-like body to produce a pulp mold intermediate. (2) Drying of pulp mold intermediate The obtained pulp mold intermediate is dried under a predetermined pressure (e.g., 0.1 to 1 MPa) from above and below with a male and female metallic mold that have been heated to a predetermined temperature (first heating temperature, e.g., 60 to 200°C), thereby producing a molded product (pulp mold) formed into the shape of a container.

[0019] The heating method in the first heating step is not limited, but may be hot pressing, hot air drying, oven heating, or the like, with hot pressing being preferred.

[0020] The first heating temperature is 35°C or higher, 40°C or higher, 50°C or higher, 60°C or higher, 70°C or higher, 80°C or higher, 90°C or higher, 100°C or higher, 110°C or higher, 120°C or higher, 130°C or higher, 140°C or higher, 150°C or higher, 160°C or higher, 170°C or higher, 180°C or higher, 190°C or higher, 200°C or higher, 210°C or higher, 220°C or higher, 230°C or higher, 240°C or higher, 250°C or higher, 260°C or higher, 270°C or higher, 280°C The temperature may be 40° C. or more, 290° C. or more, or 300° C. or more, preferably 40° C. or more, 80° C. or more, 100° C. or more, 120° C. or more, or 150° C. or more, and may be 500° C. or less, 450° C. or less, 400° C. or less, 350° C. or less, 300° C. or less, 250° C. or less, 200° C. or less, 180° C. or less, 160° C. or less, 140° C. or less, or 120° C. or less, preferably 250° C. or less, or 200° C. or less. The first heating temperature may be a temperature at which the liquid medium in the pulp composition can be distilled off.

[0021] The first heating temperature may be -40°C or higher, -30°C or higher, -20°C or higher, -10°C or higher, 0°C (melting point) or higher, +10°C or higher, +20°C or higher, +30°C or higher, +40°C or higher, +60°C or higher, +80°C or higher, +100°C or higher, +120°C or higher, +140°C or higher, or +160°C or higher, relative to the melting point of the liquid repellent compound, and is preferably -10°C or higher, 0°C (melting point) or higher. or higher, or +10°C or higher, in particular 0°C (melting point) or higher, and may be +250°C or lower, +200°C or lower, +150°C or lower, +100°C or lower, +75°C or lower, +50°C or lower, +25°C or lower, 0°C or lower, -25°C or lower, -50°C or lower, or -75°C or lower, and is preferably +200°C or lower, +150°C or lower, +100°C or lower, or +50°C or lower.

[0022] The first heating temperature may be 0.5 times or more, 0.6 times or more, 0.7 times or more, 0.8 times or more, 0.9 times or more, 1.0 times or more, 1.1 times or more, 1.2 times or more, 1.5 times or more, 1.7 times or more, 2.0 times or more, or 2.5 times or more, preferably 0.7 times or more, 1.0 times or more, or 1.2 times or more, and particularly 1.0 times or more, relative to the melting point of the liquid repellent compound, and may be 4.0 times or less, 3.5 times or less, 3.0 times or less, 2.5 times or less, 2.0 times or less, 1.5 times or less, 1.2 times or less, or 1.0 times or less, and preferably 3.0 times or less, or 2.0 times or less.

[0023] The heating in the first heating step may be performed in one stage or multiple stages, but heating is performed at least until the pulp composition reaches the first heating temperature. For example, when heating is performed in multiple stages (for example, two stages), the heating temperature in the first stage may be 60°C or higher, preferably 70°C or higher, more preferably 80°C or higher, and may be 250°C or lower, preferably 200°C or lower, more preferably 180°C or lower, more preferably 150°C or lower, and most preferably 100°C or lower. The heating temperature in the second stage is preferably higher than the heating temperature in the first stage, and may be 60°C or higher, preferably 80°C or higher, more preferably 100°C or higher, more preferably 120°C or higher, more preferably 140°C or higher, more preferably 160°C or higher, and may be 250°C or lower, preferably 200°C or lower, and more preferably 180°C or lower.

[0024] The time for which the first heating temperature is maintained is not particularly limited, but may be 10 seconds or more, 30 seconds or more, 60 seconds or more, 90 seconds or more, or 120 seconds or more, and is preferably 30 seconds or more. From the viewpoint of productivity, the time for which the first heating temperature is maintained may be preferably 1 hour or less, 30 minutes or less, 10 minutes or less, or 5 minutes or less.

[0025] [First cooling process] In the first cooling step, the precursor product obtained in the first heating step is cooled to a first cooling temperature to obtain a cooled precursor product.

[0026] The first cooling step may be performed while applying pressure to the precursor product (for example, 0.1 to 1 MPa) or without applying pressure. Preferably, no pressure is applied. For example, when cooling the precursor product, the precursor product may be cooled in the mold used in the previous step, or may be removed from the mold and cooled. Preferably, the precursor product is removed from the mold and cooled.

[0027] The cooling method in the first cooling step is not limited, but examples thereof include press cooling, heat radiation, and air cooling.

[0028] The first cooling temperature may be -10°C or higher, 0°C or higher, 10°C or higher, 20°C or higher, 25°C or higher, 30°C or higher, 40°C or higher, 50°C or higher, 60°C or higher, 70°C or higher, 80°C or higher, or 90°C or higher, and may be 150°C or lower, 125°C or lower, 100°C or lower, 90°C or lower, 80°C or lower, 70°C or lower, 60°C or lower, 50°C or lower, 40°C or lower (less than 40°C), 30°C or lower, 25°C or lower, 20°C or lower, 15°C or lower, or 10°C or lower, and is preferably 50°C or lower, 40°C or lower (less than 40°C), 30°C or lower, or 25°C or lower. The first cooling temperature may be in the range of room temperature (eg, 10° C. to 40° C., 15° C. to 35° C., 20° C. to 30° C., etc.).

[0029] The first cooling temperature may be −200° C. or higher, −175° C. or higher, −150° C. or higher, −125° C. or higher, −100° C. or higher, −75° C. or higher, −50° C. or higher, −25° C. or higher, 0° C. or higher, +5° C. or higher, or +10° C. or higher relative to the melting point of the liquid repellent compound, and is preferably −150° C. or higher, −100° C. or higher, or −50° C. or higher, and is preferably +25° C. or lower, +15° C. or higher. The temperature may be below +5°C, 0°C or below, -5°C or below, -10°C or below, -15°C or below, -20°C or below, -25°C or below, -30°C or below, -35°C or below, -40°C or below, -50°C or below, -75°C or below, -100°C or below, -125°C or below, or -150°C or below, preferably 0°C or below, -15°C or below, -30°C or below, -50°C or below, or -75°C or below.

[0030] The first cooling temperature may be 0.01 times or more, 0.03 times or more, 0.05 times or more, 0.1 times or more, 0.15 times or more, 0.20 times or more, 0.25 times or more, 0.3 times or more, 0.35 times or more, or 0.4 times or more relative to the melting point of the liquid repellent compound, and may be 2.0 times or less, 1.75 times or less, 1.5 times or less, 1.25 times or less, 1.0 times (melting point) or less, 0.9 times or less, 0.8 times or less, 0.7 times or less, 0.6 times or less, 0.5 times or less, 0.4 times or less, 0.3 times or less, 0.2 times or less, or 0.1 times or less.

[0031] The first cooling temperature may be -300°C or more, -275°C or more, -250°C or more, -225°C or more, -200°C or more, -175°C or more, -150°C or more, -125°C or more, -100°C or more, -75°C or more, -50°C or more, or -25°C or more, and may be -10°C or less, -30°C or less, -50°C or less, -75°C or less, -100°C or less, -125°C or less, -150°C or less, -175°C or less, -200°C or less, -225°C or less, or -250°C or less, and is preferably -75°C or less or -150°C or less.

[0032] The cooling in the first cooling step may be carried out in one stage or in multiple stages, but is carried out at least until the precursor product reaches the first cooling temperature.

[0033] The time for which the first cooling temperature is maintained is not particularly limited, but is preferably 10 seconds or more, 30 seconds or more, or 1 minute or more, more preferably 5 minutes or more, and even more preferably 10 minutes or more, and may be 1 hour or more, and from the viewpoint of productivity, the time for which the first cooling temperature is maintained may be preferably 48 hours or less, 24 hours or less, or 12 hours or less.

[0034] [Second heating step] In a second heating step, the cooled precursor product is heated to a second heating temperature to obtain a pulp product.

[0035] The second heating step may be performed while applying pressure (for example, 0.1 to 1 MPa) to the cooled precursor product, or may be performed without applying pressure. Preferably, no pressure is applied. For example, when the cooled precursor product is heated, the cooled precursor product may be heated in the mold used in the previous step, or may be removed from the mold and heated. Preferably, the cooled precursor product is removed from the mold and heated.

[0036] The heating method in the second heating step is not limited, but may be heat pressing, hot air drying, oven heating, etc., and preferably hot air drying and oven heating are used.

[0037] The second heating temperature may be 35°C or more, 40°C or more, 50°C or more, 60°C or more, 70°C or more, 80°C or more, 90°C or more, 100°C or more, 110°C or more, 120°C or more, 130°C or more, 140°C or more, 150°C or more, 160°C or more, 170°C or more, 180°C or more, 190°C or more, 200°C or more, 210°C or more, 220°C or more, 230°C or more, 240°C or more, 250°C or more, 260°C or more, 270°C or more, 280°C or more, 290°C or more, or 300°C or more, and is preferably 40°C or more. ° C. or higher, 50° C. or higher, 60° C. or higher, 80° C. or higher, 100° C. or higher, 120° C. or higher, or 150° C. or higher; and may be 500° C. or lower, 450° C. or lower, 400° C. or lower, 350° C. or lower, 300° C. or lower, 250° C. or lower, 200° C. or lower, 180° C. or lower, 160° C. or lower, 140° C. or lower, 120° C. or lower, 100° C. or lower, 80° C. or lower, or 60° C. or lower, and is preferably 250° C. or lower, 200° C. or lower, 180° C. or lower, 150° C. or lower, 125° C. or lower, 100° C. or lower, or 80° C. or lower.

[0038] The second heating temperature may be -100°C or higher, -80°C or higher, -60°C or higher, -50°C or higher, -40°C or higher, -30°C or higher, -20°C or higher, -10°C or higher, 0°C (melting point) or higher, +10°C or higher, +20°C or higher, +30°C or higher, +40°C or higher, +60°C or higher, +80°C or higher, +100°C or higher, +120°C or higher, +140°C or higher, or +160°C or higher, preferably -50°C or higher, It may be -30°C or higher, or 0°C (melting point) or higher, and may be +200°C or lower, +175°C or lower, +150°C or lower, +125°C or lower, +100°C or lower, +75°C or lower, +50°C or lower, +25°C or lower, +10°C or lower, 0 (melting point)°C or lower, -10°C or lower, -25°C or lower, -50°C or lower, or -75°C or lower, and is preferably +75°C or lower, +50°C or lower, +10°C or lower, 0 (melting point)°C or lower, or -10°C or lower.

[0039] The second heating temperature may be 0.5 times or more, 0.6 times or more, 0.7 times or more, 0.8 times or more, 0.9 times or more, 1.0 times or more, 1.1 times or more, 1.2 times or more, 1.5 times or more, 1.7 times or more, 2.0 times or more, or 2.5 times or more, preferably 0.7 times or more, 0.8 times or more, 1.0 times or more, or 1.2 times or more, and particularly 0.7 times or more, and may be 4.0 times or less, 3.5 times or less, 3.0 times or less, 2.5 times or less, 2.0 times or less, 1.5 times or less, 1.2 times or less, or 1.0 times or less, preferably 2.0 times or less, 1.5 times or less, or 1.2 times or less.

[0040] The second heating temperature may be -250°C or higher, -200°C or higher, -175°C or higher, -150°C or higher, -125°C or higher, -100°C or higher, -75°C or higher, -50°C or higher, -25°C or higher, 0°C or higher, +25°C or higher, +50°C or higher, +75°C or higher, or +100°C or higher, relative to the first heating temperature, and may be +100°C or lower, +80°C or lower, +60°C or lower, +40°C or lower, +20°C or lower, 0°C or lower, -20°C or lower, -40°C or lower, -60°C or lower, -80°C or lower, or -100°C or lower.

[0041] The second heating temperature may be +10°C or more, +20°C or more, +30°C or more, +40°C or more, +50°C or more, +60°C or more, +70°C or more, +80°C or more, +90°C or more, +100°C or more, +110°C or more, +120°C or more, +130°C or more, +140°C or more, +150°C or more, +160°C or more, +170°C or more, or +180°C or more, and may be +300°C or less, +275°C or less, +250°C or less, +225°C or less, +200°C or less, +180°C or less, +160°C or less, +140°C or less, +120°C or less, +100°C or less, +80°C or less, +60°C or less, or +40°C or less, relative to the first cooling temperature.

[0042] The heating in the second heating step may be performed in one stage or multiple stages, but is performed at least until the cooled precursor product reaches the second heating temperature.

[0043] The time for maintaining the second heating temperature is not particularly limited, but is preferably 1 minute or more, more preferably 5 minutes or more, even more preferably 10 minutes or more, and may be 1 hour or more. From the viewpoint of productivity, the time for maintaining the second heating temperature may be preferably 48 hours or less, 24 hours or less, or 12 hours or less.

[0044] A pulp product is obtained through a second heating step. The amount of the liquid repellent compound attached to the pulp product after the second heating step may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, and is preferably 3.0% by weight or less. According to the present disclosure, good liquid repellency can be achieved even if the amount of the liquid repellent compound is reduced.

[0045] [Pulp composition production process] A method for producing a pulp product according to the present disclosure may include treating a pulp substrate with a repellent agent to obtain a pulp composition.

[0046] Methods for treating the pulp base material include an internal treatment method in which a repellent is added to the pulp before papermaking (e.g., pulp slurry), and an external treatment method in which a repellent is applied to the pulp after papermaking (e.g., pulp product). Examples of the internal addition treatment include mixing, immersion, and the like, and may include a step of adding the repellent to the pulp slurry and stirring and mixing it.

[0047] Examples of the external additive treatment method include spraying, coating, etc., and specific examples include a pond type two-roll size press, a gate roll type, and a rod metering size press.

[0048] [Pulp / Pulp base material] The pulp composition contains pulp, and the pulp is treated with a repellent as a pulp base material. The pulp base material may be in the form of pulp alone, pulp slurry, pulp product, etc. Examples of the pulp base material include pulp such as bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp or thermomechanical pulp, pulp slurry containing the above pulp, and pulp products such as paper, paper containers, and paper molded bodies made of waste paper pulp such as recycled newspaper, recycled magazine, recycled cardboard, and deinked recycled paper. Specific examples of pulp products include food packaging materials, food containers, gypsum board base paper, coated base paper, medium quality paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-proof liners and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, and molded paper (molded containers).

[0049] The amount of pulp in the pulp composition may be 0.1% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, 75% by weight or more, or 90% by weight or more, and may be 99% by weight or less, 75% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 4% by weight or less, or 3% by weight or less. Typically, when the pulp composition is prepared by internal addition, the amount of pulp in the pulp composition is 30% by weight or less, and when the pulp composition is prepared by external addition, the amount of pulp in the pulp composition is 75% by weight or more.

[0050] [Liquid medium] The pulp composition may comprise 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 comprise a liquid medium derived from a repellent agent.

[0051] The amount of the liquid medium in the pulp composition may be 0.1% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, 75% by weight or more, 90% by weight or more, or 95% by weight or more, and may be 99% by weight or less, 75% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 4% by weight or less, or 3% by weight or less. Typically, when the pulp composition is prepared by internal addition, the amount of the liquid medium in the pulp composition is 50% by weight or more, particularly 90% by weight or more, and when the pulp composition is prepared by external addition, the amount of the liquid medium in the pulp composition is 30% by weight or less, particularly 10% by weight or less.

[0052] [Repellent] The repellent agent contains a liquid repellent compound. The repellent agent will be described in detail in the section <Repellent Agent> below. The amount of the repellent agent added to the pulp base material may be adjusted so that the amount of the liquid repellent compound is the desired amount.

[0053] The amount of the liquid repellent compound may be, relative to 100 parts by weight of pulp, 0.1 parts by weight or more, 0.3 parts by weight or more, 0.5 parts by weight or more, 0.75 parts by weight or more, 1.0 parts by weight or more, 2.0 parts by weight or more, or 3.0 parts by weight or more, and may be 10 parts by weight or less, 7.5 parts by weight or less, 5.0 parts by weight or less, 4.0 parts by weight or less, 3.0 parts by weight or less, 2.0 parts by weight or less, 1.0 parts by weight or less, 0.75 parts by weight or less, or 0.5 parts by weight or less, preferably 5.0 parts by weight or less, and more preferably 3.0 parts by weight or less.

[0054] The amount of the liquid repellent compound which is a fatty acid ester may be, relative to 100 parts by weight of pulp, 0.1 parts by weight or more, 0.3 parts by weight or more, 0.5 parts by weight or more, 0.75 parts by weight or more, 1.0 parts by weight or more, 2.0 parts by weight or more, or 3.0 parts by weight or more, and may be 10 parts by weight or less, 7.5 parts by weight or less, 5.0 parts by weight or less, 4.0 parts by weight or less, 3.0 parts by weight or less, 2.0 parts by weight or less, 1.0 parts by weight or less, 0.75 parts by weight or less, or 0.5 parts by weight or less, preferably 5.0 parts by weight or less, more preferably 3.0 parts by weight or less.

[0055] The amount of the liquid repellent compound which is a fatty acid amide may be, relative to 100 parts by weight of pulp, 0.1 parts by weight or more, 0.3 parts by weight or more, 0.5 parts by weight or more, 0.75 parts by weight or more, 1.0 parts by weight or more, 2.0 parts by weight or more, or 3.0 parts by weight or more, and may be 10 parts by weight or less, 7.5 parts by weight or less, 5.0 parts by weight or less, 4.0 parts by weight or less, 3.0 parts by weight or less, 2.0 parts by weight or less, 1.0 parts by weight or less, 0.75 parts by weight or less, or 0.5 parts by weight or less, preferably 3.0 parts by weight or less, more preferably 2.0 parts by weight or less, and even more preferably 1.0 part by weight or less.

[0056] The amount of the liquid repellent compound which is a linear hydrocarbon may be, relative to 100 parts by weight of pulp, 0.1 parts by weight or more, 0.3 parts by weight or more, 0.5 parts by weight or more, 0.75 parts by weight or more, 1.0 parts by weight or more, 2.0 parts by weight or more, or 3.0 parts by weight or more, and may be 10 parts by weight or less, 7.5 parts by weight or less, 5.0 parts by weight or less, 4.0 parts by weight or less, 3.0 parts by weight or less, 2.0 parts by weight or less, 1.0 parts by weight or less, 0.75 parts by weight or less, or 0.5 parts by weight or less, preferably 5.0 parts by weight or less, more preferably 3.0 parts by weight or less.

[0057] The amount of the amine-modified liquid repellent compound may be, relative to 100 parts by weight of pulp, 0.1 parts by weight or more, 0.3 parts by weight or more, 0.5 parts by weight or more, 0.75 parts by weight or more, 1.0 parts by weight or more, 2.0 parts by weight or more, or 3.0 parts by weight or more, and may be 10 parts by weight or less, 7.5 parts by weight or less, 5.0 parts by weight or less, 4.0 parts by weight or less, 3.0 parts by weight or less, 2.0 parts by weight or less, 1.0 parts by weight or less, 0.75 parts by weight or less, or 0.5 parts by weight or less, preferably 5.0 parts by weight or less, and more preferably 3.0 parts by weight or less.

[0058] The amount of the polyol-modified liquid repellent compound may be, relative to 100 parts by weight of pulp, 0.1 parts by weight or more, 0.3 parts by weight or more, 0.5 parts by weight or more, 0.75 parts by weight or more, 1.0 parts by weight or more, 2.0 parts by weight or more, or 3.0 parts by weight or more, and may be 10 parts by weight or less, 7.5 parts by weight or less, 5.0 parts by weight or less, 4.0 parts by weight or less, 3.0 parts by weight or less, 2.0 parts by weight or less, 1.0 parts by weight or less, 0.75 parts by weight or less, or 0.5 parts by weight or less, preferably 5.0 parts by weight or less, and more preferably 3 parts by weight or less.

[0059] The amount of the liquid repellent compound which is a polycarboxylic acid modified product may be, relative to 100 parts by weight of pulp, 0.1 parts by weight or more, 0.3 parts by weight or more, 0.5 parts by weight or more, 0.75 parts by weight or more, 1.0 parts by weight or more, 2.0 parts by weight or more, or 3.0 parts by weight or more, and may be 10 parts by weight or less, 7.5 parts by weight or less, 5.0 parts by weight or less, 4.0 parts by weight or less, 3.0 parts by weight or less, 2.0 parts by weight or less, 1.0 parts by weight or less, 0.75 parts by weight or less, or 0.5 parts by weight or less, preferably 5.0 parts by weight or less, and more preferably 3.0 parts by weight or less.

[0060] The amount of the liquid repellent compound which is a vinyl polymer may be, relative to 100 parts by weight of pulp, 0.1 parts by weight or more, 0.3 parts by weight or more, 0.5 parts by weight or more, 0.75 parts by weight or more, 1.0 parts by weight or more, 2.0 parts by weight or more, or 3.0 parts by weight or more, and may be 10 parts by weight or less, 7.5 parts by weight or less, 5.0 parts by weight or less, 4.0 parts by weight or less, 3.0 parts by weight or less, 2.0 parts by weight or less, 1.0 parts by weight or less, 0.75 parts by weight or less, or 0.5 parts by weight or less, preferably 5.0 parts by weight or less, more preferably 3.0 parts by weight or less, and even more preferably 2.0 parts by weight or less.

[0061] In the external addition treatment, the amount of the liquid repellent compound contained in the coating layer is 0.01 g / m 2 More than 0.03g / m 2 More than 0.05g / m 2 More than 0.1g / m 2 More than 0.3g / m 2 More than 0.5g / m 2 or more, or 1.0 g / m2 or more, and 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 or less than 0.1 g / m 2 It may be the following:

[0062] [Additives] In addition to the pulp and the repellent (liquid-repellent compound), the pulp composition may contain additives used in the manufacture of pulp products, such as sizing agents (e.g., cationic sizing agents, anionic sizing agents, rosin-based sizing agents (e.g., acidic rosin-based sizing agents, neutral rosin-based sizing agents)), paper strength agents, flocculants, fixing agents, retention aids, dyes, fluorescent dyes, slime control agents, and defoamers. Specific examples of additives include alkylketene dimers, alkenyl succinic anhydrides, styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, starch, modified starch, carboxymethylcellulose, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichlorides and polyalkylene polyamines, dicyandiamide-formaldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers. The pulp composition contains a component derived from the repellent, but each component contained in the repellent may be added to the pulp composition as an additive.

[0063] The additive may be nonionic, cationic, anionic or amphoteric. The ionic charge density of the additive may be -10000 to 10000 μeq / g, preferably -4000 to 8000 μeq / g, more preferably -1000 to 7000 μeq / g. In the case of a paper substrate containing a cationic additive relative to the pulp, the repellent may be anionic, and in the case of a paper substrate containing an anionic additive, the repellent may be cationic.

[0064] The amount of each of the above additives may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, or 5 parts by weight or more, and may be 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, per 100 parts by weight of pulp.

[0065] [Other processes] The method for producing a pulp product according to the present disclosure may include other steps. For example, a step of adjusting the humidity and / or temperature of the pulp product after the second heating may or may not be provided. For example, when adjusting the humidity and temperature of the pulp molded product, the pulp molded product after the second heating may be placed in a thermo-hygrostat chamber adjusted to 10°C or higher and a humidity of 20% or higher, and stored for 30 minutes or more. The temperature adjustment is preferably from 15 to 30°C, and the humidity adjustment is preferably from 20% to less than 60%, but is not limited thereto.

[0066] <Repellent> The repellent agent of the present disclosure is attached to a substrate (particularly a pulp substrate) and can impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the substrate, and can also function as a water resistance agent, an oil resistance agent, a water repellent agent, an oil repellent agent, and / or a stain resistance agent. The repellent agent of the present disclosure includes a liquid repellent compound. The liquid repellent compound itself may be used as a repellent agent, or may be used in combination with other components as described below.

[0067] The repellent agent in the present disclosure may not contain any compound selected from the group consisting of a compound having a fluoroalkyl group having 8 or more carbon atoms, a compound having a perfluoroalkyl group having 8 or more carbon atoms, a compound having a fluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The repellent agent in the present disclosure can impart liquid repellency to a substrate even if it does not contain these fluorine compounds.

[0068] The volumetric ratio of particles of 100 μm or more in the repellent of the present disclosure measured by a laser diffraction scattering method may be 0.1% or more, 0.3% or more, 0.5% or more, 1% or more, 1.5% or more, 3% or more, 4% or more, 5% or more, or 10% or more, and may be 50% or less, 30% or less, 20% or less, 15% or less, 10% or less, 5% or less, 3% or less, or 1.5% or less. The method for setting the volumetric ratio of particles of 1 μm or more measured by a laser diffraction scattering method to the above range is not limited, but for example, the particles in the raw material and / or dispersion may be finely divided using a grinder, homogenizer, or the like.

[0069] The volume median diameter of the repellent of the present disclosure measured by the laser diffraction scattering method may be 0.1 μm or more, 1 μm or more, 3 μm or more, 5 μm or more, 10 μm or more, 15 μm or more, 30 μm or more, or 50 μm or more, and may be 300 μm or less, 200 μm or less, 100 μm or less, 50 μm or less, 30 μm or less, 20 μm or less, 10 μm or less, 5 μm or less, or 1 μm or less. In the present disclosure, the volume median diameter refers to the median diameter (D50) in the volume-based particle size distribution measured by the laser diffraction scattering method.

[0070] [Liquid repellent compound] The liquid repellent compounds of the present disclosure are capable of adhering to a substrate (particularly a pulp substrate) to impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the substrate.

[0071] [Characteristics, etc.] The properties that the liquid repellent compound may have are listed below. These properties may vary depending on the type of compound.

[0072] The HD (n-hexadecane) contact angle of the liquid repellent compound may be 10° or more, 20° or more, 25° or more, 30° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 60° or more, or 65° or more, preferably 25° or more, more preferably 30° or more, and may be 100° or less, 90° or less, or 75° or less. When the liquid repellent compound has an HD contact angle equal to or greater than the above lower limit, the liquid repellency (particularly oil repellency) can be imparted to the substrate satisfactorily. The HD contact angle is the static contact angle of the liquid repellent compound with respect to the spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle 1 second after the drop lands.

[0073] The water contact angle of the liquid repellent compound may be 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more, and may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When the liquid repellent compound has a water contact angle equal to or greater than the above lower limit, the liquid repellency (particularly water repellency) can be imparted to the substrate satisfactorily. The water contact angle is the static contact angle of the liquid repellent compound with respect to the spin-coated film, and is obtained by dropping 2 μL of water onto the spin-coated film and measuring the contact angle 1 second after the drop has landed.

[0074] The liquid repellent compound is preferably a biobased compound having carbon of biobased origin. The biobased degree is measured in accordance with ASTM D6866. The biobased degree may be 20% or more, preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example, 100%. A high biobased degree means that a small amount of fossil resource-based materials, such as petroleum, is used, and from this perspective, the higher the biobased degree of the liquid repellent compound, the more preferable it is.

[0075] The biodegradability of the liquid repellent compound after 180 days is preferably 5% or more. Since the environmental load is reduced, the higher the biodegradability, the more preferable. The biodegradability of the liquid repellent compound after 180 days may be, for example, 10% or more, 20% or more, 30% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, preferably 30% or more, more preferably 50% or more, even more preferably 70% or more, and most preferably 80% or more. The biodegradability of the liquid repellent compound after 60 days is preferably 5% or more. Since the environmental load is reduced, the higher the biodegradability, the more preferable. The biodegradability of the liquid repellent compound after 60 days may be, for example, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, or 45% or more, preferably 10% or more, more preferably 30% or more. Such biodegradability may be the biodegradability defined in JIS K 6953-1 or ASTM D6400.

[0076] The melting point of the liquid repellent compound may be 30°C or more, 40°C or more, 60°C or more, 80°C or more, 100°C or more, or 120°C or more, and is preferably 40°C or more, and may be 250°C or less, 225°C or less, 200°C or less, 150°C or less, 130°C or less, 120°C or less, 110°C or less, 100°C or less, 80°C or less, or 50°C or less.

[0077] [Structure etc.] The liquid repellent compound in the present disclosure may not have any group selected from the group consisting of a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, and a fluorine atom. Even if the liquid repellent compound does not contain these fluorine-containing groups, it can impart liquid repellency to the substrate.

[0078] The liquid repellent compound may be a compound having a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group. From the viewpoint of liquid repellency, the liquid repellent compound may have a hydrocarbon group having 6 to 40 carbon atoms (e.g., an alkyl group).

[0079] (Optionally substituted monovalent hydrocarbon group) The liquid repellent compound may have a monovalent hydrocarbon group which may have a substituent.

[0080] The hydrocarbon group may be a monovalent hydrocarbon group having 1 to 40 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched, cyclic or linear, and is more preferably linear.

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

[0082] The hydrocarbon group may have a substituent, but is preferably unsubstituted. Examples of the substituent include -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms at each occurrence). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, the hydrocarbon group may have 1 to 3 (eg, 1) -OR' (particularly -OH) as a substituent (eg, other than at a terminal position).

[0083] (monovalent polysiloxane group) The liquid repellent compound may have a monovalent polysiloxane group. The (monovalent) polysiloxane group as well as the (monovalent) hydrocarbon group may impart liquid repellency to the substrate.

[0084] The polysiloxane group has the formula: -[-Si(R s )2-O-] a - [In the formula, R s is independently in each occurrence a hydrocarbon group or a reactive group having 1 to 40 carbon atoms; a is an integer between 5 and 10,000. It may be expressed as:

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

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

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

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

[0089] Examples of reactive groups include groups having functional groups (e.g., hydroxyl, amino, mercapto, epoxy, carboxyl, halogen-substituted alkyl, vinyl, (meth)acrylic, (meth)acryloyloxy, and (meth)acrylamide groups, hydrogen atoms directly bonded to silicon atoms, etc.). These functional groups may be directly bonded to silicon atoms, or may be bonded to organic groups directly bonded to silicon atoms. The organic groups may be hydrocarbon groups, such as alkylene groups or divalent aromatic groups. The hydrocarbon groups may have 2 to 12 carbon atoms, and alkylene groups preferably have 2 to 10 carbon atoms. Divalent aromatic groups preferably have 6 to 12 carbon atoms. The reactive groups may be groups selected from the group consisting of hydroxyl, epoxy rings, carboxyl, (meth)acrylic, and amino groups, and may be at least one selected from the group consisting of epoxy rings, hydroxyl, (meth)acrylic, and carboxyl groups.

[0090] a may be 3 or more, 5 or more, 10 or more, 30 or more, 50 or more, 100 or more, 500 or more, 1000 or more, 2000 or more, or 3000 or more, and is preferably 10 or more, and may be 10,000 or less, 7,500 or less, 5,000 or less, 3,000 or less, 1,500 or less, 1,000 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less, and is preferably 500 or less.

[0091] In the polysiloxane group, R is a hydrocarbon group having 1 to 5 carbon atoms. s The amount of R s With respect to the total of R, it may be 20 mol% or more, 40 mol% or more, 60 mol% or more, or 80 mol% or more, preferably 50 mol% or more, and may be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less. For example, R s Based on the total number of groups, 50 mol % or more may be methyl or ethyl groups (particularly methyl groups).

[0092] In the polysiloxane group, R is a hydrocarbon group having 6 to 40 carbon atoms. s The amount of R s and may be 100 mol % or less, 90 mol % or less, 80 mol % or less, or 70 mol % or less, based on the total of the above.

[0093] In the polysiloxane group, R s The amount of R s and may be 5 mol % or more, 10 mol % or more, 20 mol % or more, or 30 mol % or more, and may be 50 mol % or less, 40 mol % or less, 30 mol % or less, or 20 mol % or less, based on the total of the above.

[0094] R s The groups may be introduced randomly or in blocks, but are preferably introduced randomly.

[0095] The terminal structure of the polysiloxane group is not limited, but may be -OR s , -Si(R s)3, etc. s Examples of the reactive group are as described above, and may be, for example, at least one selected from the group consisting of an epoxy ring, a hydroxy group, a (meth)acrylic group, and a carboxyl group.

[0096] The polysiloxane group may have a linker, and the parent compound and the polysiloxane group may be bonded via a linker. Such a linker may be, but is not limited to, a hydrocarbon group having 1 to 40 (e.g., 1 to 20) carbon atoms which may be interrupted by an oxygen atom, for example, a (poly)oxyalkylene group having 1 to 40 (e.g., 1 to 20) carbon atoms.

[0097] Examples of polysiloxane groups include: -[-Si(R s )2-O-] a -Si(R s )3 -L s1 -[-Si(R s )2-O-] a -Si(R s )3 -L s1 -OL s1 -[-Si(R s )2-O-] a -R s -L s1 -[-Si(R s )2-O-] a -Si(R s )3 -L s1 -OL s1 -[-Si(R s )2-O-] a -R s -L s1 -[-Si(R s )2-O-] a -Si(R s ) 3、 -L s1 -[-Si(R s )2-O-] a -R s [In the formula, R s is independently in each occurrence a hydrocarbon group or a reactive group having 1 to 40 carbon atoms, s has one or more reactive groups, R s 50 mol % or more of the total groups are methyl groups, L s1 is a hydrocarbon group having 1 to 20 carbon atoms, a is between 5 and 10,000. TIFF2025044132000001.tif2169 [In the formula, a represents an integer of 0 to 150, b represents an integer of 1 to 150, (a+b) is 5 to 200, and n is an integer of 0 to 36.] etc.

[0098] [Examples of liquid repellent compounds] An example of the liquid repellent compound is a compound having a hydrocarbon group having a carbon number of 6 to 40. Examples of the hydrocarbon group and the preferred range are as described above.

[0099] An example of the liquid repellent compound is at least one compound selected from the group consisting of fatty acid esters, fatty acid amides, linear hydrocarbons, and vinyl polymers. Examples of fatty acid esters and fatty acid amides may include compounds corresponding to amine-modified compounds, polyol-modified compounds, and polycarboxylic acid-modified compounds, which will be described below. Examples of linear hydrocarbons include waxes (e.g., paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax)), etc.

[0100] An example of the liquid repellent compound is at least one selected from the group consisting of amine-modified compounds, polyol-modified compounds, polycarboxylic acid-modified compounds, and vinyl polymers (described in detail below).

[0101] The liquid repellent compound may contain an ester group, an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group (e.g., an ester group, an amide group, a urethane group, a urea group, an imide group). For example, the liquid repellent compound may contain -C(=O)-O-, -OC(=O)-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'-, or -SONR'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) in each occurrence). The liquid repellent compound may be a compound in which a raw material compound and a modifying group (particularly the monovalent hydrocarbon group which may have the above-mentioned substituent) are bonded via at least one of these groups. The liquid-repellent compound may include an amide structure. The liquid-repellent compound may have at least an amide structure, thereby improving the liquid repellency. Here, the amide structure may be an amide structure in a broad sense, and may be selected from an amide structure in an amide (acid amide) group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfone urethane group, a sulfone urea group, a sulfone imide group, and the like. The amide structure may be an amide structure selected from the group consisting of -(C=O)N(-)2, -(C=S)N(-)2, and -S(=O)2N(-)2 (each group may be inverted). Here, at least one of the bonds possessed by N in the amide structure may be bonded to a hydrogen atom. The amide structure is preferably -(C=O)N(-)2, and may be an amide structure in a group selected from the group consisting of an amide group, a urethane group, a urea group, and an imide group.

[0102] [Amount of liquid repellent compound] The amount of the liquid repellent compound in the repellent may be 0.01% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, and may be 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight or less. The liquid repellent compound alone may be used as the repellent.

[0103] [Amine Modified Compounds] As an example of the liquid repellent compound, an amine-modified compound will be described below. The amine-modified compound is an amine compound that has been chemically modified to exhibit liquid repellency.

[0104] Due to its structure, the amine-modified compound in the present disclosure has excellent dispersibility in liquid media, and the repellent of the present disclosure can have stable performance. Repellents that use polymer-type compounds as active ingredients tend to have a wide molecular weight distribution and contain relatively large amounts of impurity components. On the other hand, the amine-modified compound can be made into a low molecular weight compound, and the molecular weight distribution can be narrowed (unitized), which can result in good performance.

[0105] [Structure etc.] The molecular weight of the amine modification may be 200 or more, 300 or more, 350 or more, 400 or more, 500 or more, 550 or more, or 750 or more; and may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 900 or less, 800 or less, 750 or less, or 500 or less.

[0106] The amine modified in the present disclosure may not have an active hydrogen-containing group. Examples of the active hydrogen-containing group include an amino group (an amino group that is not adjacent to a carbonyl group, such as a primary or secondary amino group), a hydroxyl group, and a carboxyl group. In particular, the amine modified in the present disclosure may not have a primary or secondary amino group that is not adjacent to a carbonyl group.

[0107] The amine-modified product in the present disclosure may be a polyamide having a plurality of amide structures, for example, a polyamide having a plurality of modifying groups (for example, Z N ) may be a polyamide modified via an amide structure. Here, the amide may be an amide structure contained in a urethane group, a urea group, an imide, or the like.

[0108] The amine modified product may be a compound obtained by modifying an amine (raw amine compound) with a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group.

[0109] In the amine-modified product, one or more amino groups of the amine are substituted with a modifying group. The modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent. From the viewpoint of improving liquid repellency, the amine-modified product may have a structure in which an amine is modified with an alkyl group having 6 to 40 carbon atoms.

[0110] For details of the monovalent hydrocarbon group which may have a substituent and the monovalent polysiloxane group, the above explanations of (the monovalent hydrocarbon group which may have a substituent) and (the monovalent polysiloxane group) are incorporated herein.

[0111] (amine skeleton) The amine modified product in the present disclosure has an amine skeleton. The amine skeleton has one or more amino groups having a predetermined number of bonds (valences) obtained by removing a predetermined number of atoms or atomic groups (e.g., hydrogen) from an amine compound. The amino group in the amine skeleton means a group selected from the group consisting of -NH2, -NH-, and -N(-)2, and also includes an amino group adjacent to a carbonyl group contained in an amide group, a urethane group, a urea group, an imide group, etc. Note that the amine skeleton may be an aliphatic group or an aromatic group having one or more amino groups, and does not exclude the presence of heteroatoms other than nitrogen.

[0112] The molecular weight of the amine skeleton may be 30 or more, 50 or more, 100 or more, 200 or more, 300 or more, 400 or more, or 500 or more, and may be 2800 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 600 or less, 450 or less, 300 or less, or 250 or less.

[0113] The number of carbon atoms in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and may be 100 or less, 80 or less, 60 or less, 40 or less, 30 or less, 20 or less, 10 or less, or 5 or less, preferably 50 or less, and particularly 30 or less.

[0114] The amine skeleton has one or more amino groups. The amino group is a monovalent to trivalent amino group, and is one or more groups selected from the group consisting of -NH2, -NH-, and -N(-)2. The number of amino groups in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and is preferably 2 or more, and may be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0115] The amine skeleton has a hydrocarbon group (an aliphatic hydrocarbon group or an aromatic hydrocarbon group). The hydrocarbon group may be cyclic, branched, or linear. The hydrocarbon group may be saturated or unsaturated (for example, saturated). Here, the hydrocarbon group may be interrupted by an oxygen atom and / or a sulfur atom, or may be composed of only carbon atoms, nitrogen atoms, and hydrogen atoms. The hydrocarbon group may be a hydrocarbon group that may be interrupted by an oxygen atom and / or a sulfur atom (for example, a chain-like saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings), or may be a general hydrocarbon group (for example, a chain-like saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings). When the hydrocarbon group is interrupted by an oxygen atom and / or a sulfur atom, it has an ether, thioether, polyether, or polythioether structure. The number of hydrocarbon groups in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and may be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0116] The amine skeleton may be composed of a monovalent to trivalent amino group and a chain-like saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group which may be interrupted by an oxygen atom and / or a sulfur atom.

[0117] The molar ratio of carbon atoms to nitrogen atoms (C / N ratio) in the amine skeleton may be 1 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, or 4 or more, and may be 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, or 2 or less, and is preferably 6 or less or 4 or less.

[0118] (-Y N -Z N n ) The amine modification of the present disclosure has the formula: -Y N -Z N n [In the formula, Y N is a direct bond or a group having a valence of 1+n, Z N represents a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, n is an integer between 1 and 3. has one or more groups represented by At least one -Y N -Z N n is bonded to a nitrogen atom of the amine skeleton.

[0119] The amine modification has -Y N -Z N n The number may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and is preferably 2 or more, and may be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0120] At least one -Y in the amine modification N -Z N n is bonded to the nitrogen atom of the amine skeleton. All -Y N -Z N n Among the number of -Y bonded to the nitrogen atom of the amine skeleton, N -Z N n The ratio of the number of -Y that is not bonded to a nitrogen atom of the amine skeleton may be 10% or more, 30% or more, 60% or more, 80% or more, or 100%, and may be 75% or less, 50% or less, or 25% or less. N -Z N n binds to another group (e.g., a hydrocarbon group) on the amine skeleton.

[0121] (Y N ) Y N Y is a direct bond or a 1+n valent group, preferably a 1+n valent group. N is an amine skeleton and n Z N It acts as a linker connecting the

[0122] n is Y N Combined with Z N and may be an integer of 1 to 3. n may be 1 or more, 2 or more, or 3 or more, and may be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0123] Y N may be an aliphatic group (unsaturated aliphatic group or saturated aliphatic group) or an aromatic group.

[0124] Y N The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more; and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 300 or less.

[0125] Y N may have a carbonyl group. N may have one or more selected from the group consisting of an amide group, a urea group, a urethane group, and an imide group, or Y N may form one or more groups selected from the group consisting of an amide group, a urea group, a urethane group, and an imide group together with the amino group in the amine skeleton. Examples of such an amide group, a urea group, a urethane group, and an imide group include -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'- -C(=O)-NR'- -C(=O)-NR'-C(=O)- [In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).] Examples include: Y N is preferably attached to the nitrogen atom in the amine skeleton via a -(C=O)- group.

[0126] Y Nrepresents a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2, a di- to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a di- to tetravalent hydrocarbon aromatic ring, and a di- to tetravalent heterocycle. [In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).] It may be a 1+n valent group consisting of one or more groups selected from the group consisting of:

[0127] Y N is Y N1 and Y N2 is a 1+n valent group consisting of one or more selected from the group consisting of Y N1 is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)); Y N2 is a group consisting of one or more selected from the group consisting of di- to tetravalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, di- to tetravalent aromatic hydrocarbon rings, and di- to tetravalent heterocycles, In the present specification, Y N The group shown as is an amine skeleton on the left and a Z skeleton on the right. N Bind to.

[0128] 〇 Y N1 Y N1 is a non-hydrocarbon linker.

[0129] Y N1 is a direct bond or a divalent or higher group. N1 The valence of Y may be 2 to 4, 2 to 3, or 2.N1 is preferably not only a direct bond.

[0130] Y N1 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0131] Y N1 may be composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms). Y N1 Examples include: direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -C(=O)-NR'-C(=O)-, -C(=NR')-, -S-, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2 etc. [In the formula, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).] In addition, Y N1is bonded to a nitrogen atom of the amine skeleton, the nitrogen atom is considered to be part of the amine skeleton (amino group).

[0132] 〇 Y N2 Y N2 is a linker of a hydrocarbon ring which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, or a heterocycle which may have a substituent.

[0133] Y N2 Y may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). N2 Y may be aliphatic or aromatic. N2 may be linear, branched or cyclic.

[0134] Y N2 is a divalent or higher group. Y N2 The valency of may be, for example, 2 to 4, 2 to 3, or 2.

[0135] Y N2 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more; and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0136] Y N2 is composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles.

[0137] The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight chain hydrocarbon group. The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may be 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less. The valence of the aliphatic hydrocarbon group may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0138] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms at each occurrence). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the aliphatic hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0139] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from a hydrocarbon aromatic ring such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0140] The aromatic hydrocarbon ring may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms at each occurrence). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the aromatic hydrocarbon ring having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0141] The divalent to tetravalent heterocycle may be an aliphatic group or an aromatic group. Examples of the divalent to tetravalent heterocycle include groups obtained by removing 2 to 4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring-constituting atoms of the heterocycle is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the heterocycle may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0142] The heterocycle may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms at each occurrence). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the heterocycle having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more, and 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0143] Y N2 Examples include: -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali(-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or heterocycle.] etc.

[0144] Y N2 Examples of specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond, a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(q and r each independently represent an integer of 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0145] Y N Example Y N In the following, R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[0146] Y N An example of this is Y N If is bivalent, -Y N1 -, -Y N1 -Y N2 -, -Y N1 -Y N2 -Y N1 -, -Y N1 -Y N2 -Y N1 -Y N2 -, -Y N2 -, -Y N2 -Y N1 -, -Y N2 -Y N1 -Y N2 -, -Y N2 -Y N1 -Y N2 -Y N1 -, etc.

[0147] Y N An example of this is Y N If is trivalent, -Y N1 (-)2, -Y N1 -Y N2 (-)2, -Y N1 -(Y N2 -)2, -Y N1 -Y N2 -Y N1 (-)2, -Y N1 -Y N2 (-Y N1 -)2, -Y N1 -(Y N2 -YN1 -), 2, -Y N1 -Y N2 -Y N1 -Y N2 (-), 2, -Y N1 -Y N2 -Y N1 -(Y N2 -) 2、 -Y N1 -Y N2 -(Y N1 -Y N2 -) 2、 -Y N1 -(Y N2 -Y N1 -Y N2 -), 2; -Y N2 (-), 2, -Y N2 -Y N1 (-), 2, -Y N2 -(Y N1 (-), 2, -Y N2 -Y N1 -Y N2 (-), 2, -Y N2 -Y N1 (-Y N2 (-), 2, -Y N2 -(Y N1 -Y N2 (-), 2, -Y N2 -Y N1 -Y N2 -Y N1 (-), 2, -Y N2 -Y N1 -Y N2 -(Y N1 -) 2、 -Y N2 -Y N1 -(Y N2 -Y N1 -) 2、 -Y N2 -(Y N1 -Y N2 -Y N1 -), 2, etc. can be mentioned.

[0148] Y N As an example of Y N when it is tetravalent, -Y N1 (-), 3, -Y N1 -Y N2 (-), 3, -Y N1 -(YN2 -), 3, -Y N1 -Y N2 -Y N1 (-), 3, -Y N1 -Y N2 (-Y N1 -), 3, -Y N1 -(Y N2 -Y N1 -), 3, -Y N1 -Y N2 -Y N1 -Y N2 (-), 3, -Y N1 -Y N2 -Y N1 -(Y N2 -), 3、 -Y N1 -Y N2 -(Y N1 -Y N2 -), 3、 -Y N1 -(Y N2 -Y N1 -Y N2 -), 3; -Y N2 (-), 3, -Y N2 -Y N1 (-), 3, -Y N2 -(Y N1 -), 3, -Y N2 -Y N1 -Y N2 (-), 3, -Y N2 -Y N1 (-Y N2 -), 3, -Y N2 -(Y N1 -Y N2 (-), 3, -Y N2 -Y N1 -Y N2 -Y N1 (-), 3, -Y N2 -Y N1 -Y N2 -(Y N1 -), 3、 -Y N2 -Y N1 -(Y N2 -Y N1 -), 3、 -Y N2 -(Y N1 -Y N2 -Y N1 -), 3, etc. can be mentioned.

[0149] Y N Preferred examples of -Y N1 -, -Y N1 -Y N2 -, -Y N1 -Y N2 -Y N1 -, -Y N1 -Y N2 (-)2, -Y N2 -, -Y N2 -Y N1 -, -Y N2 -Y N1 -Y N2 -, -Y N2 -Y N1 (-)2, In the amine-modified product, one or more Y N However, it is preferable that the terminal on the amine skeleton side is -(C=O)- and is bonded to a nitrogen atom in the amine skeleton.

[0150] Y N is preferably -Y N1 -, -Y N1 -Y N2 -, -Y N1 -Y N2 -Y N1 -, -Y N1 -Y N2 (-)2, -Y N2 -, -Y N2 -Y N1 -, -Y N2 -Y N1 -Y N2 -, -Y N2 -Y N1 (-)2, [In the formula, Y N1 but, independently for each occurrence, direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, or -C(=O)-NR'- -C(=O)-NR'-C(=O)- (In the formula, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) and Y N2 is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a divalent aromatic group (for example, a divalent phenyl group, a divalent triazole group). This makes it possible to impart good liquid repellency to the substrate.

[0151] Y N Further specific examples of the *-(C=O)- -O-(C=O)-NR'- [In the formula, * means bonding to a nitrogen atom of an amine skeleton, R' is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).] etc.

[0152] (Z N ) Z N represents a monovalent hydrocarbon group having 1 to 40 carbon atoms which may be substituted or a monovalent polysiloxane group, and the above descriptions of (monovalent hydrocarbon group which may be substituted) and (monovalent polysiloxane group) are incorporated herein.

[0153] [Examples of amine modifications] (Amine modification example 1) Examples of amine modifications include those of the formula: N(-Y N -Z N n ) p (-H) q -L1 -[N(-Y N -Z N n ) r (-H) s -L 1 -] t -N(-Y N -Z N n ) p (-H) q [In the formula, Y N is independently in each occurrence a direct bond or a group with a valence of 1+n; Z N represents, independently in each occurrence, a linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent; L 1 represents, independently in each occurrence, a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by an oxygen atom and / or a sulfur atom; n, independently in each occurrence, is an integer between 1 and 3, inclusive; p, in each occurrence, is an integer greater than or equal to 0 and less than or equal to 2; q, independently in each occurrence, is an integer greater than or equal to 0 and less than or equal to 2; p+q is the sum of each N(-Y N -Z N n ) p (-H) q In, 2, r is independently in each occurrence 0 or 1; s is independently in each occurrence 0 or 1; r+s is the sum of each N(-Y N -Z N n ) r (-H) s In, the sum of all p's and all r's is greater than or equal to 1; t is an integer between 0 and 10. The compound represented by the following formula (amine modified example 1) is exemplified.

[0154] In the amine modification example 1, Y N , Z N For details of , and n, the above explanation is referred to.

[0155] In the amine modification example 1, L 1 L is a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be interrupted by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched, or straight-chain hydrocarbon group, and is preferably a straight-chain hydrocarbon group or an aromatic hydrocarbon. 1 The hydrocarbon group in the above description of the [amine skeleton] may be used as L, and the hydrocarbon group may be interrupted by oxygen atoms and / or sulfur atoms, or may consist of only carbon atoms, nitrogen atoms, and hydrogen atoms. 1 L may be, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 aromatic hydrocarbon rings. 1 is preferably a cyclic group having both a ring (e.g., an aromatic ring) and a chain structure (e.g., a straight-chain structure, ether oxygen, or thioether sulfur), and specific examples thereof include a 1,3-phenylenebisalkylene group, a 1,4-phenylenebisalkylene group, a diphenyletherdiyl group, and a diphenylthioetherdiyl group. 1 may have 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more carbon atoms; and may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less.

[0156] In the amine modification example 1, p, in each occurrence, is independently an integer between 0 and 2, inclusive; q, in each occurrence, is independently an integer between 0 and 2, inclusive; and p+q is equal to the sum of each N(-Y N -Z N n ) p (-H) q In the formula, p is 2. Preferably, p, independently at each occurrence, may be 1 or more, for example 2.

[0157] In the amine modification example 1, r is independently at each occurrence 0 or 1, s is independently at each occurrence 0 or 1, and r+s is independently at each occurrence 0 or 1. N -Z N n ) r (-H) s In the formula, p is 1. Preferably, p, independently at each occurrence, may be 1 or more, for example 2.

[0158] The sum of all p's and all r's is 1 or greater, i.e., the amine modification example 1 contains one or more -Y N -Z N n The sum of all p's and all r's may be 1 or more, 3 or more, 5 or more, 7 or more, 9 or more, 12 or more (the sum of all q's and all s's may be 0), and may be 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, or 4 or less.

[0159] In the amine modification example 1, t is an integer of 0 or more and 10 or less. t may be 0 or more, 1 or more, 2 or more, 4 or more, or 6 or more, preferably 0 or more or 2 or more, and may be 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1 or less, for example, 0 or 1.

[0160] (Amine modification example 2) Other examples of amine modifications include those of the formula: N(-Y N -Z N n ) p (-H) q -L 2 (-Y N -Z N n ) u [In the formula, Y N is independently in each occurrence a direct bond or a group with a valence of 1+n; Z N represents, independently in each occurrence, a linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent; L2 represents an aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms and a valence of 1+u, which may be interrupted by an oxygen atom and / or a sulfur atom, n, independently in each occurrence, is an integer between 1 and 3, inclusive; p is an integer between 0 and 2, q is an integer between 0 and 2, p+q is 2, u is an integer between 1 and 3, The sum of p and u is 1 or greater.] The compound represented by the following formula (amine modified example 2) is also included.

[0161] In the amine modification example 2, Y N , Z N For details of and n, the above explanation is incorporated herein.

[0162] In the amine modification example 2, L 2 is an aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms and a valence of 1+u, which may be interrupted by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched, or straight-chain hydrocarbon group, and is preferably a straight-chain hydrocarbon group or an aromatic hydrocarbon. 2 The hydrocarbon group in the above description of the [amine skeleton] may be used as L, and the hydrocarbon group may be interrupted by oxygen atoms and / or sulfur atoms, or may consist of only carbon atoms, nitrogen atoms, and hydrogen atoms. 2 L may be, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 aromatic hydrocarbon rings. 2 is preferably a cyclic group having both a ring (e.g., an aromatic ring) and a chain structure (e.g., a straight-chain structure, ether oxygen, or thioether sulfur), and specific examples thereof include a 1,3-phenylenebisalkylene group, a 1,4-phenylenebisalkylene group, a diphenyletherdiyl group, and a diphenylthioetherdiyl group. 2may have 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more carbon atoms; and may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less.

[0163] In the amine modification example 2, p is an integer of 0 to 2, q is an integer of 0 to 2, and p+q is 2. Preferably, p may be 1 or more, for example 2.

[0164] In the amine modification example 2, u is an integer of 1 to 3. u is 1, 2, or 3, for example, 2 or 3.

[0165] In the amine modification example 2, the sum of p and u is 1 or more, i.e., the amine modification example 2 has one or more -Y N -Z N n The sum of all p's and u's may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more (the sum of all q's may be 0, or may be 5 or less, 4 or less, 3 or less, or 2 or less.

[0166] (Specific examples) Specific examples of the amine-modified product include compounds represented by the following formula: N , Z N For details of , and n, the above explanation is referred to.

[0167] TIFF2025044132000002.tif35154

[0168] TIFF2025044132000003.tif28160

[0169] TIFF2025044132000004.tif31167

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[0173] TIFF2025044132000008.tif18158

[0174] The amine-modified wax may be a synthetic wax derived from animal or vegetable oils. The synthetic wax may be obtained by condensing a fatty acid derived from animal or vegetable oils with an aliphatic amine or an amine containing an aromatic group. Examples of synthetic waxes include fatty acid amide compounds such as hydroxy fatty acid amide compounds, palmitic acid amide compounds, octadecanoic acid amide compounds, stearic acid amide compounds, arachidic acid amide compounds, behenic acid amide compounds, lignoceric acid amide compounds, oleic acid amide compounds, linoleic acid amide compounds, α-linolenic acid amide compounds, γ-linolenic acid amide compounds, arachidonic acid amide compounds, icosapentaenoic acid amide compounds, and docosahexaenoic acid amide compounds.

[0175] [Manufacturing method] The method for producing the amine modified product is not limited, but may be carried out by reacting various amines (raw amines) with Z N A method of synthesis by reacting a carboxylic acid containing a Z group with various amines. N and a synthesis method in which a group-containing carboxylic acid chloride, an acid anhydride, an isocyanate, etc. are reacted with the condensing agent may be a known condensing agent, and examples of the condensing agent include DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA, and Py-Bop.

[0176] (Amine (raw amine)) Examples of amines (raw amines) that are precursors of the amine skeleton include those that can form an amine skeleton, such as alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine; alkylene diamines such as ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine, cyclohexanediamine, and methylenebiscyclohexylamine; diethylenetriamine, triethylenetetramine, tris(2-aminoethyl)amine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tris(2-aminopropyl)amine, tetrapropylenepentamine, pentapropylenehexamine, iminobispropylamine, dibutylenetriamine, bis(2-aminoethoxy)ethane, bis(2-aminoethyl)ether, bis[2-(2-aminoethoxy)ethyl]ether, and bis[2-(3-aminopropyl)ethyl]ether. polyalkylenepolyamines such as ether, spermine, and spermidine; oxygen- or sulfur-containing aliphatic amines such as 1-aminopropanediol, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, polyoxypropylenediamine, and polyoxyethylenediamine; aromatic monoamines such as aniline, 1- or 2-naphthylamine, 1-, 2-, or 9-aminoanthracene, 9-aminophenanthracene, and 2-, 3-, or 4-aminobiphenyl; monocyclic aromatic polyamines such as o-, m-, or p-phenylenediamine, o-, m-, or p-xylylenediamine, diaminotoluene, and 2,3-, 2,4-, or 2,5-tolylenediamine;Diaminobiphenyl, bisaminophenoxyphenylpropane, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl sulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenyl ethane, bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, aminophenoxybiphenyl, aminophenoxyphenylketone, bisaminoditrifluoromethylbenzylbenzene, aminophenoxyphenyl sulfone, aminophenoxyphenyl ether, aminophenoxyphenylpropane, bis(aminophenoxybenzoyl)benzene, bis(aminophenoxy-α,α-dimethylbenzyl)benzene, bis[(aminoaryloxy)benzoyl]diphenyl ether, bis(amino-α,α-dimethylbenzylphenoxy)benzophenone, aminophenoxyphenyl sulfide, bis[amino-α, α-dimethylbenzylphenoxy]diphenyl sulfone, 4,4'-bis[aminophenoxyphenoxy]diphenyl sulfone, diaminodiaryloxybenzophenone, Polycyclic aromatic polyamines such as diaminoaryloxybenzophenone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminotriphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenebisaniline, 4,4'-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 4,4'-diaminodiphenyl ether, and 4,4'-bis(aminophenyl)amine; oxygen- or sulfur-containing polycyclic aromatic polyamines such as 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 3,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl sulfide;Examples of the polyamine include hydroxyl group-containing polyamines such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine. The polyamine may be a polymerized compound such as allylamine.

[0177] [Modified polyol] As an example of the liquid repellent compound, a modified polyol will be described below. The modified polyol is a compound obtained by chemically modifying a polyol so as to exhibit liquid repellency.

[0178] [Structure etc.] The polyol modified product may be a polymer having a degree of polymerization of at least 1. From the viewpoint of improving liquid repellency, the degree of polymerization of the polyol modified product may be 2 or more, 3 or more, 5 or more, 6 or more, preferably 7 or more, more preferably 8 or more, and even more preferably 9 or more, and from the viewpoint of improving the handleability of the repellent, it may be 100 or less, preferably 50 or less, more preferably 30 or less, and even more preferably 15 or less. The degree of polymerization means the number of repeating monomer units constituting the polymer.

[0179] The degree of polymerization in the present disclosure means an average degree of polymerization. The average degree of polymerization in the present disclosure means a degree of polymerization measured under the following conditions. In the present disclosure, when the polyol modified product is a polyglycerin modified product obtained by modifying polyglycerin, the degree of polymerization of the polyol modified product means the average degree of polymerization of the polyglycerin. The average degree of polymerization of polyglycerin is the average degree of polymerization (n) calculated from the hydroxyl value by the terminal group analysis method. In detail, the average degree of polymerization and the average molecular weight are calculated from the following formulas (Formula 1) and (Formula 2). (Formula 1) Average molecular weight=74n+18 (Equation 2) Hydroxyl value = 56110 (n + 2) / average molecular weight The hydroxyl value in the above formula (2) is a numerical value that is an index of the number of hydroxyl groups contained in polyglycerol. The hydroxyl value is calculated from the amount of potassium hydroxide required to neutralize the acetic acid required to acetylate the free hydroxyl groups contained in 1 g of polyglycerol, and is calculated in accordance with "Standard Methods for Analysis of Fats, Oils and Related Compounds (I), 2003 Edition, Established by the Japan Oil Chemists' Society." The hydroxyl value of the raw material polyglycerol is actually measured according to the above-mentioned Standard Methods for Analysis of Fats, Oils and Related Compounds, and the average degree of polymerization and average molecular weight of polyglycerol can be calculated from the above-mentioned formula.

[0180] In the present disclosure, when the polyol modified product is a polyvinyl alcohol modified product obtained by modifying polyvinyl alcohol, the degree of polymerization of the polyol modified product means the average degree of polymerization of the polyvinyl alcohol. The average degree of polymerization of polyvinyl alcohol can be measured in accordance with JIS K 6726 polyvinyl alcohol test method.

[0181] In the present disclosure, when the polyol-modified product is a polysaccharide-modified product obtained by modifying a polysaccharide, the degree of polymerization of the polyol-modified product means the average degree of polymerization of the polysaccharide. The average degree of polymerization of a polysaccharide can be analyzed as follows. The degree of polymerization is the number of monosaccharide units (fructose and glucose units) in the polysaccharide, and the average degree of polymerization is, for example, the average degree of polymerization determined by the top of the peaks of each analysis result obtained by a normal analysis method such as HPLC, GC, and HPAEC as follows. The measurement can be performed by using, for example, ULTRON PS-80N (8×300 mm) (solvent: water, flow rate: 0.5 ml / min, temperature: 50° C.) manufactured by Shinwa Chemical Industry Co., Ltd. or TSK-GEL G30000 PWXL (7.8×300 mm) (solvent: water, flow rate: 0.5 ml / min, temperature: 50° C.) manufactured by TOSOH Co., Ltd. as a column, and a differential refractometer as a detector.

[0182] The modified polyol may be low molecular weight (eg, weight average molecular weight less than 1500, less than 1000, 500 or less) and / or high molecular weight. The weight average molecular weight of the modified polyol may be 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 30000 or more, or 500000 or more; and may be 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 100000 or less, 9000 or less, 8000 or less, 7000 or less, 6000 or less, 5000 or less, 3000 or less, 2000 or less, 1000 or less, or 500 or less.

[0183] The substitution rate of the hydroxyl group in the polyol modification may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%, preferably 10% or more, for example 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, particularly 50% or more, for example 80% or more, and may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, for example 95% or less. Here, the "substitution rate" means the proportion (mol%) of the hydroxyl group derived from the polyol that is modified, and may mean the proportion (mol%) of the hydroxyl group that is modified with a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group that may have a substituent.

[0184] The residual rate of hydroxyl groups in the polyol modification may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, for example, 5% or more, and may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, or 5% or less, for example, 50% or less, 30% or less, or 10% or less. Here, the "residual rate" refers to the proportion (mol%) of hydroxyl groups derived from the polyol that are not modified.

[0185] The number of modifying groups in the polyol modified product may be 2 or more, 5 or more, 7 or more, 8 or more, 9 or more, 10 or more, 12 or more, 15 or more, 30 or more, or 50 or more, and may be 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent.

[0186] The modifying group equivalent of the polyol modified product may be 150 or more, 250 or more, 350 or more, 450 or more, 550 or more, 650 or more, 750 or more, or 1000 or more, and may be 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 400 or less. It is the value obtained by dividing the weight average molecular weight of the polyol modified product by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent.

[0187] In the polyol modification, one or more hydroxyl groups of the polyol are substituted with a modifying group. The modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent. From the viewpoint of improving liquid repellency, the polyol modification may have a structure in which a polyol is modified with an alkyl group having 6 to 40 carbon atoms.

[0188] For details of the monovalent hydrocarbon group which may have a substituent and the monovalent polysiloxane group, the above explanations of (the monovalent hydrocarbon group which may have a substituent) and (the monovalent polysiloxane group) are incorporated herein.

[0189] (-Y O -Z O n ) In the present disclosure, modified polyols are those in which one or more of the hydroxy groups of the polyol has the formula: -Y O -Z O n [In the formula, Y O is Y O1 and Y O2 is a 1+n valent group consisting of one or more selected from the group consisting of Y O1 is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)); Y O2 is a group consisting of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles, Z O represents a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, n is an integer between 1 and 3. It may be substituted with a group represented by the following formula:

[0190] (Y O ) Y O is Y O1 and Y O2is a 1+n valent group consisting of one or more selected from the group consisting of Y O1 is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)); Y O2 is a group composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles.

[0191] n is Y O Combined with Z O and may be an integer of 1 to 3. n may be 1 or more, 2 or more, or 3 or more, and may be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0192] Y O The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more; and may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[0193] Y O may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. For example, Y O may include -C(=O)-NR'-, -C(=S)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'-. OBy including these groups, the liquid repellency can be improved.

[0194] ○ Y O1 Y O1 is a non-hydrocarbon linker.

[0195] Y O1 is a direct bond or a divalent or higher group. O1 The valence of Y may be 2 to 4, 2 to 3, or 2. O1 is preferably not only a direct bond.

[0196] Y O1 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0197] Y O1 may be composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2 (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms). Y O1 Examples include: direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2 etc. (In the formula, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) Examples include:

[0198] Y O1 may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. For example, Y O2 may include -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'-. O1 By including these groups, the liquid repellency can be improved.

[0199] ○ Y O2 Y O2 is a linker of a hydrocarbon ring which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, or a heterocycle which may have a substituent.

[0200] Y O2 Y may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). O2 Y may be aliphatic or aromatic. O2 may be linear, branched or cyclic.

[0201] Y O2 is a divalent or higher group. Y O2 The valency of may be, for example, 2 to 4, 2 to 3, or 2.

[0202] Y O2 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more; and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0203] Y O2is composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles.

[0204] The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight chain hydrocarbon group. The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may be 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less. The valence of the aliphatic hydrocarbon group may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0205] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms at each occurrence). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the aliphatic hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0206] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from a hydrocarbon aromatic ring such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0207] The aromatic hydrocarbon ring may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms at each occurrence). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the aromatic hydrocarbon ring having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0208] The divalent to tetravalent heterocycle may be an aliphatic group or an aromatic group. Examples of the divalent to tetravalent heterocycle include groups obtained by removing 2 to 4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring-constituting atoms of the heterocycle is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the heterocycle may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0209] The heterocycle may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms at each occurrence). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the heterocycle having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more, and 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0210] Y O2 Examples include: -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali(-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or heterocycle.] etc.

[0211] Y O2 Examples of specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond, a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(q and r each independently represent an integer of 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0212] (Y O Example of Y O In the following, R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[0213] Y O An example of this is Y O If is bivalent, -Y O1 -, -Y O1 -Y O2 -, -Y O1 -Y O2 -Y O1 -, -Y O1 -Y O2 -Y O1 -Y O2 -, -Y O2 -, -Y O2 -Y O1 -, -Y O2 -YO1 -Y O2 -,-Y O2 -Y O1 -Y O2 -Y O1 -etc. can be mentioned.

[0214] Y O As an example of Y O when Y is trivalent, -Y O1 (-), -Y O1 -Y O2 (-), -Y O1 -(Y O2 -), -Y O1 -Y O2 -Y O1 (-), -Y O1 -Y O2 (-Y O1 -), -Y O1 -(Y O2 -Y O1 -), -Y O1 -Y O2 -Y O1 -Y O2 (-), -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 (-), -Y O2 -Y O1 (-), -Y O2 -(Y O1 -), -Y O2 -Y O1 -Y O2 (-), -Y O2 -Y O1 (-Y O2 -), -Y O2 -(Y O1 -Y O2 -), -Y O2 -Y O1 -Y O2 -YO1 (-)2, -Y O2 -Y O1 -Y O2 -(Y O1 -) 2、 -Y O2 -Y O1 -(Y O2 -Y O1 -) 2、 -Y O2 -(Y O1 -Y O2 -Y O1 -)2, etc. can be mentioned.

[0215] Y O As an example of Y O when it is tetravalent, -Y O1 (-)3, -Y O1 -Y O2 (-)3, -Y O1 -(Y O2 -)3, -Y O1 -Y O2 -Y O1 (-)3, -Y O1 -Y O2 (-Y O1 -)3, -Y O1 -(Y O2 -Y O1 -)3, -Y O1 -Y O2 -Y O1 -Y O2 (-)3, -Y O1 -Y O2 -Y O1 -(Y O2 -) 3、 -Y O1 -Y O2 -(Y O1 -Y O2 -) 3、 -Y O1 -(Y O2 -Y O1 -Y O2 )3; -Y O2 (-)3, -Y O2 -Y O1 (-)3, -Y O2 -(Y O1 -)3, -Y O2 -Y O1 -Y O2 (-)3, -YO2 -Y O1 (-Y O2 -)3, -Y O2 -(Y O1 -Y O2 -)3, -Y O2 -Y O1 -Y O2 -Y O1 (-)3, -Y O2 -Y O1 -Y O2 -(Y O1 -) 3、 -Y O2 -Y O1 -(Y O2 -Y O1 -) 3、 -Y O2 -(Y O1 -Y O2 -Y O1 -)3; etc.

[0216] Y O Preferred examples of -Y O1 -, -Y O1 -Y O2 -, -Y O1 -Y O2 -Y O1 -, -Y O1 -Y O2 (-)2, -Y O2 -, -Y O2 -Y O1 -, -Y O2 -Y O1 -Y O2 -, -Y O2 -Y O1 (-)2, etc.

[0217] (Preferred Y O Example of Preferably, Y O but -OY O11 -or -OY O11 -Y O21 -Y O12 - wherein each symbol represents independently at each occurrence: YO11 is a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-; Y O21 is a hydrocarbon group having 1 to 40 carbon atoms, Y O12 is -O-, -OC(=O)-, -OC(=O)-O-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, or -C(OR')(-)2. It may be.

[0218] Y O11 is a non-hydrocarbon linker, which is a direct bond or a divalent or higher group.

[0219] Y O11 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0220] Y O11 may be a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-.

[0221] Y O21 is a divalent hydrocarbon linker, which may be a hydrocarbon group having 1 to 40 carbon atoms.

[0222] Y O21 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more; and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0223] Here, the hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched or straight chain hydrocarbon group, and may be a saturated or unsaturated (eg saturated) aliphatic hydrocarbon group.

[0224] Y O21 Examples of specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(q and r each independently represent an integer of 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0225] Y O12 may be -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, or -C(OR')(-)2.

[0226] Y O12 may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. For example, Y O12 may be -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'-. C12 By including these groups, the liquid repellency can be improved.

[0227] (Z O ) Z Orepresents a monovalent hydrocarbon group having 1 to 40 carbon atoms which may be substituted or a monovalent polysiloxane group, and the above descriptions of (monovalent hydrocarbon group which may be substituted) and (monovalent polysiloxane group) are incorporated herein.

[0228] [Other modifying groups] The hydroxy group of the polyol is -Y O -Z O n Examples of modifying groups are anionic and / or cationic groups.

[0229] The anionic group may be a monomer having a carboxyl group, a sulfonic acid group, or a phosphoric acid group.

[0230] Salts of anionic groups include alkali metal salts, alkaline earth metal salts, or ammonium salts, such as methylammonium salts, ethanolammonium salts, and triethanolammonium salts.

[0231] The cationic group is an amino group, preferably a tertiary amino group and a quaternary amino group. In the tertiary amino group, the two groups bonded to the nitrogen atom are preferably the same or different and are an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example, a benzyl group (C6H5-CH2-)). In the quaternary amino group, the three groups bonded to the nitrogen atom are preferably the same or different and are an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example, a benzyl group (C6H5-CH2-)). In the tertiary amino group and the quaternary amino group, the remaining group bonded to the nitrogen atom may have a carbon-carbon double bond. The cationic group may be in the form of a salt.

[0232] The cationic group that is a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, for example, carboxylic acids having 1 to 20 carbon atoms (particularly, monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid) are preferred.

[0233] [Manufacturing method] The modified polyol may be prepared by reacting a modifying agent having a modifying group (or a precursor structure of the modifying group) with a hydroxy group of the polyol.

[0234] (Polyol) A polyol is a compound having two or more hydroxyl groups, and is a compound that is a raw material for a modified polyol. A polyol is a compound having two or more hydroxyl groups in the molecule. The polyol may be aliphatic or aromatic, but is preferably aliphatic.

[0235] The polyol may have an ether bond. Preferably, the polyol may have two or more ether bonds. Specifically, the polyol is preferably a compound having two or more hydroxy groups and two or more ether bonds. In other words, the polyol is preferably a polyether having two or more hydroxy groups.

[0236] When the polyol is a polymer, it may have a hydroxy group and an ether bond in the repeating structure of the monomer unit.

[0237] The polyol may be low molecular weight (e.g., weight average molecular weight less than 1000, 500 or less) and / or high molecular weight. The weight average molecular weight of the polyol may be 50 or more, 100 or more, 300 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may be 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 5000 or less, 30000 or less, 2000 or less, 1000 or less, or 500 or less.

[0238] The number of hydroxy groups in the polyol may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more, and may be 3000 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.

[0239] The hydroxy group equivalent of the polyol may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, or 150 or more, and may be 1000 or less, 800 or less, 600 or less, 400 or less, 200 or less, 100 or less, or 75 or less. The hydroxy group equivalent of the polyol is the value obtained by dividing the weight average molecular weight of the polyol by the number of hydroxyl groups.

[0240] The polyol may be a natural product. The natural product may be a high molecular weight natural product, a low molecular weight natural product, or a derivative thereof. The above natural products also include compounds converted from microorganisms. Examples of polyols include monosaccharides, oligosaccharides, polysaccharides, sugar alcohols (reducing sugars), hydroxy acids, amino acids, vitamins, flavonols, hydroxy hydrocarbons, hydroxy group-containing compound polymers, polyether polyols, polymer polyols, polyester polyols, and other polyols.

[0241] Examples of monosaccharides include glucose, fructose, galactose, xylose, and the like.

[0242] Examples of oligosaccharides include sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, and sucralose.

[0243] Examples of sugar alcohols (reducing sugars) include sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, lactitol, and the like.

[0244] Examples of polysaccharides include starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa carrageenan, iota carrageenan, isomaltodextrin, gellan gum, and tamarind seed gum.

[0245] Examples of hydroxy acids include ascorbic acid, kojic acid, quinic acid, chlorogenic acid, and gluconic acid.

[0246] Examples of amino acids include glucosamine.

[0247] Examples of vitamins include ascorbic acid and inositol.

[0248] Examples of flavonols include catechin, quercetin, and anthocyanin.

[0249] Examples of hydroxyhydrocarbons include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerin, trimethylolpropane, trimethylolethane, etc. Hydroxyhydrocarbons are hydrocarbons having a hydroxy group and may be aromatic or aliphatic, but are preferably aliphatic. Hydroxyhydrocarbons may also refer to hydroxyhydrocarbons other than compounds included in other groups such as polysaccharides (other hydroxyhydrocarbons).

[0250] Examples of the hydroxy group-containing compound polymer include polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, and hydroxybutyl (meth)acrylate polymer.

[0251] An example of a polyether polyol may be a compound obtained by addition polymerization of an alkylene oxide to an initiator. Examples of initiators include compounds having a hydroxyl group with two or more functional groups. Examples of initiators include propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, glycerin, polyglycerin, trimethylolpropane, triethanolamine, pentaerythritol, ethylenediamine, aromatic diamine, diethylenetriamine, sorbitol, and sucrose. Examples of alkylene oxides include ethylene oxide and propylene oxide. Polyether polyols obtained by addition polymerization of an alkylene oxide to the above initiators are also called polyoxyalkylene polyols or oxyalkylene derivatives of polyols. Representative examples of polyether polyols include polyoxypropylene triols obtained by addition polymerization of propylene oxide to glycerin, and polyoxypropylene polyglyceryl ethers obtained by addition polymerization of propylene oxide to polyglycerin.

[0252] An example of a polymer polyol is a compound obtained by polymerizing at least a portion of a polyether polyol with an ethylenically unsaturated monomer, such as acrylonitrile or styrene.

[0253] Examples of polyester polyols may be compounds obtained by dehydration condensation of a compound having a carboxyl group with two or more functional groups and a compound having a hydroxyl group with two or more functional groups. Examples of compounds having a carboxyl group with two or more functional groups include terephthalic acid, isophthalic acid, phthalic acid, methylphthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, and acid anhydrides thereof. Examples of compounds having a hydroxyl group with two or more functional groups include ethylene glycol, propylene glycol, propanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and polymers thereof.

[0254] (Modifier) The modifying agent is a compound that is reactive with a polyol and is preferably a compound having the above-mentioned monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group.

[0255] Examples of modifying agents are as follows: Acid halide G(O=)CZ O Acid anhydride O(C(=O)-Z O )2 Carboxylic acid HO(O=)CZ O Isocyanate O=C=NZ O Thioisocyanate S=C=NZ O Epoxy (CH2OCH)CH2O-Z O Halide GZ O Amine H2N-Z O Hydroxy HO-Z O [In the formula, Z O is as defined above, and G is a halogen atom (e.g., F, Cl, Br, or I).

[0256] Z in the structure of the above modifier O may be replaced with any group constituting a modifying group, for example, Z O may be a group having a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group, or, for example, Z O -Y O -Z O n It is also possible to use the following.

[0257] The modified polyol may be synthesized by reacting a polyol with a modifying agent. For example, a modified polyol can be synthesized by reacting a modifying agent that is an acid halide compound, an acid anhydride, or a carboxylic acid with a hydroxy group of a polyol to form an ester bond. Alternatively, a modified polyol can be produced by reacting a modifying agent that is a halide or an epoxy compound with a hydroxy group of a polyol to form an ether bond. Those skilled in the art can appropriately design the reaction conditions between the polyol and the modifying agent, such as using a catalyst (e.g., an acid catalyst or a base catalyst) or using a condensing agent, depending on the target product.

[0258] [Polycarboxylic acid modified product] As an example of the liquid repellent compound, a polycarboxylic acid modified compound will be described below. The polycarboxylic acid modified compound is a compound obtained by chemically modifying a polycarboxylic acid so as to exhibit liquid repellency.

[0259] [Structure, etc.] The polycarboxylic acid modifications may be low molecular weight (eg, weight average molecular weight less than 1500, less than 1000, 500 or less) and / or high molecular weight. The weight average molecular weight of the polycarboxylic acid modified product may be 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 30000 or more, or 500000 or more; and may be 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 100000 or less, 9000 or less, 8000 or less, 7000 or less, 6000 or less, 5000 or less, 3000 or less, 2000 or less, 1000 or less, or 500 or less.

[0260] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polycarboxylic acid modified product may be values ​​measured by GFC analysis using polyethylene glycol / polyethylene oxide as standard samples with the following apparatus and conditions. Separation column: SB-806M (8mm x 30mm, Shodex) Column temperature: 40℃ Mobile phase solvent: Ion-exchanged water Mobile phase flow rate: 1.0 mL / min Sample concentration: 0.5wt% Injection volume: 50μL Detector: RI detector (Waters2414, Waters)

[0261] The weight average molecular weight (Mw), number average molecular weight (Mn) and polydispersity (Mw / Mn) of the polycarboxylic acid modified product in terms of polystyrene may be determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent and Shodex KF400RL and KF400RH columns (polystyrene gel) manufactured by Showa Denko K.K.

[0262] The substitution rate of hydroxyl groups for carboxyl groups in the polycarboxylic acid modified product may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%, and is preferably 10% or more, for example, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, particularly 80% or more, and may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, for example, 95% or less. Here, the "substitution rate" refers to the proportion (mol %) of hydroxy groups of carboxyl groups derived from polycarboxylic acid that are modified, and may refer to the proportion (mol %) that are modified with a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent.

[0263] The residual ratio of hydroxyl groups of carboxyl groups in the polycarboxylic acid modified product may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, for example, 5% or more, and may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, or 5% or less, for example, 50% or less, 30% or less, or 10% or less. Here, the "residual ratio" refers to the ratio (mol%) of unmodified hydroxyl groups of carboxyl groups derived from polycarboxylic acid.

[0264] The number of modifying groups in the polycarboxylic acid modified product may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, or 50 or more, and may be 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent.

[0265] The modifying group equivalent of the polycarboxylic acid modified product may be 150 or more, 250 or more, 350 or more, 450 or more, 550 or more, 650 or more, 750 or more, or 1000 or more, and may be 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 400 or less. It is the value obtained by dividing the weight average molecular weight of the polycarboxylic acid modified product by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent.

[0266] In the polycarboxylic acid modified product, one or more hydroxyl groups of the polycarboxylic acid are substituted with a modifying group. The modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent. From the viewpoint of improving liquid repellency, the polycarboxylic acid modified product may have an alkyl group having 6 to 40 carbon atoms relative to the polycarboxylic acid.

[0267] For details of the monovalent hydrocarbon group which may have a substituent and the monovalent polysiloxane group, the above explanations of (the monovalent hydrocarbon group which may have a substituent) and (the monovalent polysiloxane group) are incorporated herein.

[0268] (-Y C -Z C n ) In the present disclosure, the modified polycarboxylic acid is a polycarboxylic acid in which the hydroxy group of one or more carboxyl groups is replaced by the following formula: -Y C -Z C n [In the formula, Y C is Y C1 and Y C2 is a 1+n valent group consisting of one or more selected from the group consisting of Y C1is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)); Y C2 is a group consisting of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles, Z C represents a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, n is an integer between 1 and 3. It may be substituted with a group represented by the following formula:

[0269] (Y C ) Y C is Y C1 and Y C2 is a 1+n valent group consisting of one or more selected from the group consisting of Y C1 is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)); Y C2 is a group composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles.

[0270] n is Y C Combined with ZC and may be an integer between 1 and 3. n may be 1 or more, 2 or more, or 3 or more. n may be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0271] Y C The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more; and may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[0272] Y C may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. For example, Y C may be -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'-. C By including these groups, the liquid repellency can be improved.

[0273] ○ Y C1 Y C1 is a non-hydrocarbon linker.

[0274] Y C1 is a direct bond or a divalent or higher group. C1 The valence of Y may be 2 to 4, 2 to 3, or 2. C1 is preferably not only a direct bond.

[0275] Y C1 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0276] Y C1may be composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2 (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms). Y C1 Examples include: direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2 etc. (In the formula, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) Examples include:

[0277] Y C1 may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. For example, Y C1 may include -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'-. C1 By including these groups, the liquid repellency can be improved.

[0278] ○ Y C2 YC2 is a linker of a hydrocarbon ring which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, or a heterocycle which may have a substituent.

[0279] Y C2 Y may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). C2 Y may be aliphatic or aromatic. C2 may be linear, branched or cyclic.

[0280] Y C2 is a divalent or higher group. Y C2 The valency of may be, for example, 2 to 4, 2 to 3, or 2.

[0281] Y C2 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more; and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0282] Y C2 is composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles.

[0283] The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight chain hydrocarbon group. The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may be 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less. The valence of the aliphatic hydrocarbon group may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0284] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms at each occurrence). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the aliphatic hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0285] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from a hydrocarbon aromatic ring such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0286] The aromatic hydrocarbon ring may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms at each occurrence). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the aromatic hydrocarbon ring having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0287] The divalent to tetravalent heterocycle may be an aliphatic group or an aromatic group. Examples of the divalent to tetravalent heterocycle include groups obtained by removing 2 to 4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring-constituting atoms of the heterocycle is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the heterocycle may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0288] The heterocycle may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms at each occurrence). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the heterocycle having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more, and 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0289] Y C2 Examples include: -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali(-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or heterocycle.] etc.

[0290] Y C2 Examples of specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(q and r each independently represent an integer of 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0291] (Y C Example of Y C In the following, R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[0292] Y C An example of this is Y C If is bivalent, -Y C1 -, -Y C1 -Y C2 -, -Y C1 -Y C2 -Y C1 -, -Y C1 -Y C2 -Y C1 -Y C2 -, -Y C2 -, -Y C2 -Y C1 -, -Y C2 -Y C1 -Y C2 -, -Y C2 -Y C1 -Y C2 -Y C1 --etc.

[0293] Y C An example of this is Y C If is trivalent, -Y C1 (-)2, -Y C1 -Y C2 (-)2, -Y C1 -(Y C2 -)2, -Y C1 -Y C2 -Y C1 (-)2, -Y C1 -Y C2 (-Y C1 -)2, -Y C1 -(Y C2 -YC1 -), 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 -(Y C1 -) 2、 -Y C2 -Y C1 -(Y C2 -Y C1 -) 2、 -Y C2 -(Y C1 -Y C2 -Y C1 -), 2, etc. can be mentioned.

[0294] Y C As an example of Y C When it is tetravalent, -Y C1 (-), 3, -Y C1 -Y C2 (-), 3, -Y C1 -(YC2 -)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 -Y C1 -Y C2 -Y C1 (-)3, -Y C2 -Y C1 -Y C2 -(Y C1 -) 3、 -Y C2 -Y C1 -(Y C2 -Y C1 -) 3、 -Y C2 -(Y C1 -Y C2 -Y C1 -)3; etc. can be mentioned.

[0295] Y C Preferred examples of -Y C1 -, -Y C1 -Y C2 -, -Y C1 -Y C2 -Y C1 -, -Y C1 -Y C2 (-)2, -Y C2 -, -Y C2 -Y C1 -, -Y C2 -Y C1 -Y C2 -, -Y C2 -Y C1 (-)2, etc.

[0296] (Preferred Y C Example of Preferably, Y C but -Y C11 -or -Y C11 -Y C21 -Y C12 - wherein each symbol represents independently at each occurrence: Y C11 is -O- or -NR'-, Y C21 is a hydrocarbon group having 1 to 40 carbon atoms, Y C12 is -O-, -OC(=O)-, -OC(=O)-O-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, or -C(OR')(-)2. It may be.

[0297] Y C11 is a non-hydrocarbon linker, which is a direct bond or a divalent or higher group.

[0298] Y C11 The molecular weight may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less, and may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more.

[0299] Y C11 may be a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-.

[0300] Y C21 is a divalent hydrocarbon linker, which may be a hydrocarbon group having 1 to 40 carbon atoms.

[0301] Y C21 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more; and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0302] Here, the hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched or straight chain hydrocarbon group, and may be a saturated or unsaturated (eg saturated) aliphatic hydrocarbon group.

[0303] Y C21 Examples of specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond, a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(q and r each independently represent an integer of 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0304] Y C12may be -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, or -C(OR')(-)2.

[0305] Y C12 may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. For example, Y C12 may be -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'-. C12 By including these groups, the liquid repellency can be improved.

[0306] (Z C ) Z C represents a monovalent hydrocarbon group having 1 to 40 carbon atoms which may be substituted or a monovalent polysiloxane group, and the above descriptions of (monovalent hydrocarbon group which may be substituted) and (monovalent polysiloxane group) are incorporated herein.

[0307] [Other modifying groups] The hydroxy group of the polycarboxylic acid is -Y C -Z C n The modified group may be substituted with a modifying group other than the above. Examples of the modifying group include an anionic group and / or a cationic group. The explanation of the [Other modifying groups] in the above polyol is applied to the anionic group and / or the cationic group.

[0308] [Manufacturing method] The polycarboxylic acid modification may be prepared by reacting a modifying agent having a modifying group (or a precursor structure of the modifying group) with a hydroxy group of the polycarboxylic acid.

[0309] (Polycarboxylic acid) Polycarboxylic acid is a compound having two or more carboxyl groups, and is a compound that is a raw material for polycarboxylic acid modification. Polycarboxylic acid is a compound having two or more carboxyl groups in the molecule. Polycarboxylic acid may be aliphatic or aromatic, but is preferably aliphatic.

[0310] The polycarboxylic acid may be a low molecular weight (e.g., weight average molecular weight less than 1000, 500 or less) and / or a polymer. The weight average molecular weight of the polycarboxylic acid may be 100 or more, 300 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may be 1000000 or less, 7500000 or less, 500000 or less, 3000000 or less, 100000 or less, 75000 or less, 500000 or less, 300000 or less, 100000 or less, 5000 or less, 30000 or less, 2000 or less, 1000 or less, or 500 or less.

[0311] The number of carboxyl groups in the polycarboxylic acid may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more, and may be 3000 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.

[0312] The carboxyl group equivalent of the polycarboxylic acid may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, or 150 or more, and may be 1000 or less, 800 or less, 600 or less, 400 or less, 200 or less, 100 or less, or 75 or less. The carboxyl equivalent of the polycarboxylic acid is the value obtained by dividing the weight average molecular weight of the polycarboxylic acid by the number of carboxyl groups.

[0313] The polycarboxylic acid may be a natural product. The natural product may be a high molecular weight natural product, a low molecular weight natural product, or a derivative thereof. The above natural products also include compounds converted from microorganisms.

[0314] The polycarboxylic acid may be at least one selected from the group consisting of dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, carboxyl group-containing compound polymers, and salts thereof.

[0315] Dicarboxylic acids are compounds having two carboxyl groups, and examples thereof include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid, terephthalic acid, malic acid, tartaric acid, aldaric acid, and salts thereof.

[0316] Tricarboxylic acids are compounds having three carboxyl groups, such as citric acid, tricarballylic acid, t-aconitic acid, trimellitic acid, and salts thereof.

[0317] Tetracarboxylic acids are compounds having four carboxyl groups, such as pyromellitic acid and its salts.

[0318] The carboxyl group-containing compound polymer is a compound having five or more carboxyl groups, and examples thereof include alginic acid, tragacanth gum, gum arabic, polyacrylic acid, polymethacrylic acid, polymaleic acid, polyaspartic acid, polyglutamic acid, hyaluronic acid, heparin, xanthan gum, gellan gum, carboxymethylcellulose alginate, galacturonic acid, mannuronic acid, and salts thereof.

[0319] (Modifier) The modifying agent is a compound that is reactive with polycarboxylic acid and is preferably a compound having the above-mentioned monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group.

[0320] Examples of modifying agents are as follows: Epoxy (CH2OCH)CH2O-Z C Amine H2N-Z C Hydroxy HO-Z C [In the formula, Z C is as stated above.]

[0321] Z in the structure of the above modifier C may be replaced with any group constituting a modifying group, for example, Z C may be a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, for example, Z C -Y C -Z C n It is also possible to use the following.

[0322] The modified polycarboxylic acid may be synthesized by reacting a polycarboxylic acid with a modifying agent. For example, a modifying agent that is an epoxy compound may be reacted with a carboxy group of a polycarboxylic acid to form an ester bond, thereby producing a modified polycarboxylic acid. Those skilled in the art can appropriately design the reaction conditions between the polycarboxylic acid and the modifying agent, such as by using a catalyst (e.g., an acid catalyst or a base catalyst) or a condensing agent, depending on the desired product.

[0323] [Vinyl polymer] As an example of a liquid-repellent compound, a vinyl polymer will be described. A vinyl polymer is a polymer obtained by polymerizing a vinyl monomer, and exhibits liquid repellency. Here, the vinyl monomer may be any compound having a polymerizable carbon-carbon double bond (>C=C<), and may be a monomer containing a vinyl group, a vinylene group, a vinylidene group, an acryloyl group, a methacryloyl group, or a derivative group thereof. The vinyl polymer may in particular be a (meth)acrylic polymer.

[0324] [Characteristics, etc.] The vinyl polymer is preferably a compound having carbon of bio-based origin. The bio-based degree is measured in accordance with ASTM D6866. The bio-based degree of the vinyl polymer may be 20% or more, preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example 100%. A high bio-based degree means that the amount of fossil resource-based materials, such as petroleum, used is small, and from this perspective, the higher the bio-based degree of the vinyl polymer, the more preferable it is.

[0325] The melting point of the vinyl polymer may be 30°C or more, 40°C or more, 60°C or more, 80°C or more, 100°C or more, or 120°C or more, and is preferably 40°C or more, and may be 250°C or less, 225°C or less, 200°C or less, 150°C or less, 130°C or less, 120°C or less, 110°C or less, 100°C or less, 80°C or less, or 50°C or less.

[0326] [Structure, etc.] The weight average molecular weight of the vinyl polymer may be 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may be 5000000 or less, 3000000 or less, 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, or 5000 or less. The weight average molecular weight may be a polystyrene-equivalent molecular weight measured by GPC.

[0327] (a) Hydrocarbon group-containing monomer The vinyl polymer may have a repeating unit derived from a monomer (a) having a hydrocarbon group having 6 to 40 carbon atoms.

[0328] The hydrocarbon group of the monomer (a) may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group is branched or linear, and more preferably linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl group). The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 10 or more, 12 or more, 14 or more, or 16 or more, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, and preferably 30 or less, 25 or less, or 20 or less.

[0329] The monomer (a) may contain an amide group, a urea group, or a urethane group. The hydrocarbon monomer may be a combination of a hydrocarbon monomer having an amide group, a urea group, or a urethane group and a hydrocarbon monomer not having an amide group, a urea group, or a urethane group. By including such a group in the monomer (a), the effect of the present disclosure can be well achieved.

[0330] The monomer (a) having a hydrocarbon group having 6 to 40 carbon atoms is formula: CH2=C(-X a )-C(=O)-Y a (R a ) k [In the formula, R a are each independently a hydrocarbon group having 6 to 40 carbon atoms, X a is a hydrogen atom, a monovalent organic group, or a halogen atom, Y a is a group consisting of at least one selected from a divalent to tetravalent hydrocarbon group having one carbon atom (particularly, -CH2-, -CH(-)2), -CH4-, -O-, -C(=O)-, -S(=O)2- and -NH-; k is 1 to 3. It is preferable that the monomer is represented by the following formula:

[0331] X a X may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. a Examples of X are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. a is preferably a hydrogen atom, a methyl group, or a chlorine atom. a is particularly preferably a hydrogen atom.

[0332] Y a is a divalent to tetravalent group. Y a is preferably a divalent group. Y a is preferably a group composed of at least one selected from a hydrocarbon group having one carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2-, and -NH-. a is preferably not a hydrocarbon group. Examples of the hydrocarbon group having one carbon atom include -CH2-, -CH(-)2, and -C(-)3. When the hydrocarbon group having one carbon atom is repeated, -(CH2) m Y may form a hydrocarbon group having two or more carbon atoms, such as -(m is an integer of 1 to 5). a may have an NH group.

[0333] Y a -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'- , -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- [In the formula, Y' is a direct bond, -O-, -NH- or -S(=O)2-; R' is -(CH2) m - (wherein m is an integer of 1 to 5) or -C6H4- (phenylene group). It may be.

[0334] Y aSpecific examples thereof include -O-, -NH-, -O-C(=O)-, -C(=O)-NH-, -NH-C(=O)-, -O-C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -O-C(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -O-C(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -O-C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, -NH-(CH2) m -NH-C6H4-, -NH-(CH2) m -NH-S(=O)2-, or -NH-(CH2) m -S(=O)2-NH- [wherein, m is 1 to 5, particularly 2 or 4].

[0335] Y a is -O-, -NH-, -O-(CH2) m-OC(=O)-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -NH-S(=O)2- or -NH-(CH2) m -S(=O)2-NH- [In the formula, m is an integer of 1 to 5, particularly 2 or 4.] It is preferable that Y a is -O- or -O-(CH2) m -NH-C(=O)-, especially -O-(CH2) m It is more preferably -NH-C(=O)-.

[0336] R a is preferably a linear or branched hydrocarbon group. The hydrocarbon group may particularly be a linear hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. The number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example 16 to 26 or 15 to 26, particularly 18 to 22 or 17 to 22.

[0337] Examples of monomer (a) are: Formula (a1): CH2=C(-X a1 )-C(=O)-Y a1 -R a1 [In the formula, R a1 is a hydrocarbon group having 6 to 40 carbon atoms, X a1 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y a1 is -O- or -NH-.] A monomer represented by the formula: Formula (a2): CH2=C(-Xa2 )-C(=O)-Y a21 -Z(-Y a22 -R a2 ) n [In the formula, R a2 are each independently a hydrocarbon group having 6 to 40 carbon atoms, X a2 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y a21 is -O- or -NH-, Y a22 each independently represents a direct bond or a group consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, and -CH2-; Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms; n is 1 or 2. It is a monomer represented by the formula:

[0338] (a1) Monomer The monomer (a1) has the formula: CH2=C(-X a1 )-C(=O)-Y a1 -R a1 [In the formula, R a1 is a hydrocarbon group having 6 to 40 carbon atoms, X a1 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y a1 is -O- or -NH-.] It is a compound represented by the formula:

[0339] The monomer (a1) is Y a1 a long chain acrylate ester monomer in which Y is -O-; a1 is a long chain acrylamide monomer in which is -NH-. R a1 R is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group. a1In the above formula, the hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 carbon atoms, and particularly preferably 18 to 22 carbon atoms. X a1 may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0340] Preferred specific examples of long chain acrylate ester monomers are lauryl (meth)acrylate, stearyl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl alpha chloroacrylate, icosyl alpha chloroacrylate, and behenyl alpha chloroacrylate. Specific preferred examples of the long-chain acrylamide monomer are stearyl (meth)acrylamide, icosyl (meth)acrylamide, and behenyl (meth)acrylamide.

[0341] (a2) Monomer The monomer (a2) is a monomer different from the monomer (a1). The monomer (a2) is a (meth)acrylate or (meth)acrylamide having at least one group selected from -O-, -C(=O)-, -S(=O)2-, -NH-, or -CH2-. The monomer (a2) has the formula: CH2=C(-X a2 )-C(=O)-Y a21 -Z(-Y a22 -R a2 ) n [In the formula, R a2 are each independently a hydrocarbon group having 6 to 40 carbon atoms, X a2 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y a21 is -O- or -NH-, Y a22 each independently represents a direct bond or a group consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, and -CH2-; Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms; n is 1 or 2. The compound may be represented by the formula: Y a22 And / or Z may not be a direct bond. a22 and Z may not simultaneously be a direct bond.

[0342] R a2 R is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group. a2 In the above formula, the hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 or 15 to 26, and particularly preferably 18 to 22 or 17 to 22 carbon atoms.

[0343] X a2 may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0344] Y a22 -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'- , -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- [In the formula, each Y' is independently a direct bond, -O-, -NH-, or -S(=O)2-, R' is -(CH2) m -(m is an integer of 1 to 5), a linear hydrocarbon group having an unsaturated bond of 1 to 5 carbon atoms, a hydrocarbon group having a branched structure having 1 to 5 carbon atoms, or -(CH2) l -C6H4-(CH2) l - (each 1 is independently an integer of 0 to 5, and -C6H4- is a phenylene group). It may be.

[0345] Y a22Specific examples thereof include direct bonding, -O-, -NH-, -O-C(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O)2-, -S(=O)2-NH-, -O-C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, -NH-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -O-C(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -O-C(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -NH-(CH2) m -O-C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, -NH-(CH2) m -NH-C6H4- [wherein, m is an integer of 1 to 5.] is as follows.

[0346] Y a22is preferably -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O)2-, -S(=O)2-NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-. Y a22 More preferably, Y is -NH-C(=O)-, -C(=O)-NH-, -OC(=O)-NH-, -NH-C(=O)-O- or -NH-C(=O)-NH-. a22 Y does not have to be a direct bond. a22 may have an NH group.

[0347] Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and may have a straight chain structure or a branched structure. The number of carbon atoms in Z is preferably 2 to 4, particularly 2. Specific examples of Z are a direct bond, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH(-)2, -CH2(CH-)CH2-, -CH2CH2CH(-)2, -CH2CH2CH2CH2CH(-)2, -CH2CH2(CH-)CH2-, and -CH2CH2CH2CH(-)2. Z does not have to be a direct bond.

[0348] Monomer (a2) is CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-R a2 , CH2=C(-X a2 )-C(=O)-O-(CH2) m -OC(=O)-NH-R a2 , CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-OR a2 , CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-NH-R a2 [wherein R a2 and X a2 has the same meaning as above.] Monomer (a2) is CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-R a2 It is particularly preferred that:

[0349] Monomer (a2) can be produced by reacting a hydroxyalkyl (meth)acrylate or a hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate, such as lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, or behenyl isocyanate. Alternatively, the monomer (a2) can be produced by reacting a (meth)acrylate having an isocyanate group in the side chain, such as 2-methacryloyloxyethyl methacrylate, with a long-chain alkylamine or a long-chain alkyl alcohol. Examples of long-chain alkylamines include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine. Examples of long-chain alkyl alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

[0350] Preferred examples of the monomer (a) are as follows: Stearyl (meth)acrylate, behenyl (meth)acrylate, stearyl alpha chloroacrylate, behenyl alpha chloroacrylate; Stearyl (meth)acrylamide, behenyl (meth)acrylamide;

[0351] TIFF2025044132000009.tif2453

[0352] TIFF2025044132000010.tif2253 TIFF2025044132000011.tif2152 TIFF2025044132000012.tif2155

[0353] TIFF2025044132000013.tif2357 TIFF2025044132000014.tif2256 TIFF2025044132000015.tif2156

[0354] TIFF2025044132000016.tif2051 TIFF2025044132000017.tif2054 TIFF2025044132000018.tif2352 TIFF2025044132000019.tif2659

[0355] TIFF2025044132000020.tif2046

[0356] TIFF2025044132000021.tif2249 [In the above formula, n is a number from 6 to 40, and m is a number from 1 to 5.] The compound of the above formula is an acryl compound in which the α-position is a hydrogen atom, but specific examples may be methacryl compounds in which the α-position is a methyl group and α-chloroacryl compounds in which the α-position is a chlorine atom.

[0357] The monomer (a2) has the formula: R a22 -C(=O)-NH-R a23 -OR a21 [In the formula, R a21 represents an organic residue having an ethylenically unsaturated polymerizable group, R a22 is a hydrocarbon group having 6 to 40 carbon atoms, R a23 is a hydrocarbon group having 1 to 5 carbon atoms.] It is preferable that the monomer is an amide group-containing monomer represented by the following formula:

[0358] R a21 is an organic residue having an ethylenically unsaturated polymerizable group, and is not particularly limited as long as it has a carbon-carbon double bond. a211 =CH2, -CHR a211 =CH2, -CH2CHR a211 Examples of the organic residue include an ethylenically unsaturated polymerizable group such as ═CH2. a211 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 21 R may have various organic groups other than the ethylenically unsaturated polymerizable group, such as organic groups of chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, polysiloxane groups, etc., and these organic groups may be substituted with various substituents. a21 is -C(=O)CR a211 It is preferred that =CH2.

[0359] R a22 R is a hydrocarbon group having 6 to 40 carbon atoms, preferably an alkyl group, and examples thereof include chain hydrocarbon groups and cyclic hydrocarbon groups. Among these, a chain hydrocarbon group is preferred, and a linear saturated hydrocarbon group is particularly preferred. a22 The number of carbon atoms is 6 or more and 40 or less, preferably 11 to 27, and particularly preferably 15 to 23.

[0360] R a23 R is a hydrocarbon group having 1 to 5 carbon atoms, preferably an alkyl group. The hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched and may have an unsaturated bond, but is preferably linear. a23 The number of carbon atoms in R is preferably 2 to 4, and more preferably 2. a23 is preferably an alkylene group.

[0361] The amide group-containing monomer is R a22 There is only one type (e.g., R a22 (Only compounds with 17 carbon atoms) or R a22 is a combination of multiple a22 A compound having 17 carbon atoms, Ra22 and a compound having 15 carbon atoms.

[0362] An example of an amide group-containing monomer is a carboxylic acid amide alkyl (meth)acrylate. Specific examples of the amide group-containing monomer include palmitic acid amidoethyl (meth)acrylate, stearic acid amidoethyl (meth)acrylate, behenic acid amidoethyl (meth)acrylate, myristic acid amidoethyl (meth)acrylate, lauric acid amidoethyl (meth)acrylate, isostearic acid ethyl amido (meth)acrylate, oleic acid ethyl amido (meth)acrylate, tertiary butyl cyclohexyl caproic acid amidoethyl (meth)acrylate, adamantane carboxylic acid ethyl amido (meth)acrylate, naphthalene carboxylic acid amidoethyl (meth)acrylate, anthracene carboxylic acid amidoethyl (meth)acrylate, palmitic acid amidopropyl (meth)acrylate, stearic acid amidopropyl (meth)acrylate, palmitic acid amidoethyl vinyl ether, stearic acid amidoethyl vinyl ether, palmitic acid amidoethyl allyl ether, stearic acid amidoethyl allyl ether, or mixtures thereof.

[0363] The amide group-containing monomer is preferably stearamidoethyl (meth)acrylate. The amide group-containing monomer may be a mixture containing stearamidoethyl (meth)acrylate. In the mixture containing stearamidoethyl (meth)acrylate, the amount of stearamidoethyl (meth)acrylate may be, for example, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and may be 90% by weight or less, 80% by weight or less, or 70% by weight or less, based on the weight of the entire amide group-containing monomer. The remaining monomer may be, for example, palmitamidoethyl (meth)acrylate.

[0364] In the monomer (a), the amount of monomer (a2) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, or 80% by weight or more, and is preferably 30% by weight or more.

[0365] (b) Hydrophilic group-containing monomer The vinyl polymer may contain a hydrophilic group-containing monomer (b). The monomer (b) is a monomer other than the monomer (a) and has a hydrophilic group. The hydrophilic group is preferably an oxyalkylene group (the alkylene group has 2 to 6 carbon atoms), particularly an oxyethylene group. In particular, the monomer (b) is preferably an oxyalkylene (meth)acrylate, such as polyalkylene (or monoalkylene) glycol mono(meth)acrylate and / or polyalkylene (or monoalkylene) glycol di(meth)acrylate, or polyalkylene (or monoalkylene) glycol mono(meth)acrylamide.

[0366] The monomer (b) is formula: CH2=CX b C(=O)-Y b -(R b O) n -A b [In the formula, X b is a hydrogen atom or a methyl group, Y b is -O- or -NH-, R b are each independently an alkylene group having 2 to 6 carbon atoms, A b is a hydrogen atom, an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, or CH2=CX b C(=O)-Yes, n is an integer from 1 to 90. It is preferable that the oxyalkylene (meth)acrylate is represented by the following formula:

[0367] An example of the monomer (b) is a monomer having the formula: CH2=CX b C(=O)-O-(R b O) n -A bi (b1) and CH2=CX b C(=O)-O-(R b O) n -C(=O)CX b =CH2(b2), CH2=CX b C(=O)-NH-(R b O) n -A bi (b3) [In the formula, X b are each independently a hydrogen atom or a methyl group, A bi each independently represents a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, R b are each independently an alkylene group having 2 to 6 carbon atoms, n is an integer between 1 and 90 It is.] It is preferable that the formula is represented by the following formula:

[0368] n may be, for example, 1 to 50, particularly 1 to 30, and especially 1 to 15 or 2 to 15. Alternatively, n may be, for example, 1. R b may be a linear or branched alkylene group, for example of the formula -(CH2) x -or-(CH2) x1 -(CH(CH3)) x2 -[In the formula, x1 and x2 are 0 to 6, for example, 2 to 5, and the sum of x1 and x2 is 1 to 6. -(CH2) x1 - and - (CH(CH3)) x2 The order of - is not limited to the depicted formula and may be random. -(R b O) n In -, R may be two or more types (for example, two to four types, particularly two types), and -(R b O) n- is, for example, -(R 1 O) n1 -and-(R 2 O) n2 -[wherein, R 1 and R 2 are different from each other and are alkylene groups having 2 to 6 carbon atoms, n1 and n2 are numbers of 1 or more, and the sum of n1 and n2 is 2 to 90.

[0369] R in formulas (b1), (b2) and (b3) b In particular, R is preferably an ethylene group, a propylene group or a butylene group, and more preferably a butylene group. b R may be a combination of two or more alkylene groups. In that case, it is preferable that at least one of R is an ethylene group, a propylene group, or a butylene group. b Examples of the combination include an ethylene group / propylene group combination, an ethylene group / butylene group combination, and a propylene group / butylene group combination. The monomer (b) may be a mixture of two or more kinds. In that case, at least one of the monomers (b) is a mixture of R b is preferably an ethylene group, a propylene group, or a butylene group. In addition, when using a polyalkylene glycol di(meth)acrylate represented by formula (b2), it is not preferable to use it alone as the monomer (b), but it is preferable to use it in combination with the monomer (b1). In that case, it is also preferable to keep the compound represented by formula (b2) to less than 30% by weight of the monomer (b) used.

[0370] Specific examples of the monomer (b) include, but are not limited to, the following: CH2=CHCOO-CH2CH2O-H CH2=CHCOO-CH2CH2CH2O-H CH2=CHCOO-CH2CH(CH3)OH CH2=CHCOO-CH(CH3)CH2O-H CH2=CHCOO-CH2CH2CH2CH2O-H <h2 style=";text-align:left;direction:ltr">CH2=CHCOO-CH2CH2CH(CH3)OH<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-CH2CH(CH3)CH2O-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-CH(CH3)CH2CH2O-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-CH2CH(CH2CH3)OH<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-CH2C(CH3)2O-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-CH(CH2CH3)CH2O-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-C(CH3)2CH2O-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-CH(CH3)CH(CH3)OH<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-C(CH3)(CH2CH3)OH<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)2-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)4-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)5-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)6-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)5-CH3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)9-CH3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)<h2 style=";text-align:left;direction:ltr"> 23 <h2 style=";text-align:left;direction:ltr"> -CH3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)<h2 style=";text-align:left;direction:ltr"> 90 <h2 style=";text-align:left;direction:ltr"> -CH3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0371] <h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH(CH3)O)9-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH(CH3)O)9-CH3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH(CH3)O)<h2 style=";text-align:left;direction:ltr"> 12 <h2 style=";text-align:left;direction:ltr"> -CH3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)2-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9<h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O) 23 -OOC(CH3)C=CH2 CH2=CHCOO-(CH2CH2O) 20 -(CH2CH(CH3)O)5-CH2-CH=CH2

[0372] CH2=CHCOO-(CH2CH2O)9-H CH2=C(CH3)COO-CH2CH2O-H CH2=C(CH3)COO-CH2CH2CH2O-H CH2=C(CH3)COO-CH2CH(CH3)O-H CH2=C(CH3)COO-CH(CH3)CH2O-H CH2=C(CH3)COO-CH2CH2CH2CH2O-H CH2=C(CH3)COO-CH2CH2CH(CH3)O-H CH2=C(CH3)COO-CH2CH(CH3)CH2O-H CH2=C(CH3)COO-CH(CH3)CH2CH2O-H CH2=C(CH3)COO-CH2CH(CH2CH3)O-H CH2=C(CH3)COO-CH2C(CH3)2O-H CH2=C(CH3)COO-CH(CH2CH3)CH2O-H CH2=C(CH3)COO-C(CH3)2CH2O-H CH2=C(CH3)COO-CH(CH3)CH(CH3)O-H CH2=C(CH3)COO-C(CH3)(CH2CH3)O-H CH2=C(CH3)COO-(CH2CH2O)2-H CH2=C(CH3)COO-(CH2CH2O)4-H CH2=C(CH3)COO-(CH2CH2O)5-H CH2=C(CH3)COO-(CH2CH2O)6-H CH2=C(CH3)COO-(CH2CH2O)9-H CH2=C(CH3)COO-(CH2CH2O)5-CH3 CH2=C(CH3)COO-(CH2CH2O)9-CH3 CH2=C(CH3)COO-(CH2CH2O) 23 -CH3 CH2=C(CH3)COO-(CH2CH2O) 90 -CH3 CH2=C(CH3)COO-(CH2CH(CH3)O)9-H

[0373] CH2=C(CH3)COO-(CH2CH(CH3)O)9-CH3 CH2=C(CH3)COO-(CH2CH(CH3)O) 12 -CH3 CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=C(CH3)COO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9 CH2=C(CH3)COO-(CH2CH2O) 23 -OOC(CH3)C=CH2 CH2=C(CH3)COO-(CH2CH2O) 20 -(CH2CH(CH3)O)5-CH2-CH=CH2

[0374] CH2=CH-C(=O)-NH-CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH(CH3)O-H CH2=CH-C(=O)-NH-CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH(CH3)O-H CH2=CH-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH(CH3)CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH(CH2CH3)OH CH2=CH-C(=O)-NH-CH2C(CH3)2O-H CH2=CH-C(=O)-NH-CH(CH2CH3)CH2O-H CH2=CH-C(=O)-NH-C(CH3)2CH2O-H CH2=CH-C(=O)-NH-CH(CH3)CH(CH3)OH CH2=CH-C(=O)-NH-C(CH3)(CH2CH3)OH CH2=CH-C(=O)-NH-(CH2CH2O)2-H CH2=CH-C(=O)-NH-(CH2CH2O)4-H CH2=CH-C(=O)-NH-(CH2CH2O)5-H CH2=CH-C(=O)-NH-(CH2CH2O)6-H CH2=CH-C(=O)-NH-(CH2CH2O)9-H CH2=CH-C(=O)-NH-(CH2CH2O)5-CH3 CH2=CH-C(=O)-NH-(CH2CH2O)9-CH3 CH2=CH-C(=O)-NH-(CH2CH2O) 23 -CH3 CH2=CH-C(=O)-NH-(CH2CH2O) 90 -CH3

[0375] CH2=CH-C(=O)-NH-(CH2CH(CH3)O)9-H CH2=CH-C(=O)-NH-(CH2CH(CH3)O)9-CH3 CH2=CH-C(=O)-NH-(CH2CH(CH3)O) 12 -CH3 CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=CH-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0376] CH2=C(CH3)-C(=O)-NH-CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)OH CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH(CH3)OH CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH2CH3)OH CH2=C(CH3)-C(=O)-NH-CH2C(CH3)2O-H CH2=C(CH3)-C(=O)-NH-CH(CH2CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-C(CH3)2CH2O-H CH2=C(CH3)-C(=O)-NH-CH(CH3)CH(CH3)OH CH2=C(CH3)-C(=O)-NH-C(CH3)(CH2CH3)OH CH2=C(CH3)-C(=O)-NH-(CH2CH2O)2-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)4-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)6-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 23 -CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 90 -CH3

[0377] CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)9-H CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)9-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O) 12 -CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0378] As the monomer (b), X 2 is a hydrogen atom. The monomer (b) is particularly preferably hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxyethyl acrylamide.

[0379] (c) Ionic group-containing monomer The vinyl polymer may contain an ionic group-containing monomer (c). The monomer (c) is preferably a monomer containing an olefinic carbon-carbon double bond and an ionic group (particularly, an acrylic monomer). The ionic group is an anionic group and / or a cationic group.

[0380] Examples of the monomer having an anionic group include a monomer having a carboxyl group, a sulfonic acid group, or a phosphoric acid group.Specific examples of the monomer having an anionic group include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, (meth)acrylate phosphate, vinylbenzenesulfonic acid, acrylamido tertiary butylsulfonic acid, and the like, or salts thereof.

[0381] Salts of anionic groups include alkali metal salts, alkaline earth metal salts, or ammonium salts, such as methylammonium salts, ethanolammonium salts, and triethanolammonium salts.

[0382] In the monomer having a cationic group, examples of the cationic group are amino groups, preferably tertiary amino groups and quaternary amino groups. In the tertiary amino group, the two groups bonded to the nitrogen atom are preferably the same or different and are an aliphatic group (particularly an alkyl group) having 1 to 5 carbon atoms, an aromatic group (aryl group) having 6 to 20 carbon atoms, or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example, a benzyl group (C6H5-CH2-)). In the quaternary amino group, the three groups bonded to the nitrogen atom are preferably the same or different and are an aliphatic group (particularly an alkyl group) having 1 to 5 carbon atoms, an aromatic group (aryl group) having 6 to 20 carbon atoms, or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example, a benzyl group (C6H5-CH2-)). In the tertiary amino group and the quaternary amino group, the remaining group bonded to the nitrogen atom may have a carbon-carbon double bond. The cationic group may be in the form of a salt.

[0383] The cationic group that is a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, such as carboxylic acids having 1 to 20 carbon atoms (particularly monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid) are preferred. Dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate and salts thereof are preferred.

[0384] Specific examples of the monomer having a cationic group are as follows. CH2=CHCOO-CH2CH2-N(CH3)2 and its salts (e.g. acetate) CH2=CHCOO-CH2CH2-N(CH2CH3)2 and its salts (e.g. acetate) CH2=C(CH3)COO-CH2CH2-N(CH3)2 and its salts (e.g. acetate) CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2 and its salts (e.g. acetate salts) CH2=CHC(O)N(H)-CH2CH2CH2-N(CH3)2 and its salts (e.g. acetate) CH2=CHCOO-CH2CH2-N(-CH3)(-CH2-C6H5) and its salts (e.g. acetate) CH2=C(CH3)COO-CH2CH2-N(-CH2CH3)(-CH2-C6H5) and its salts (e.g. acetate) CH2=CHCOO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH2-N + (-CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (-CH2CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Br - CH2=C(CH3)COO-CH2CH2-N + (CH3)3I- CH2=C(CH3)COO-CH2CH2-N + (CH3)3O - SO3CH3 CH2=C(CH3)COO-CH2CH2-N + (CH3)(-CH2-C6H5)2Br -

[0385] The ionic group-containing monomer (c) is preferably methacrylic acid, acrylic acid, or dimethylaminoethyl methacrylate, and more preferably methacrylic acid or dimethylaminoethyl methacrylate.

[0386] (d) Halogenated olefin monomers The vinyl polymer may have a repeating unit derived from a halogenated olefin monomer (d). The halogenated olefin monomer (d) may not have a fluorine atom. The halogenated olefin monomer (d) is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms, or iodine atoms. The halogenated olefin monomer (d) is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms and having 1 to 5 chlorine atoms. Preferred specific examples of the halogenated olefin monomer (d) are vinyl halides, such as vinyl chloride, vinyl bromide, vinyl iodide, and vinylidene halides, such as vinylidene chloride, vinylidene bromide, and vinylidene iodide. Vinyl chloride or vinylidene chloride is preferred because it enhances water repellency (particularly durability of water repellency). The presence of a repeating unit derived from a halogenated olefin monomer (d) enhances the washing durability of the vinyl polymer.

[0387] (e) Crosslinking monomer The vinyl polymer has a crosslinkable monomer having at least two reactive groups and / or ethylenically unsaturated double bonds (preferably (meth)acrylate groups), and the crosslinkable monomer (e) may be a monomer that does not contain fluorine atoms. It may be a compound that does not contain fluorine atoms. The crosslinkable monomer (e) may be a compound having at least two ethylenically unsaturated double bonds (preferably (meth)acrylate groups), or a compound having at least one ethylenically unsaturated double bond and at least one reactive group. Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, a carboxyl group, and the like.

[0388] The crosslinking monomer may be a mono(meth)acrylate, di(meth)acrylate or di(meth)acrylamide having a reactive group.

[0389] One example of a crosslinkable monomer is a vinyl monomer having a reactive group.

[0390] Examples of crosslinkable monomers include, but are not limited to, diacetone (meth)acrylamide, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

[0391] (f) Cyclic Hydrocarbon Group-Containing Monomer The vinyl polymer may have a repeating unit derived from a cyclic hydrocarbon group-containing monomer (f). The cyclic hydrocarbon group-containing monomer (f) is a monomer having a cyclic hydrocarbon group, and may be a monomer having one ethylenically unsaturated double bond and a cyclic hydrocarbon group.

[0392] The cyclic hydrocarbon group-containing monomer (f) preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, and may, for example, have a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0393] The cyclic hydrocarbon group may be alicyclic or aromatic, preferably alicyclic. The cyclic hydrocarbon group may be saturated or unsaturated, preferably saturated. The cyclic hydrocarbon group may be a monocyclic group, a polycyclic group, or a bridged ring group, preferably a bridged ring group. The cyclic hydrocarbon group may have a chain group (e.g., a straight-chain or branched-chain hydrocarbon group).

[0394] The cyclic hydrocarbon group may have 4 or more, 6 or more, or 8 or more carbon atoms, and may have 30 or less, 26 or less, 22 or less, 18 or less, or 14 or less carbon atoms.

[0395] Specific examples of cyclic hydrocarbon groups include cyclohexyl, t-butylcyclohexyl, adamantyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, bornyl, isobornyl, norbornyl, dicyclopentanyl, dicyclopentenyl, benzyl, phenyl, naphthyl, 2-t-butylphenyl, residues in which one or more hydrogen atoms have been removed from these groups (e.g., cyclohexylene, adamantylene, phenylene, naphthylene, etc.), and groups which are substitution products thereof.

[0396] Specific examples of the cyclic hydrocarbon group-containing monomer include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and compounds in which these acrylates are substituted with acrylamide, etc. These may be used alone or in combination of two or more.

[0397] (g) Other monomers The other monomers are not limited to these examples, and include acrylonitrile, organosiloxane-containing (meth)acrylates, short-chain alkyl (meth)acrylates, vinyl acetate, styrene, α-methylstyrene, p-methylstyrene, vinyl alkyl ethers, etc. The other monomers (g) may be used alone or in combination of two or more.

[0398] [Polymer composition] The combination of the monomers (a) to (g) constituting the repeating units of the vinyl polymer is not particularly limited, and examples are as follows (parentheses are omitted): a a+b a+b+c a+c a+d a+b+c+d a+b+c+d+e a+b+c+d+e+f Further, other monomers (g) may be used in combination with the above combination. In the case of pulp products, it is preferable to use the monomers (a), (b) and (c) in combination.

[0399] The amount of the repeating units derived from the monomer (a) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the vinyl polymer.

[0400] The amount of the repeating units derived from the monomer (b) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the vinyl polymer. The amount of the repeating units derived from monomer (b) may be, relative to 100 parts by weight of the amount of the repeating units derived from monomer (a), 0.01 part by weight or more, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less.

[0401] The amount of the repeating units derived from the monomer (c) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the vinyl polymer. The amount of the repeating units derived from monomer (c) may be, relative to 100 parts by weight of the amount of the repeating units derived from monomer (a), 0.01 part by weight or more, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less.

[0402] The amount of the repeating units derived from the monomer (d) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the vinyl polymer. The amount of the repeating units derived from monomer (d) may be, relative to 100 parts by weight of the amount of the repeating units derived from monomer (a), 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less.

[0403] The amount of the repeating units derived from the monomer (e) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the vinyl polymer. The amount of the repeating units derived from monomer (e) may be, relative to 100 parts by weight of the amount of the repeating units derived from monomer (a), 0.01 part by weight or more, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less.

[0404] The amount of the repeating units derived from the monomer (f) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the vinyl polymer. The amount of the repeating units derived from monomer (f) may be, relative to 100 parts by weight of the amount of the repeating units derived from monomer (a), 0.01 part by weight or more, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less.

[0405] The amount of repeating units derived from monomer (g) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the vinyl polymer. The amount of the repeating units derived from monomer (g) may be, relative to 100 parts by weight of the amount of the repeating units derived from monomer (a), 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less.

[0406] [Polymerization method] The vinyl polymer can be produced by a known polymerization method, and the polymerization reaction conditions can be selected arbitrarily. Examples of such polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization.

[0407] In solution polymerization, a method is adopted in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, the mixture is heated and stirred at a temperature in the range of 30 to 120°C for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, relative to 100 parts by weight of the monomer.

[0408] The organic solvent is inactive to the monomers and dissolves them, and may be, for example, an ester (e.g., an ester having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), a ketone (e.g., a ketone having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone), or an alcohol (e.g., an alcohol having 1 to 40 carbon atoms, specifically, ethanol, butanol, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, and the like. The organic solvent is used in an amount of 10 to 3000 parts by weight, for example, 50 to 2000 parts by weight, based on 100 parts by weight of the total of the monomers.

[0409] In emulsion polymerization, a method is adopted in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, the monomer is polymerized by stirring at a temperature in the range of 50 to 80°C for 1 to 20 hours. As the polymerization initiator, water-soluble initiators such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, sodium peroxide, potassium persulfate, and ammonium persulfate, and oil-soluble initiators such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate are used. The polymerization initiator is used in the range of 0.01 to 10 parts by weight relative to 100 parts by weight of the monomer.

[0410] In order to obtain a polymer aqueous dispersion having excellent shelf stability, it is desirable to polymerize the monomer by dispersing it in water into fine particles using an emulsifier capable of applying strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. As the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and are used in the range of 0.5 to 20 parts by weight per 100 parts by weight of the monomer. It is preferable to use an anionic and / or nonionic and / or cationic emulsifier. When the monomers are not completely compatible with each other, it is preferable to add a compatibilizer that can sufficiently make these monomers compatible, such as a water-soluble organic solvent or a low molecular weight monomer. The addition of a compatibilizer can improve emulsifiability and copolymerizability.

[0411] The water-soluble organic solvent may be the organic solvent described above. For example, acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, etc. may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, based on 100 parts by weight of water. In addition, the low molecular weight monomer may be methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, based on 100 parts by weight of the total amount of the monomers.

[0412] In the polymerization, a chain transfer agent may be used. The molecular weight of the polymer can be changed depending on the amount of the chain transfer agent used. Examples of the chain transfer agent include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (e.g., having 1 to 40 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite. The amount of the chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the monomers.

[0413] [Dispersant] The repellent of the present disclosure may include a dispersant. The dispersant may be at least one selected from an organic dispersant and an inorganic dispersant. The dispersant may be at least one selected from an anionic dispersant, a nonionic dispersant, a cationic dispersant, an amphoteric dispersant, and an inorganic dispersant.

[0414] As the dispersant, an organic dispersant and an inorganic dispersant may be used separately, or an organic dispersant and an inorganic dispersant may be used in combination.

[0415] An organic dispersant may be used as the dispersant. The organic dispersant can be classified into a nonionic dispersant, an anionic dispersant, a cationic dispersant, and an amphoteric dispersant, and the organic dispersant may mean a surfactant.

[0416] The dispersant may be fluorine-free.

[0417] [Nonionic dispersant] The dispersant may include a nonionic dispersant. The nonionic dispersant may be a nonionic surfactant.

[0418] The nonionic dispersant may be a low molecular weight or a high molecular weight dispersant. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0419] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols and amine oxides.

[0420] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0421] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a monohydric to tridehydric (particularly dihydric to decahydric) alcohol (e.g., an aliphatic alcohol) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0422] An example of the ester ether is a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. An example of the alcohol is a monohydric to tridecahydric (particularly dihydric to decahydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0423] An example of an alkanolamide is formed from a fatty acid and an alkanolamine. The alkanolamide may be a monoalkanolamide or a dialkanolamine. An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0424] The polyol may be a di- to penta-hydric alcohol having 10 to 30 carbon atoms. The amine oxide may be an oxide (eg, having 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0425] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic dispersant is generally preferably 2 to 100.

[0426] The nonionic dispersant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyols and amine oxides, and is preferably a nonionic dispersant having an oxyalkylene group.

[0427] The nonionic dispersant may be an alkylene oxide adduct of a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sorbitan ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a glycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyglycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sucrose ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, and the like. Among these, those in which the structure of the alkylene oxide adduct portion and the polyalkylene glycol portion is polyoxyethylene (POE) or polyoxypropylene (POP) or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Additionally, the nonionic dispersant need not contain aromatic groups.

[0428] The nonionic dispersant has the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [In the formula, R 1 is an alkyl group having 1 to 22 carbon atoms or an alkenyl group or acyl group having 2 to 22 carbon atoms, R 2 each is independently the same or different and is an alkylene group having 3 or more carbon atoms (e.g., 3 to 10), R 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number equal to or greater than 2, q is a number equal to or greater than 0. The compound may be represented by the formula:

[0429] R 1 R preferably has 8 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms. 1 Preferred specific examples include an octyl group, a nonyl group, a trimethylnonyl group, a lauryl group, a tridecyl group, an oleyl group, and a stearyl group. R 2 Examples are a propylene group and a butylene group. In the nonionic dispersant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R 2 O) q may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) in the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, and among these, an oxypropylene chain is preferred.

[0430] Examples of nonionic dispersants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkanes (C 12 -C 16 ) Thiol, Sorbitan Mono Fatty Acid (C7-C 19 ) or alkyl(C 12 -C 18) amines, etc., sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lecithin derivatives, etc. Examples of nonionic dispersants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycol, polyethyleneimine ethoxylates, etc.

[0431] The proportion of the polyoxyethylene block may be 5 to 80% by weight, for example 30 to 75% by weight, particularly 40 to 70% by weight, based on the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of the nonionic dispersant is generally 300 to 5,000, for example, 500 to 3,000. The nonionic dispersant may be a single type, or a mixture of two or more types. The nonionic dispersant may be a mixture of a compound having an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. Specifically, it is preferable to select from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, and polyoxypropylenes having an HLB value of 1 to 18, and sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, and polyoxyethylene sorbitan fatty acid esters having an HLB value of less than 7.

[0432] [Cationic dispersants] The dispersant may include a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a compound having no amide group.

[0433] The cationic dispersant may be a low molecular weight type (e.g., molecular weight of 2000 or less, particularly 10000 or less) or a polymer type (e.g., molecular weight of 2000 or more). The molecular weight of the cationic dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 1000000 or less, 750000 or less, 500000 or less, 250000 or less, 100000 or less, 50000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0434] The cationic dispersant may be aliphatic or aromatic, and may be, for example, an ammonium salt (e.g., a quaternary ammonium salt). The cationic dispersant may be an oxyethylene adduct ammonium salt. Specific examples include amine salt-type dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazoline; quaternary ammonium salt-type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, and benzethonium chloride; and polymer-type cationic dispersants such as polyquaternium-1 to 47. Examples of cationic dispersants include alkylamine salts and quaternary ammonium salts.

[0435] Low molecular weight cationic dispersants are R 21 -N + (-R 22 )(-R 23 )(-R 24 )X - [In the formula, R 21 , R 22 , R 23 and R 24 is hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, X is an anionic group. R 21 , R 22 , R23 and -R 24 Specific examples of X are alkyl groups (e.g., methyl, butyl, stearyl, and palmityl groups). Specific examples of X are halogens (e.g., chlorine) and acids (e.g., hydrochloric acid and acetic acid). The cationic dispersant may be a monoalkyltrimethylammonium salt (alkyl having 4 to 40 carbon atoms).

[0436] Specifically, the low molecular weight cationic dispersant is represented by the formula: R 1 p -N + R 2 q X - [In the formula, R 1 is C12 or higher (e.g. C 12 ~C 50 ) linear and / or branched aliphatic (saturated and / or unsaturated) groups, R 2 is H, a C1-4 alkyl group, a benzyl group, or a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50) (CH3 and C2H5 are particularly preferred), X is a halogen atom (e.g., chlorine), or a C1-C4 fatty acid salt, or a C1-C4 sulfonic acid salt; p is 1 or 2, q is 2 or 3, and p+q=4. R 1 may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0437] Low molecular weight cationic dispersants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride, and the like.

[0438] The polymeric cationic dispersant may be any of various polymers (e.g., polyquaternium-1 to 47) having a cationic group (e.g., ammonium group, quaternary ammonium group). Examples of the polymeric cationic dispersant include cationic starch, cationic cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propyl hydroxyethyl cellulose chloride), cationic guar gum, cationic xanthan gum, chitosan, and other cationic natural products (particularly cationic sugars); aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternary dimethylammonium ethyl methacrylic acid, diallyldimethylammonium chloride, dimethylaminopropylamine, quaternary vinylimidazole, and other cationic group-containing monomer polymers.

[0439] [Anionic dispersant] The dispersant may comprise an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may be free of an anionic dispersant.

[0440] The anionic dispersant may be a low molecular weight or a high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0441] Examples of anionic dispersants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonic acid salts, N-acylamino acid type dispersants, phosphoric acid mono- or diester type dispersants, and sulfosuccinates. Examples of anionic dispersants include carboxylates (e.g., fatty acid salts).

[0442] [Amphoteric dispersant] The dispersant may comprise an amphoteric dispersant, which may be an amphoteric surfactant.

[0443] The amphoteric dispersant may be a low molecular weight or a high molecular weight dispersant. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0444] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amido betaines, and betaine acetate. Specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetate betaine, and fatty acid amidopropyl dimethylamino acetate betaine.

[0445] [Inorganic dispersant] The dispersant may comprise an inorganic dispersant.

[0446] The average primary particle size of the inorganic dispersant may be 5 nm or more, 30 nm or more, 100 nm or more, 1 μm or more, 10 μm or more, or 25 μm or more, and may be 100 μm or less, 50 μm or less, 10 μm or less, 1 μm or less, 500 nm or less, or 300 nm or less. The average primary particle size can be measured, for example, by observation with a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant may be a hydrophilic particle.

[0447] Examples of inorganic dispersants include polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and hydroxyapatite; carbonates such as calcium carbonate and magnesium carbonate; silicates such as calcium metasilicate; sulfates such as calcium sulfate and barium sulfate; and hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

[0448] [Amount of dispersant] The amount of the dispersant may be, relative to 100 parts by weight of the liquid repellent compound, 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

[0449] [Liquid medium] The repellent of the present disclosure may include a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The repellent may be a dispersion or a solution. The repellent of the present disclosure may include at least water.

[0450] Examples of the organic solvent include esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically, naphtha, kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxyl group (e.g., alcohol, polyols such as glycol-based solvents, ethers of polyols (e.g., monoethers), etc.). These may be used alone or in combination of two or more.

[0451] [Amount of liquid medium] The amount of the liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the liquid repellent compound.

[0452] The amount of water may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the liquid repellent compound.

[0453] The amount of the organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the liquid repellent compound.

[0454] 〔silicone〕 The repellent in the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, it is possible to obtain good texture and durability in addition to good liquid repellency.

[0455] As the silicone, known silicones can be used, and examples of silicones include polydimethylsiloxane and modified silicones (amino-modified, epoxy-modified silicone, carboxy-modified silicone, methylhydrogen silicone, etc.). The silicone may be a silicone wax having wax-like properties. These may be used alone or in combination of two or more.

[0456] The weight average molecular weight of the silicone may be 1,000 or more, 10,000 or more, or 50,000 or more, and may be 500,000 or less, 2,500,000 or less, 100,000 or less, or 50,000 or less.

[0457] [Amount of silicone] The amount of silicone may be, relative to 100 parts by weight of the liquid repellent compound, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0458] 〔wax〕 The repellent in the present disclosure may contain a wax. By containing a wax, it is possible to impart good liquid repellency to the substrate.

[0459] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, silicone wax, animal and vegetable wax, mineral wax, etc. Hydrocarbon waxes, particularly paraffin wax, are preferred. Specific examples of compounds constituting the wax include normal alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane), and normal alkenes (e.g., 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene, 1-hentriacontene, 1-dotriacontene, 1-tritriacontene, 1-tetratriacontene, 1-pentatriacontene, 1-hexatriacontene). The carbon number of the compound constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be from 200 to 2000, for example, from 250 to 1500, or from 300 to 1000. These may be used alone or in combination of two or more.

[0460] The melting point of the wax may be 50° C. or higher, 55° C. or higher, 60° C. or higher, 65° C. or higher, or 70° C. or higher, preferably 55° C. or higher, more preferably 60° C. or higher. The melting point of the wax is measured in accordance with JIS K 2235-1991.

[0461] [Amount of wax] The amount of wax may be, relative to 100 parts by weight of the liquid repellent compound, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0462] [Organic acid] The repellent of the present disclosure may contain an organic acid. As the organic acid, a known one may be used. As the organic acid, carboxylic acid, sulfonic acid, sulfinic acid, etc. are preferably mentioned, and carboxylic acid is particularly preferable. As the carboxylic acid, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc. are mentioned, and formic acid or acetic acid is particularly preferable. In the present disclosure, the organic acid may be used alone or in combination of two or more kinds. For example, formic acid and acetic acid may be used in combination.

[0463] [Amount of organic acid] The amount of the organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the liquid repellent compound. The amount of the organic acid may be adjusted so that the pH of the repellent is 3 to 10, for example, 5 to 9, particularly 6 to 8. The repellent may be acidic (pH 7 or less, for example 6 or less).

[0464] [Hardening agent] The repellent of the present disclosure may include a curing agent (an active hydrogen reactive compound or an active hydrogen containing compound).

[0465] The curing agent (crosslinking agent) in the repellent agent can effectively cure the liquid repellent compound. The curing agent may be an active hydrogen reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen reactive group of the liquid repellent compound. Examples of the active hydrogen reactive compound are isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of the active hydrogen-containing compound are hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0466] The curing agent may include an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound acts as a crosslinking agent. Examples of the polyisocyanate compound include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (e.g., a blocked polyisocyanate compound). The blocked isocyanate compound is a compound in which the isocyanate group of the isocyanate compound is masked with a blocking agent to suppress the reaction.

[0467] Examples of aliphatic polyisocyanates are trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-di ... Aliphatic diisocyanates such as cyanatomethyl caproate, and aliphatic triisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, etc. These may be used alone or in combination of two or more.

[0468] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used alone or in combination of two or more.

[0469] Examples of the araliphatic polyisocyanate are araliphatic diisocyanate and araliphatic triisocyanate.Specific examples of the araliphatic polyisocyanate are 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene.These may be used alone or in combination of two or more.

[0470] Examples of aromatic polyisocyanates are aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates are m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used alone or in combination of two or more.

[0471] Examples of the polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biurets, allophanates, carbodiimides, uretdione, uretoimine, isocyanurates, iminooxadiazinedione, etc. These may be used alone or in combination of two or more.

[0472] These polyisocyanates can be used alone or in combination of two or more. As the polyisocyanate compound, it is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of the polyisocyanate compound is blocked with a blocking agent. It is preferable to use a blocked polyisocyanate compound because it is relatively stable even in a solution and can be used in the same solution as the repellent.

[0473] The blocking agent blocks free isocyanate groups. When the blocked polyisocyanate compound is heated to, for example, 100°C or higher, for example, 130°C or higher, the isocyanate group is regenerated and can easily react with the hydroxyl group. Examples of the blocking agent include phenol-based compounds, lactam-based compounds, aliphatic alcohol-based compounds, and oxime-based compounds. The polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0474] The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. The chloromethyl group-containing compound is a compound having a chloromethyl group. An example of the chloromethyl group-containing compound is chloromethyl polystyrene. The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound include (poly)acrylic acid and (poly)methacrylic acid.

[0475] Specific examples of the ketone group-containing compound include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of the hydrazide compound include hydrazine, carbohydrazide, adipic acid hydrazide, and the like. Specific examples of the melamine compound include melamine resins and methyl etherified melamine resins.

[0476] [Amount of hardener] The amount of the curing agent may be, relative to 100 parts by weight of the liquid repellent compound, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0477] [Other ingredients] The repellent may contain other components in addition to the above components. Examples of the other components include polysaccharides, paper strength agents, flocculants, retention aids, coagulants, binder resins, slip prevention agents, sizing agents, paper strength agents, fillers, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above-mentioned components, other components include other water and / or oil repellents, dispersants, texture adjusters, softeners, flame retardants, paint fixing agents, anti-wrinkle agents, drying speed adjusters, crosslinking agents, film-forming agents, compatibilizers, antifreeze agents, viscosity adjusters, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrink prevention agents, laundry wrinkle prevention agents, shape retention agents, drape retention agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, dye transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, dirt removers, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Ciba Specialty Chemicals' Chinopearl CBS-X), dye fixatives, and discoloration inhibitors such as 1,4-bis(3-aminopropyl)piperazine. The following can be blended: stain removers, enzymes such as cellulase, amylase, protease, lipase, keratinase, etc. as fiber surface modifiers, foam inhibitors, silk protein powders, their surface modified products or emulsified dispersions (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemicals), hydrolyzed silk liquid (Jomo), Silkgen G Soluble S (Ichimaru Falcos)), stain prevention agents (e.g., nonionic polymer compounds consisting of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by GOO Chemical Industry Co., Ltd., SRC-1 manufactured by Clariant Japan, etc.), etc. These may be used alone or in combination of two or more.

[0478] [Polysaccharides] Examples of polysaccharides include starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, chitin nanofiber, cellulose nanofiber, pullulan, etc. The polysaccharide may be a substituted modified polysaccharide (excluding the above-mentioned liquid repellent compounds), in particular a modified polysaccharide into which a hydroxyl group or a cationic group has been introduced.

[0479] [Paper strength agents, flocculants, retention aids or coagulants] Examples of paper strength enhancers, flocculants, retention improvers or coagulants include styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichlorides and polyalkylene polyamines, dicyandiamide-formaldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0480] [Sizing agent] Examples of sizing agents include cellulose-reactive sizing agents, e.g., rosin-based sizing agents such as rosin-based soaps, rosin-based emulsions / dispersions, cellulose-reactive sizing agents, e.g., emulsions / dispersions of acid anhydrides such as alkyl and alkenyl succinic anhydrides (ASA), alkenyl and alkyl ketene dimers (AKD) and polymers, and anionic, cationic and amphoteric polymers of ethylenically unsaturated monomers, e.g., copolymers of styrene and acrylates.

[0481] [Antistatic agent] Examples of the antistatic agent include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfates, phosphonates, and phosphates; amphoteric antistatic agents such as alkylbetaines and their derivatives, imidazolines and their derivatives, alanines and their derivatives, nonionic antistatic agents such as aminoalcohols and their derivatives, glycerin and its derivatives, and polyethylene glycols and its derivatives. The antistatic agent may be an ion-conductive polymer obtained by polymerizing or copolymerizing monomers having these cationic, anionic, or amphoteric ion-conductive groups. These may be used alone or in combination of two or more.

[0482] [Preservatives] The preservatives are mainly used to enhance the preservative and bactericidal power and maintain the preservative properties during long-term storage. Examples of the preservatives include isothiazolone organic sulfur compounds, benzisothiazolone organic sulfur compounds, benzoic acids, 2-bromo-2-nitro-1,3-propanediol, etc.

[0483] [Ultraviolet absorber] An ultraviolet absorber is a drug that has an ultraviolet protection effect, and is a component that absorbs ultraviolet light and converts it into infrared light, visible light, etc. Examples of ultraviolet absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, 4-t-butyl-4'-methoxybenzoylmethane, etc.

[0484] [Antibacterial agents] Antibacterial agents are components that have the effect of suppressing the growth of bacteria on fibers and further suppressing the generation of unpleasant odors resulting from the decomposition products of microorganisms. Examples of antibacterial agents include cationic bactericides such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide) zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, polylysine, etc.

[0485] [Deodorant] Examples of deodorants include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, and aminocarboxylic acid metal complexes (zinc complex of trisodium methylglycinediacetate described in WO 2012 / 090580).

[0486] [Amount of other ingredients] The amount or total amount of the other components may be, relative to 100 parts by weight of the liquid repellent compound, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0487] Although the embodiments have been described above, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims. EXAMPLES

[0488] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0489] <Test Method> The test procedure is as follows.

[0490] [Practical oil resistance test] The mold was pretreated by storing it at 23°C and 50% humidity for 12 hours. 100 ml of corn oil at 65°C was poured into the mold, and after leaving it at room temperature for 45 minutes, the corn oil was removed from the mold and the degree of oil staining of the mold was evaluated. The following evaluation values ​​were set depending on the degree of staining. 5: No stains on the inside. 4: Stain on the inside. No stain on the back. 3: Stain on the inside. Slight seepage on the back. 2: Stain on the inside. Less than 50% of the area has seeped through to the back. 1: Stain on the inside. Stain on the back is 50% or more but less than 100% of the area. 0: Seeping through to the entire back side.

[0491] [Practical water resistance test] The mold was pretreated by storing it for 12 hours under conditions of 23°C and 50% humidity. 100ml of 100°C water was poured into the mold, and after leaving it at room temperature for 30 minutes, the water was removed from the mold and the degree of staining of the mold was evaluated. The following evaluation values ​​were set depending on the degree of staining. 5: No stains on the inside 4: Stain on the inside. No stain on the back. 3: Stain on the inside. Slight seepage on the back. 2: Stain on the inside. Less than 50% of the area has seeped through to the back. 1: Stain on the inside. Stain on the back is 50% or more but less than 100% of the area. 0: Seeping through to the entire back side.

[0492] [Adhesion amount evaluation] The amount of the liquid repellent compound attached to the pulp mold is less than the amount of the liquid repellent compound added. The amount of the attached liquid repellent compound can be calculated by the following procedure. In the first step, the paper plate of the pulp mold is weighed. In the second step, an internal standard (for example, toluene or DMF) is added to a solvent (for example, chloroform) in which the liquid-repellent compound dissolves to create an evaluation solvent. In the third step, the evaluation solvent is weighed, the weighed paper plate is immersed in it, and heated as necessary to extract the liquid-repellent compound. In the fourth step, a portion of the solution in which the liquid-repellent compound has been extracted is taken out, diluted with a heavy solvent, and 1H-NMR measurement is performed. If a heavy solvent is used as the evaluation solvent, the solution in which the liquid-repellent compound has been extracted is measured as is without dilution. The amount of liquid-repellent compound attached to the mold is calculated from the obtained 1H-NMR measurement results.

[0493] <Examples 1-1 to 1-5, Comparative Example 1-1> [Preparation of repellent] As a liquid repellent compound, 2 g of decaglycerol dodecabehenyl ester (polymerization degree 10, hydroxyl group substitution rate: 12 / 12*100 [100%], bio-based ratio: 100%, melting point: 69°C), 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 to 16 HLB: 7), and 17.8 g of water were mixed to obtain a precursor A of a water-dispersed repellent. This precursor A of a water-dispersed repellent was heated to 80°C, and then cooled while stirring with a magnetic stirrer to obtain a precursor B of a water-dispersed repellent. The precursor B of a water-dispersed repellent was treated twice under conditions of 80 MPa in a high-pressure wet microparticulation device to obtain a water-dispersed repellent. The volumetric ratio of particles of 100 μm or more in the obtained water-dispersed repellent was 2%, and the median diameter D50 was 16.2 μm.

[0494] [Preparation of pulp composition (pulp slurry)] 1300 ml of water was added to 700 g of a 1.4% by weight aqueous dispersion of a mixture of 70 parts of bleached hardwood kraft pulp and 30 parts of bleached softwood kraft pulp beaten to a freeness of 550 cc (Canadian freeness). With stirring, the water-dispersed repellent obtained above and a liquid repellent compound were added in an amount of 3 parts by weight in terms of solid content concentration per pulp weight to prepare a pulp composition.

[0495] [Making pulp molds] A pulp mold was formed using an automatic molding machine. A mesh body was placed on a metal pulp mold forming die with many suction holes at the bottom, and a metal tank was placed at the top, with the pulp composition being placed in the upper metal tank. The pulp composition was sucked and dehydrated through the pulp mold forming die and mesh body by a vacuum pump from the side opposite to the side where the mesh body was placed in the pulp mold forming die, and the solid content (pulp, etc.) contained in the pulp composition was deposited on the mesh body to obtain a pulp mold intermediate. Next, the obtained pulp mold intermediate was heated from above and below using heated male and female metal molds under a pressure of 0.3 MPa at 80°C for 10 seconds (preheating), followed by a first heating at the temperature and time shown in the table below, and then heated and dried until the amount of liquid medium was 10% by weight, yielding a pulp mold (a deep-dish shaped paper plate). Thereafter, the pulp mold was left at room temperature until its temperature reached room temperature (15 to 40° C.) (first cooling). Subsequently, the pulp mold after the first cooling was subjected to a second heating under the conditions shown in the table below. The pulp mold obtained after the second heating was returned to room temperature (after the second cooling), and then the above-mentioned tests were carried out. The results are shown in the following table.

[0496] TIFF2025044132000022.tif130164

[0497] The amount of the liquid repellent compound attached in Example 1-3 was 1.9% by weight based on the weight of the pulp.

[0498] <Examples 2-1 to 2-3, Comparative Examples 2-1 to 2-2> [Preparation of repellent] As the liquid repellent compound, a compound having the following formula: 2 g of dry-ground ethylene bisstearic acid amide powder (biobased content: 97%, melting point: 143°C) represented by TIFF2025044132000023.tif1863, 0.2 g of polyethylene glycol trimethyl nonyl ether (HLB13), and 17.8 g of water were mixed to obtain a water-dispersible repellent (volume abundance ratio of particles 100 μm or larger: 4.5%, volume median diameter: 19.2 μm).

[0499] [Preparation of pulp composition (pulp slurry)] 1300 ml of water was added to 700 g of a 1.4% by weight aqueous dispersion of a mixture of 70 parts of bleached hardwood kraft pulp and 30 parts of bleached softwood kraft pulp beaten to a freeness of 550 cc (Canadian freeness). With stirring, the above-obtained aqueous dispersion-type repellent and 1 part by weight of a liquid repellent compound in terms of solid content concentration were added per pulp weight to prepare a pulp composition.

[0500] [Making pulp molds] Pulp molds were prepared and tests were carried out in the same manner as in Example 1-1, except that the above pulp composition was used and the heating and cooling treatment was carried out under the conditions shown in the following table. The results are shown in the following table. TIFF2025044132000024.tif82164

Claims

1. a first heating step of heating a pulp composition containing pulp and a liquid repellent compound to a first heating temperature to obtain a precursor product in which the liquid repellent compound is adhered to the pulp; a first cooling step of cooling the precursor product to a first cooling temperature to obtain a cooled precursor product; and a second heating step of heating the cooled precursor product to a second heating temperature to obtain a pulp product; A method for producing a pulp product comprising:

2. The first heating temperature is 40° C. or more, The first cooling temperature is less than 40° C., The method for producing a pulp product according to claim 1 , wherein the second heating temperature is 40° C. or higher.

3. the first heating temperature is equal to or higher than the melting point of the liquid repellent compound, The method for producing a pulp product according to claim 1 or 2, wherein the first cooling temperature is below the melting point of the liquid repellent compound.

4. The method for producing a pulp product according to claim 3, wherein the second heating temperature is 0.7 times or more the melting point of the liquid repellent compound.

5. The method for producing a pulp product according to claim 3, wherein the second heating temperature is equal to or higher than the first cooling temperature +30°C and equal to or higher than the melting point of the liquid repellent compound -50°C.

6. the first heating temperature is equal to or higher than the melting point of the liquid repellent compound, The first cooling temperature is less than 40° C., 3. The method for producing a pulp product according to claim 1, wherein the second heating temperature is not less than the melting point of the liquid repellent compound minus 50°C and not more than the melting point of the liquid repellent compound plus 100°C.

7. the pulp composition comprises a liquid medium; The method for producing a pulp product according to claim 1 or 2, wherein in the first heating step, the liquid medium is removed until the amount of the liquid medium in the pulp composition is 10% by weight or less.

8. In the first heating step, the pulp composition is shaped, The method for producing a pulp product according to claim 1 or 2, wherein the precursor product is a pulp mould.

9. The method for producing a pulp product according to claim 1 or 2, wherein the bio-based content of the liquid repellent compound is 30% or more.

10. The method for producing a pulp product according to claim 1 or 2, wherein the liquid repellent compound is a compound having a hydrocarbon group having 6 to 40 carbon atoms.

11. The method for producing a pulp product according to claim 1 or 2, wherein the liquid repellent compound is at least one selected from the group consisting of fatty acid esters, fatty acid amides, linear hydrocarbons, and vinyl polymers.

12. The pulp composition contains at least one repellent selected from the group consisting of a water-resistant agent, an oil-resistant agent, a water-repellent agent, an oil-repellent agent, and a stain-resistant agent; The method for producing a pulp product according to claim 1 or 2, wherein the repellent agent comprises the liquid repellent compound.

13. The method for producing a pulp product according to claim 12, wherein the repellent agent is at least one selected from the group consisting of a water-resistant agent and an oil-resistant agent.

14. The method of claim 12 , wherein the repellent agent comprises a dispersant and water.

15. The method for producing a pulp product according to claim 1 or 2, wherein the pulp product has the liquid repellent compound added thereto.

16. The method for producing a pulp product according to claim 1 or 2, wherein the amount of the liquid repellent compound attached to the pulp product is 3.0% by weight or less.

17. the liquid repellent compound is a polyol-modified compound or an amine-modified compound, The polyol modification product is a product in which a hydroxy group possessed by a polyglycerol having a polymerization degree of 1 to 15 is converted into a hydroxy group represented by the following formula: -O-C(=O)-Z Ｏ [In the formula, Z Ｏ is an alkyl group having 14 to 24 carbon atoms. is a compound substituted with a group represented by the hydroxyl group substitution rate in the modified polyol is 50% or more, The amine modification has the following formula: N(-C(=O)-Z N ) p (-H) q -L 1 -[N(-C(=O)-Z N ) r (-H) s -L 1 -] t -N(-C(=O)-Z N ) p (-H) q [In the formula, Z Ｎ is independently in each occurrence an alkyl group having from 14 to 24 carbon atoms; L 1 is independently in each occurrence a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms; p, in each occurrence, is independently an integer between 1 and 2, inclusive; q is independently in each occurrence 0 or 1; p+q is each N(-C(=O)-Z N ) p (-H) q In the above, r is independently in each occurrence 0 or 1; s is independently in each occurrence 0 or 1; r+s is each N(-C(=O)-Z N ) r (-H) s In t is an integer of 0 to 3. The method for producing a pulp product according to claim 1 or 2, wherein the compound is represented by the formula:

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