Method for manufacturing pulp product

Abstract

Provided is a novel method for manufacturing a pulp product endowed with liquid repellency by using a method for manufacturing a pulp product, said method 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.

Description

Pulp product manufacturing method

[0001] FIELD OF THE DISCLOSURE The present disclosure relates to a method for producing a pulp product.

[0002] Patent Document 1 discloses that a method for manufacturing 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 up, before or while vacuum suction is being applied to the backside of the pulp molded body, can enhance the effects of the coating agent (waterproofness, strength, etc.) and be economical.

[0003] Japanese Patent Application Laid-Open No. 2002-129499

[0004] Patent Document 1 does not mention or suggest the use of multiple heating steps or a cooling step in the manufacturing process, nor does it consider the oil resistance of the product.

[0005] An object of the present disclosure is to provide a novel method for producing a pulp product that has been given liquid repellency.

[0006] The present disclosure includes the following aspects: [Item 1] A method for producing a pulp product, comprising: 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. [Item 2] The method for producing a pulp product according to Item 1, wherein the first heating temperature is 40°C or higher, the first cooling temperature is lower than 40°C, and the second heating temperature is 40°C or higher. [Item 3] The method for producing a pulp product according to Item 1 or 2, wherein the first heating temperature is equal to or higher than the melting point of the liquid-repellent compound, and the first cooling temperature is lower than the melting point of the liquid-repellent compound. [Item 4] The method for producing a pulp product according to Item 3, wherein the second heating temperature is 0.7 times or higher than the melting point of the liquid-repellent compound. [Item 5] 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 minus 50°C. [Item 6] The method for producing a pulp product according to any one of Items 1 to 5, wherein 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, and the second heating temperature is equal to or higher than the melting point of the liquid repellent compound minus 50°C and equal to or lower than the melting point of the liquid repellent compound +100°C. [Item 7] The method for producing a pulp product according to any one of Items 1 to 6, wherein the pulp composition contains a liquid medium, and the amount of the liquid medium in the pulp composition is removed in the first heating step until it is 10% by weight or less. [Item 8] The method for producing a pulp product according to any one of Items 1 to 7, wherein the pulp composition is molded in the first heating step, and the precursor product is a pulp mold. [Item 9] The method for producing a pulp product according to any one of Items 1 to 8, wherein the biobased content of the liquid repellent compound is 30% or more. [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 from 6 to 40 carbon atoms. [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.[Item 12] The method for producing a pulp product according to any one of Items 1 to 11, wherein the pulp composition contains at least one repellent selected from the group consisting of a water-proofing agent, an oil-proofing agent, a water-repellent agent, an oil-repellent agent, and an antifouling agent, and the repellent contains the liquid-repellent compound. [Item 13] The method for producing a pulp product according to any one of Items 12, wherein the repellent is at least one selected from the group consisting of a water-proofing agent and an oil-proofing agent. [Item 14] The method for producing a pulp product according to any one of Items 12 or 13, wherein the repellent contains a dispersant and water. [Item 15] The method for producing a pulp product according to any one of Items 1 to 14, wherein the liquid-repellent compound is internally added to the pulp product. [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. [Item 17] The liquid repellent compound is a polyol-modified compound or an amine-modified compound, and the polyol-modified compound converts a hydroxy group of a polyglycerin having a polymerization degree of 1 to 15 into a hydroxy group of the following formula: -O-C(=O)-Z. Ｏ [In the formula, Z Ｏ is an alkyl group having 14 to 24 carbon atoms.], wherein the hydroxy group substitution rate in the polyol modified product is 50% or more, and the amine modified product is a compound substituted with a group represented by 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; 1 is independently in each occurrence a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, p is independently in each occurrence an integer of 1 to 2, q is independently in each occurrence 0 or 1, and p+q is independently in each occurrence an integer of 1 to 2, N )p (-H) q In the formula, r is 2, r in each occurrence is independently 0 or 1, s in each occurrence is independently 0 or 1, and r+s is each N(-C(=O)-Z N ) r (-H) s Item 17. The method for producing a pulp product according to any one of Items 1 to 16, wherein the compound is a compound represented by the formula:

[0007] According to the present disclosure, a pulp product having liquid repellency can be produced.

[0008] <Definition of Terms> As used herein, an "n-valent group" refers to a group having n bonds, i.e., a group that forms n bonds. Furthermore, an "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. A hydrocarbon group derivative refers to a group having one or more of N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc. at the end or molecular chain of the hydrocarbon group.

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

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

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

[0012] <Method for manufacturing a pulp product> The method for manufacturing a pulp product in 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 adheres 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.

[0013] In one embodiment of the present disclosure, a pulp product can be produced that is imparted with good liquid repellency (particularly high-temperature oil resistance). 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 the active ingredient of the repellent, adheres to the interior 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 at 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 a Pulp Molded Intermediate: A mesh is placed on a metal pulp mold die provided with suction holes for the slurry, and a pulp slurry is poured into the mesh. A liquid-repellent compound may be added to the pulp slurry. The pulp slurry is sucked and dehydrated through the pulp mold die and mesh to prepare a pulp molded intermediate. (2) Drying of the Pulp Molded Intermediate: The obtained pulp molded intermediate is dried from above and below under a predetermined pressure (e.g., 0.1 to 1 MPa) in a metal male-female mold heated to a predetermined temperature (first heating temperature, e.g., 60 to 200°C). This allows the production of a molded body (pulp mold) formed into the shape of a container.

[0019] The heating method in the first heating step is not limited, but examples thereof include heat pressing, hot air drying, oven heating, etc., and heat pressing is preferably used.

[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 first heating temperature may be 500° C. or less, 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 preferably −10° C. or higher, 0° C. (melting point) or higher. or +10°C or higher, particularly 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, 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 relative to the melting point of the liquid-repellent compound, and is 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 (e.g., 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, even 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, even more preferably 120°C or higher, even more preferably 140°C or higher, even more preferably 160°C or higher, and may be 250°C or lower, preferably 200°C or lower, more preferably 180°C or lower.

[0024] The time for which the first heating temperature is maintained is not particularly limited, and 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 preferably be 1 hour or less, 30 minutes or less, 10 minutes or less, or 5 minutes or less.

[0025] [First Cooling Step] 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 carried out while pressurizing the precursor product (for example, 0.1 to 1 MPa) or without pressurization. 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 then cooled. Preferably, the precursor product is removed from the mold and then 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, or 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, 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 (e.g., 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 also 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, and is 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 relative to the melting point of the liquid repellent compound.

[0031] The first cooling temperature may be −300° C. or higher, −275° C. or higher, −250° C. or higher, −225° 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, or −25° C. or higher, and may be −10° C. or lower, −30° C. or lower, −50° C. or lower, −75° C. or lower, −100° C. or lower, −125° C. or lower, −150° C. or lower, −175° C. or lower, −200° C. or lower, −225° C. or lower, or −250° C. or lower, and is preferably −75° C. or lower or −150° C. or lower, relative to the first heating temperature.

[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, even more preferably 10 minutes or more, and may be 1 hour or more. 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 the 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 carried out while applying pressure (for example, 0.1 to 1 MPa) to the cooled precursor product, or may be carried out without applying pressure. Preferably, pressure is not applied. For example, when heating the cooled precursor product, the cooled precursor product may be heated in the mold used in the previous step, or may be heated after being removed from the mold. Preferably, the cooled precursor product is heated after being removed from the mold.

[0036] The heating method in the second heating step is not limited, but includes 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 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 or higher, 290°C or higher, or 300°C or higher, and is preferably 40°C or higher. ° 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, The temperature 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 relative to the melting point of the liquid-repellent compound, and is 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 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 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, or 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, relative to the first heating temperature.

[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 relative to the first cooling temperature, 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.

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

[0043] The time for which the second heating temperature is maintained 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 which the second heating temperature is maintained 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 wt% or more, 0.3 wt% or more, 0.5 wt% or more, 0.75 wt% or more, 1.0 wt% or more, 2.0 wt% or more, or 3.0 wt% or more, or may be 10 wt% or less, 7.5 wt% or less, 5.0 wt% or less, 4.0 wt% or less, 3.0 wt% or less, 2.0 wt% or less, 1.0 wt% or less, 0.75 wt% or less, or 0.5 wt% or less, preferably 3.0 wt% or less. According to the present disclosure, good liquid repellency can be achieved even when the amount of the liquid-repellent compound is reduced.

[0045] Pulp Composition Preparation Step The method for producing a pulp product according to the present disclosure may include a step of treating a pulp base material with a repellent to obtain a pulp composition.

[0046] The pulp base material can be treated by an internal treatment method in which a repellent is added to pulp before papermaking (e.g., pulp slurry), or an external treatment method in which a repellent is applied to pulp after papermaking (e.g., pulp product). Examples of internal treatments include mixing and immersion, and may include a step of adding a repellent to a pulp slurry and stirring and mixing it.

[0047] Examples of the external addition treatment method include spraying and coating, 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 molded paper products made from recycled paper pulp such as recycled newspaper, recycled magazine paper, recycled corrugated cardboard, and deinked recycled paper. Specific examples of pulp products include food packaging materials, food containers, gypsum board base paper, coated base paper, medium-quality paper, general liners and 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 contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent, and is typically an aqueous medium, particularly water. The liquid medium may also contain a liquid medium derived from 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 contains a liquid-repellent compound. The repellent will be described in detail in the section <Repellent> below. The amount of the repellent 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 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, relative to 100 parts by weight of pulp, 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.

[0054] The amount of the liquid-repellent compound which is a fatty acid ester may be 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, relative to 100 parts by weight of pulp, 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 fatty acid amide liquid repellent compound may be 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, relative to 100 parts by weight of pulp, 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 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, relative to 100 parts by weight of pulp, 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 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, relative to 100 parts by weight of pulp, 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.

[0058] The amount of the polyol-modified liquid-repellent compound may be 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, relative to 100 parts by weight of pulp, 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 parts by weight or less.

[0059] The amount of the polycarboxylic acid-modified liquid-repellent compound may be 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, relative to 100 parts by weight of pulp, 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.

[0060] The amount of the liquid-repellent compound which is a vinyl polymer may be 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, relative to 100 parts by weight of pulp, or 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 Above, 0.03g / m ２ Above, 0.05g / m ２ Above, 0.1g / m ２ Above, 0.3g / m ２ Above, 0.5g / m ２ or more, or 1.0 g / m ２ or more, and ２ Below, 4.0g / m ２ Below, 3.0g / m ２ Below, 2.0g / m ２ Below, 1.0g / m ２ Below, 0.5g / m ２ Below, 0.3g / m ２ or less, or 0.1 g / m ２ It may be the following:

[0062] [Additives] In addition to the pulp and the repellent (liquid-repellent compound), the pulp composition may contain additives used in the production 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 defoaming agents. Specific examples of additives include alkyl ketene dimers, alkenyl succinic anhydrides, styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, starch, modified starch, carboxymethyl cellulose, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichloride and polyalkylene polyamines, dicyandiamide-formaldehyde condensates, dimethyldiallylammonium chloride polymers, olefin / maleic anhydride polymers, etc. The pulp composition contains components derived from the repellent, but each component contained in the repellent may be added separately 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 from -10,000 to 10,000 μeq / g, preferably from -4,000 to 8,000 μeq / g, and more preferably from -1,000 to 7,000 μeq / g. For paper substrates containing cationic additives relative to pulp, the repellent may be anionic, and for paper substrates containing anionic additives, 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 Steps] 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 included. For example, when adjusting the humidity and temperature of the molded pulp product, the molded pulp product after the second heating may be placed in a thermo-humidistat chamber adjusted to 10°C or higher and a humidity of 20% or higher, and stored for 30 minutes or longer. The adjusted temperature is preferably 15°C or higher and 30°C or lower, and the adjusted humidity is 20% or higher but lower than 60%, but is not limited thereto.

[0066] <Repellent Agent> The repellent agent of the present disclosure adheres to a substrate (particularly a pulp substrate) and can impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the substrate, and can also function as a water resistance agent, oil resistance agent, water repellent agent, oil repellent agent, and / or stain resistance agent. The repellent agent of the present disclosure includes a liquid repellent compound. The liquid repellent compound may be used as the repellent agent itself, 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 abundance ratio of particles of 100 μm or larger in the repellent agent of the present disclosure, as measured by laser diffraction scattering, may be 0.1% or larger, 0.3% or larger, 0.5% or larger, 1% or larger, 1.5% or larger, 3% or larger, 4% or larger, 5% or larger, or 10% or larger, or may be 50% or smaller, 30% or smaller, 20% or smaller, 15% or smaller, 10% or smaller, 5% or smaller, 3% or smaller, or 1.5% or smaller. The method for achieving the volumetric abundance ratio of particles of 1 μm or larger, as measured by laser diffraction scattering, within the above range is not limited, and may involve, for example, micronizing the particles in the raw material and / or dispersion using a grinder, homogenizer, or the like.

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

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

[0071] [Characteristics, etc.] The characteristics, etc. that the liquid repellent compound may have are listed below. These characteristics, etc. 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, it can impart good liquid repellency (particularly oil repellency) to the substrate. The HD contact angle is the static contact angle of the liquid-repellent compound with respect to a spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle 1 second after the drop has landed.

[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, it can impart good liquid repellency (particularly water repellency) to the substrate. The water contact angle is the static contact angle of the liquid-repellent compound with respect to a spin-coated film, and is obtained by dropping 2 μL of water on 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 containing carbon of biobased origin. The biobased content is measured in accordance with ASTM D6866. The biobased content 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 content means that the amount of fossil resource-based materials, such as petroleum, used is small. From this perspective, the higher the biobased content of the liquid-repellent compound, the better.

[0075] The biodegradability of the liquid-repellent compound after 180 days is preferably 5% or more. Since this reduces the environmental impact, 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 this reduces the environmental impact, 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 biodegradability as defined in JIS K 6953-1 or ASTM D6400.

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

[0077] [Structure, etc.] The liquid-repellent compound in the present disclosure does not necessarily 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 a 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 (e.g., an alkyl group) having 6 to 40 carbon atoms.

[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 from 1 to 40 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, 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, 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, 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' and -N(R'). ２ , —COOR′, and halogen atoms (wherein R′, in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, the hydrocarbon group may have 1 to 3 (e.g., 1) —OR′ (particularly —OH) as a substituent (e.g., other than at the terminal).

[0083] (Monovalent Polysiloxane Group) The liquid repellent compound may have a monovalent polysiloxane group. Like a (monovalent) hydrocarbon group, the (monovalent) polysiloxane group can impart liquid repellency to the substrate.

[0084] The polysiloxane group has the following formula: —[—Si(R ｓ ) ２ -O-] ａ - [wherein, R ｓ is independently in each occurrence a hydrocarbon group or a reactive group having 1 to 40 carbon atoms, and a is an integer of 5 or more and 10,000 or less.

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

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

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

[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 It may be 20 mol% or more, 40 mol% or more, 60 mol% or more, or 80 mol% or more, preferably 50 mol% or more, and may be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less, based on the total of R ｓ With respect to the total number of groups, 50 mol % or more may be methyl groups 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 ｓand may be 100 mol % or less, 90 mol % or less, 80 mol % or less, or 70 mol % or less, based on the total of

[0093] In the polysiloxane group, the reactive 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

[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. The R of the terminal structure 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 -O-Lｓ１ -[-Si(R ｓ ) ２ -O-] ａ -R ｓ -L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -Si(R ｓ ) ３ -L ｓ１ -O-L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -R ｓ -L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -Si(R ｓ ) ３、 -L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -R ｓ [In the formula, R ｓ is independently in each occurrence a hydrocarbon group or a reactive group having 1 to 40 carbon atoms, and the terminal R ｓ has one or more reactive groups, and R ｓ 50 mol % or more of the total groups are methyl groups, and L ｓ１ is a hydrocarbon group having 1 to 20 carbon atoms, and a is 5 or more and 10,000 or less. [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.]

[0098] [Examples of Liquid-Repellent Compounds] Examples of liquid-repellent compounds include compounds having a hydrocarbon group having a carbon number of 6 to 40. Examples and preferred ranges of the hydrocarbon group 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 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 include 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, or an imide group). For example, the liquid repellent compound may include —C(═O)—O—, —O—C(═O)—, —C(═O)—NR′—, —O—C(═O)—NR′—, —NR′—C(═O)—NR′—, or —SO ２ The liquid repellent compound may contain NR'- (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)). 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 contain an amide structure. When the liquid repellent compound contains at least an amide structure, the liquid repellency can be improved. Here, the amide structure may be an amide structure in a broad sense, and may be selected from amide structures in amide (acid amide) groups, urethane groups, urea groups, imide groups, thioamide groups, thiourethane groups, thiourea groups, thioimide groups, sulfonamide groups, sulfoneurethane groups, sulfoneurea groups, sulfonimide groups, etc. The amide structure is -(C=O)N(-) ２, -(C=S)N(-) ２ , and -S(=O) ２ N (-) ２ (Note that each group may be inverted). At least one of the bonds of N in the amide structure may be bonded to a hydrogen atom. The amide structure is preferably -(C=O)N(-) ２ and may be an amide structure in a group selected from the group consisting of an amide group, a 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 agent 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, or 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 agent.

[0103] [Amine-modified compound] As an example of a liquid-repellent compound, an amine-modified compound will be described. The amine-modified compound is a compound obtained by chemically modifying an amine compound so as to exhibit liquid-repellency.

[0104] Due to their structure, the amine-modified compounds disclosed herein have excellent dispersibility in liquid media, and the repellents disclosed herein can have stable performance. Repellents that use polymeric compounds as active ingredients tend to have broad molecular weight distributions and contain relatively large amounts of impurities. On the other hand, amine-modified compounds can be made into low-molecular-weight compounds, narrowing (uniformizing) the molecular weight distribution, and can therefore have good performance.

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

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

[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 descriptions of the (monovalent hydrocarbon group which may have a substituent) and (monovalent polysiloxane group) are incorporated herein by reference.

[0111] (Amine skeleton) The amine modified product in the present disclosure has an amine skeleton. The amine skeleton has one or more amino groups with a predetermined number of bonds (valence) obtained by removing a predetermined number of atoms or atomic groups (e.g., hydrogen) from an amine compound. The amino group in the amine skeleton has one or more —NH ２ , -NH-, and -N(-) ２and includes an amino group adjacent to a carbonyl group contained in an amide group, a urethane group, a urea group, an imide group, etc. The amine skeleton may be an aliphatic or 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, 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 has the structure -NH ２ , -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 (e.g., saturated). Here, the hydrocarbon group may be interrupted by oxygen atoms and / or sulfur atoms, or may consist of only carbon atoms, nitrogen atoms, and hydrogen atoms. The hydrocarbon group may be a hydrocarbon group that may be interrupted by oxygen atoms and / or sulfur atoms (e.g., a chain-like saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having one to two hydrocarbon aromatic rings), or may be a general hydrocarbon group (e.g., a chain-like saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having one to two hydrocarbon aromatic rings). When the hydrocarbon group is interrupted by oxygen atoms and / or sulfur atoms, it has an ether, thioether, polyether, or polythioether structure. The number of hydrocarbon groups in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and may be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0116] The amine skeleton may be composed of a monovalent to trivalent amino group and a chain saturated aliphatic hydrocarbon group or 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-modified compound in the present disclosure is represented by the following formula: Ｎ -Z Ｎ ｎ [In the formula, Y Ｎ is a direct bond or a group having a valence of 1+n; Z Ｎis a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, and n is an integer of 1 to 3.] Ｎ -Z Ｎ ｎ is bonded to the nitrogen atom of the amine skeleton.

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

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

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

[0122] n is Y Ｎ Z combines with Ｎand may be an integer of 1 or more and 3 or less. n may be 1 or more, 2 or more, or 3 or more, and may 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 or saturated) or an aromatic group.

[0124] Y Ｎ The molecular weight of may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more, and may be 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: -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'- -C(=O)-NR'- -C(=O)-NR'-C(=O)- (wherein 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).) Ｎ is preferably bonded to the nitrogen atom in the amine skeleton via a —(C═O)— group.

[0126] Y Ｎ represents a direct bond, —O—, —C(═O)—, —C(═NR′)—, —S—, —S(═O) ２ -, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , -N(-) ２a di- to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a di- to tetravalent hydrocarbon aromatic ring, and a di- to tetravalent heterocyclic ring (wherein 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)).

[0127] Y Ｎ Is Y Ｎ１ and Y Ｎ２ Y is a 1+n valent group consisting of one or more groups selected from the group consisting of Ｎ１ represents 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), and Y Ｎ２ is a group consisting of one or more selected from the group consisting of divalent to tetravalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, divalent to tetravalent hydrocarbon aromatic rings, and divalent to tetravalent heterocycles, and may be a 1+n-valent group consisting of one or more selected from the group consisting of. Ｎ The group shown as follows has an amine skeleton on the left and Z on the right. Ｎ Combine with.

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

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

[0130] Y Ｎ１The molecular weight of may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0131] Y Ｎ１ represents 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).) Ｎ１ Examples of include a direct bond, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′-C(═O)—O—, —NR′-C(═O)—NR′—, —C(═O)—O—, —C(═O)—NR′—, —C(═O)—NR′—, —C(═O)—NR′—C(═O)—NR′—, —C(═NR′)—, —S—, and —SO ２ -, -SO ２ NR'-, -C(OR')R'-, -C(OR')(-) ２ , -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).] Ｎ１ is bonded to a nitrogen atom of the amine skeleton, the nitrogen atom is considered to be part of the amine skeleton (amino group).

[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 heterocyclic ring which may have a substituent.

[0133] Y Ｎ２ Y may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). Ｎ２Y may be aliphatic or aromatic. Ｎ２ may be linear, branched or cyclic.

[0134] Y Ｎ２ is a divalent or higher valent group. Ｎ２ The valency of may be, for example, 2-4, 2-3, 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 carbon atoms, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

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

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

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

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

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

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

[0144] Y Ｎ２ Specific examples of -(CH ２ ) 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, -(CH ２ ) ｑ -Cy-(CH ２ ) ｒ -(q and r each independently represent a number from 0 to 20, for example, from 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle), and the like.

[0145] ・Y Ｎ Example of 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 When is divalent, -Y Ｎ１ -, -Y Ｎ１ -Y Ｎ２ -, -Y Ｎ１ -Y Ｎ２ -Y Ｎ１ -, -Y Ｎ１ -Y Ｎ２ -Y Ｎ１ -Y Ｎ２ -, -Y Ｎ２ -, -Y Ｎ２ -Y Ｎ１ -, -Y Ｎ２ -Y Ｎ１ -Y Ｎ２ -, -Y Ｎ２ -Y Ｎ１ -Y Ｎ２ -Y Ｎ１ -, etc.

[0147] Y ＮAs an example, Y Ｎ When it 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 -Y Ｎ１ -) ２ , -Y Ｎ１ -Y Ｎ２ -Y Ｎ１ -Y Ｎ２ (-) ２ , -Y Ｎ１ -Y Ｎ２ -Y Ｎ１ -(Y Ｎ２ -) ２、 -Y Ｎ１ -Y Ｎ２ -(Y Ｎ１ -Y Ｎ２ -) ２、 -Y Ｎ１ -(Y Ｎ２ -Y Ｎ１ -Y Ｎ２ -) ２ ; -Y Ｎ２ (-) ２ , -Y Ｎ２ -Y Ｎ１ (-) ２ , -Y Ｎ２ -(Y Ｎ１ -) ２ , -Y Ｎ２ -Y Ｎ１ -Y Ｎ２ (-) ２ , -Y Ｎ２ -Y Ｎ１ (-Y Ｎ２ -) ２ , -Y Ｎ２ -(Y Ｎ１ -Y Ｎ２ -) ２ , -Y Ｎ２ -Y Ｎ１ -YＮ２ -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 cited.

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

[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 compound, one or more Y ＮHowever, it is preferred that the terminal on the amine skeleton side is —(C═O)— and that it is bonded to a nitrogen atom in the amine skeleton.

[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 , [wherein, Y Ｎ１ is independently in each occurrence a direct bond, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′-C(═O)—O—, —NR′-C(═O)—NR′—, —C(═O)—O—, or —C(═O)-NR′— —C(═O)-NR′-C(═O)— (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), and Y Ｎ２ is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a divalent aromatic group (for example, a divalent phenyl group or a divalent triazole group). This makes it possible to impart good liquid repellency to the substrate.

[0151] Y Ｎ Further specific examples include *-(C=O)- -O-(C=O)-NR'- (wherein * means that the group is bonded to the nitrogen atom of the amine skeleton, and 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)).

[0152] (Z Ｎ ) Z Ｎrepresents a monovalent hydrocarbon group or monovalent polysiloxane group having from 1 to 40 carbon atoms which may have a substituent, and the above descriptions of (the monovalent hydrocarbon group which may have a substituent) and (the monovalent polysiloxane group) are incorporated herein by reference.

[0153] [Examples of Amine Modified Compounds] (Amine Modified Compound Example 1) Examples of amine modified compounds include those having the following formula: N(-Y Ｎ -Z Ｎ n ) p (-H) q -L 1 -[N(-Y Ｎ -Z Ｎ n ) r (-H) s -L 1 -] t -N(-Y Ｎ -Z Ｎ n ) p (-H) q [In the formula, Y Ｎ is independently in each occurrence a direct bond or a group with a valence of 1+n; Z Ｎ is independently in each occurrence an optionally substituted linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms; L 1 is independently in each occurrence a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by an oxygen atom and / or a sulfur atom, n is independently in each occurrence an integer of 1 or more and 3 or less, p is independently in each occurrence an integer of 0 or more and 2 or less, q is independently in each occurrence an integer of 0 or more and 2 or less, and p+q is a substituted or unsubstituted group of each N(-Y Ｎ -Z Ｎ n ) p (-H) q In the formula, r is 2, r is independently in each occurrence 0 or 1, s is independently in each occurrence 0 or 1, and r+s is a 0 or 1 group for each N(-Y Ｎ -Z Ｎ n ) r (-H) sIn the formula (Amine Modification Example 1), p is 1, the sum of all p's and all r's is 1 or more, and t is an integer of 0 or more and 10 or less.

[0154] In the amine modified example 1, Y Ｎ , Z Ｎ , and n are described in detail above.

[0155] In the amine modified example 1, L １ 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 an oxygen atom and / or a sulfur atom, or may consist of only carbon atoms, nitrogen atoms, and hydrogen atoms. １ L may be, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings. １ is preferably a cyclic group having both a ring (for example, an aromatic ring) and a chain structure (for example, a linear structure, ether oxygen, or thioether sulfur), and specific examples 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 Amine Modification Example 1, p, in each occurrence, is independently an integer of 0 to 2, and q, in each occurrence, is independently an integer of 0 to 2, and p+q is a sum of the ... Ｎ -Z Ｎ n ) p (-H) qIn the formula, p is 2. Preferably, p may be independently in each occurrence 1 or more, for example 2.

[0157] In Amine Modification Example 1, r is independently in each occurrence 0 or 1, s is independently in each occurrence 0 or 1, and r+s is independently in each occurrence 0 or 1. Ｎ -Z Ｎ n ) r (-H) s In the formula, p is 1. Preferably, p is independently in each occurrence 1 or more, for example 2.

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

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

[0160] (Amine Modification Example 2) Other examples of amine modifications include those represented by the following formula: N(-Y Ｎ -Z Ｎ n ) p (-H) q -L ２ (-Y Ｎ -Z Ｎ n ) u [In the formula, Y Ｎ is independently in each occurrence a direct bond or a group with a valence of 1+n; Z Ｎ is independently in each occurrence an optionally substituted linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms; L ２is a 1+u valent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be interrupted by oxygen atoms and / or sulfur atoms, n is independently an integer of 1 or greater and 3 or less in each occurrence, p is an integer of 0 or greater and 2 or less, q is an integer of 0 or greater and 2 or less, p+q is 2, u is an integer of 1 or greater and 3 or less, and the sum of p and u is 1 or greater.] (Amine Modification Example 2)

[0161] In the amine modified example 2, Y Ｎ , Z Ｎ The above explanation is used for details of and n.

[0162] In the amine modified 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 an oxygen atom and / or a sulfur atom, or may consist of only carbon atoms, nitrogen atoms, and hydrogen atoms. ２ L may be, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings. ２ is preferably a cyclic group having both a ring (for example, an aromatic ring) and a chain structure (for example, a linear structure, ether oxygen, or thioether sulfur), and specific examples include a 1,3-phenylenebisalkylene group, a 1,4-phenylenebisalkylene group, a diphenyletherdiyl group, and a diphenylthioetherdiyl group. ２ 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.

[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 or more and 3 or less. u is 1, 2, or 3, for example, 2 or 3.

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

[0166] (Specific Example) Specific examples of the amine-modified compound include compounds represented by the following formula: Ｎ , Z Ｎ , and n are described in detail above.

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[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 aromatic amine. Examples of the synthetic wax include fatty acid amide compounds such as hydroxy fatty acid amide compounds, palmitic acid amide compounds, octadecanoic acid amide compounds, stearic acid amide compounds, arachidic acid amide compounds, behenic acid amide compounds, lignoceric acid amide compounds, oleic acid amide compounds, linoleic acid amide compounds, α-linolenic acid amide compounds, γ-linolenic acid amide compounds, arachidonic acid amide compounds, eicosapentaenoic acid amide compounds, and docosahexaenoic acid amide compounds.

[0175] [Production Method] The method for producing the amine-modified compound is not limited, but may be carried out by reacting various amines (raw material amines) with Z in the presence of a condensing agent as needed. Ｎ A method for synthesizing by reacting a carboxylic acid containing a Z group with various amines. Ｎ Examples of the synthesis method include a method of reacting a group-containing carboxylic acid with an acid chloride, acid anhydride, isocyanate, etc. The condensing agent may be a known condensing agent, such as DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA, or Py-Bop.

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

[0177] [Modified Polyol] As an example of a liquid-repellent compound, a modified polyol will be described. 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 1 or more. From the viewpoint of improving liquid repellency, the degree of polymerization of the polyol-modified product may be 2 or more, 3 or more, 5 or more, 6 or more, preferably 7 or more, more preferably 8 or more, and even more preferably 9 or more. 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. Here, the degree of polymerization refers to the number of repeating monomer units constituting the polymer.

[0179] The degree of polymerization in the present disclosure refers to the average degree of polymerization. The average degree of polymerization in the present disclosure refers to the polymerization obtained by measurement under the following conditions. When the polyol-modified product in the present disclosure is a polyglycerol-modified product obtained by modifying polyglycerol, the degree of polymerization of the polyol-modified product refers to the average degree of polymerization of the polyglycerol. The average degree of polymerization of polyglycerol is the average degree of polymerization (n) calculated from the hydroxyl value by end group analysis. Specifically, the average degree of polymerization and the average molecular weight are calculated from the following formulas (Formula 1) and (Formula 2). (Formula 1) Average molecular weight = 74n + 18 (Formula 2) Hydroxyl value = 56110(n + 2) / average molecular weight The hydroxyl value in the above (Formula 2) is a numerical value that serves as an index of the number of hydroxyl groups contained in the 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 Test Methods for the Analysis of Fats, Oils and Related Compounds (I), 2003 Edition," compiled by the Japan Oil Chemists' Society. The hydroxyl value of the raw material polyglycerol is measured according to the above-mentioned Standard Test Methods for the Analysis of Fats, Oils and Related Compounds, and the average degree of polymerization and average molecular weight of the polyglycerol can be calculated from the above-mentioned relational equation.

[0180] When the polyol-modified product in the present disclosure is a polyvinyl alcohol-modified product obtained by modifying polyvinyl alcohol, the degree of polymerization of the polyol-modified product refers to the average degree of polymerization of the polyvinyl alcohol, which can be measured in accordance with JIS K 6726, Testing Method for Polyvinyl Alcohol.

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

[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 polyol-modified product may be 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more; or may be 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 9,000 or less, 8,000 or less, 7,000 or less, 6,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,000 or less, or 500 or less.

[0183] The substitution rate of hydroxy groups in the modified polyol may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%, and is 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" refers to the proportion (mol %) of hydroxy groups derived from a polyol that are modified, and may refer to the proportion (mol %) that are modified with a monovalent hydrocarbon group having from 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group.

[0184] The residual rate of hydroxyl groups in the polyol-modified product may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 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. This is the value obtained by dividing the weight average molecular weight of the polyol modified product by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent.

[0187] The polyol-modified product has one or more hydroxy groups of a polyol substituted with a modifying group. The modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent. From the viewpoint of improving liquid repellency, the polyol-modified product may have a structure in which a polyol is modified with an 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 descriptions of the (monovalent hydrocarbon group which may have a substituent) and (monovalent polysiloxane group) are incorporated herein by reference.

[0189] (-Y Ｏ -Z Ｏ ｎ In the present disclosure, the modified polyol is a polyol in which one or more hydroxy groups of the polyol are represented by the following formula: Ｏ -Z Ｏ ｎ [In the formula, Y Ｏ Is Y Ｏ１ and Y Ｏ２ Y is a 1+n valent group consisting of one or more groups selected from the group consisting of Ｏ１ represents 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), and Y Ｏ２is a group consisting of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles, Ｏ is a monovalent hydrocarbon group having from 1 to 40 carbon atoms which may have a substituent, or a monovalent polysiloxane group, and n is an integer of from 1 to 3.

[0190] (Y Ｏ ) Y Ｏ Is Y Ｏ１ and Y Ｏ２ Y is a 1+n valent group consisting of one or more groups selected from the group consisting of Ｏ１ represents 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), and Y Ｏ２ is a group composed of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles.

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

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

[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. Ｏ is -C(=O)-NR'-, -C(=S)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO ２ It may contain NR'-. Ｏ By 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 valent group. Ｏ１ The valence of Y may be 2 to 4, 2 to 3, or 2. Ｏ１ is preferably not only a direct bond.

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

[0197] Y Ｏ１ represents a direct bond, —O—, —C(═O)—, —S(═O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) Ｏ１Examples of include a direct bond, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′-C(═O)—O—, —NR′-C(═O)—NR′—, —C(═O)—, —C(═O)—O—, —C(═O)—NR′—, —SO ２ -, -SO ２ NR'-, -C(OR')R'-, -C(OR')(-) ２ and the like (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (eg, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[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. Ｏ２ is -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO ２ It may contain NR'-. 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 heterocyclic ring 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 valent group. Ｏ２ The valency of may be, for example, 2-4, 2-3, or 2.

[0202] Y Ｏ２may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more carbon atoms, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0203] Y Ｏ２ is composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles.

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

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

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

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

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

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

[0211] Y Ｏ２ Specific examples of -(CH ２ ) 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, -(CH ２ ) ｑ -Cy-(CH ２ ) ｒ -(q and r each independently represent a number from 0 to 20, for example, from 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle), and the like.

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

[0213] Y Ｏ An example of this is Y Ｏ When is divalent, -Y Ｏ１ -, -Y Ｏ１ -Y Ｏ２ -, -Y Ｏ１ -Y Ｏ２ -Y Ｏ１ -, -Y Ｏ１ -Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -, -Y Ｏ２ -, -Y Ｏ２ -Y Ｏ１ -, -Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -, -Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -Y Ｏ１ - etc.

[0214] Y Ｏ An example of this is YＯ When it is trivalent, -Y Ｏ１ (-) ２ , -Y Ｏ１ -Y Ｏ２ (-) ２ , -Y Ｏ１ -(Y Ｏ２ -) ２ , -Y Ｏ１ -Y Ｏ２ -Y Ｏ１ (-) ２ , -Y Ｏ１ -Y Ｏ２ (-Y Ｏ１ -) ２ , -Y Ｏ１ -(Y Ｏ２ -Y Ｏ１ -) ２ , -Y Ｏ１ -Y Ｏ２ -Y Ｏ１ -Y Ｏ２ (-) ２ , -Y Ｏ１ -Y Ｏ２ -Y Ｏ１ -(Y Ｏ２ -) ２、 -Y Ｏ１ -Y Ｏ２ -(Y Ｏ１ -Y Ｏ２ -) ２、 -Y Ｏ１ -(Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -) ２ ; -Y Ｏ２ (-) ２ , -Y Ｏ２ -Y Ｏ１ (-) ２ , -Y Ｏ２ -(Y Ｏ１ -) ２ , -Y Ｏ２ -Y Ｏ１ -Y Ｏ２ (-) s ２ , -Y Ｏ２ -Y Ｏ１ (-Y Ｏ２ -) ２ , -Y Ｏ２ -(Y Ｏ１ -Y Ｏ２ -) ２ , -Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -YＯ１ (-) ２ 、 -Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -(Y Ｏ１ -) ２、 -Y Ｏ２ -Y Ｏ１ -(Y Ｏ２ -Y Ｏ１ -) ２、 -Y Ｏ２ -(Y Ｏ１ -Y Ｏ２ -Y Ｏ１ -) ２ etc. can be cited.

[0215] Y Ｏ As an example of Y Ｏ when Y is tetravalent, -Y Ｏ１ (-) ３ 、 -Y Ｏ１ -Y Ｏ２ (-) ３ 、 -Y Ｏ１ -(Y Ｏ２ -) ３ 、 -Y Ｏ１ -Y Ｏ２ -Y Ｏ１ (-) ３ 、 -Y Ｏ１ -Y Ｏ２ (-Y Ｏ１ -) ３ 、 -Y Ｏ１ -(Y Ｏ２ -Y Ｏ１ -) ３ 、 -Y Ｏ１ -Y Ｏ２ -Y Ｏ１ -Y Ｏ２ (-) ３ 、 -Y Ｏ１ -Y Ｏ２ -Y Ｏ１ -(Y Ｏ２ -) ３、 -Y Ｏ１ -Y Ｏ２ -(Y Ｏ１ -Y Ｏ２ -) ３、 -Y Ｏ１ -(Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -) ３ ; -Y Ｏ２ (-) ３ 、 -Y Ｏ２-Y Ｏ１ (-) ３ , -Y Ｏ２ -(Y Ｏ１ -) ３ , -Y Ｏ２ -Y Ｏ１ -Y Ｏ２ (-) ３ , -Y Ｏ２ -Y Ｏ１ (-Y Ｏ２ -) ３ , -Y Ｏ２ -(Y Ｏ１ -Y Ｏ２ -) ３ , -Y Ｏ２ -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 Preferably, Y Ｏga -O-Y Ｏ１１ - or -O-Y Ｏ１１ -Y Ｏ２１ -Y Ｏ１２ wherein each symbol represents independently at each occurrence: Y Ｏ１１ 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, and 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'-, -SO ２ -, -SO ２ NR'-, -C(OR')R'-, or -C(OR')(-) ２ ], or

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

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

[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 carbon atoms, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[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 Specific examples of -(CH ２ ) 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, -(CH ２ ) ｑ -Cy-(CH ２ ) ｒ -(q and r each independently represent a number from 0 to 20, for example, from 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle), and the like.

[0225] Y Ｏ１２ -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'-, -SO ２ -, -SO ２ NR'-, -C(OR')R'-, or -C(OR')(-) ２ It may be.

[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. Ｏ１２ is -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO ２ It may be NR'-. Ｃ１２ By including these groups, the liquid repellency can be improved.

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

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

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

[0231] The cationic group is an amino group, preferably a tertiary amino group or a quaternary amino group. In the tertiary amino group, two groups bonded to the nitrogen atom may be the same or different and may be 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 (C ６ H ５ -CH ２ In the quaternary amino group, the three groups bonded to the nitrogen atom are 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 (C ６ H ５ -CH ２ 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 in the form of a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, such as carboxylic acids having 1 to 20 carbon atoms (particularly monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid) are preferred.

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

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

[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, the repeating structure of the monomer unit may contain a hydroxy group and an ether bond.

[0237] The polyol may be low molecular weight (e.g., weight average molecular weight less than 1,000, 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, 1,000 or more, 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more; or 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,000 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 weight of the polyol may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, or 150 or more, and may be 1000 or less, 800 or less, 600 or less, 400 or less, 200 or less, 100 or less, or 75 or less. The hydroxy group equivalent weight of the polyol is the value obtained by dividing the weight average molecular weight of the polyol by the number of hydroxyl groups.

[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, and xylose.

[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, and lactitol.

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

[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 with an initiator. Examples of initiators include compounds having two or more functional hydroxyl groups. Examples of initiators include propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, glycerin, polyglycerin, trimethylolpropane, triethanolamine, pentaerythritol, ethylenediamine, aromatic diamines, diethylenetriamine, sorbitol, and sucrose. Examples of alkylene oxides include ethylene oxide and propylene oxide. Polyether polyols obtained by addition polymerization of alkylene oxide with the above initiators are also referred to as polyoxyalkylene polyols or oxyalkylene derivatives of polyols. Representative examples of polyether polyols include polyoxypropylene triols obtained by addition polymerization of propylene oxide with glycerin, and polyoxypropylene polyglyceryl ethers obtained by addition polymerization of propylene oxide with 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 include compounds obtained by dehydration condensation of a compound having a bifunctional or higher carboxyl group and a compound having a bifunctional or higher hydroxyl group. Examples of compounds having a bifunctional or higher carboxyl group 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 bifunctional or higher hydroxyl group include ethylene glycol, propylene glycol, propanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and polymers thereof.

[0254] (Modifying Agent) The modifying agent is a compound 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: Acid halides G(O=)C-Z Ｏ Acid anhydride O(C(=O)-Z Ｏ ) ２ Carboxylic acid HO(O=)C-Z Ｏ Isocyanate O=C=N-Z Ｏ Thioisocyanate S=C=N-Z Ｏ Epoxy (CH ２ OCH)CH ２ O-Z Ｏ Halide G-Z Ｏ Amine H ２ N-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-mentioned modifier Ｏmay be replaced with any group constituting the modifying group, for example, Z Ｏ may be a group having a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group, or, for example, Z Ｏ Wo-Y Ｏ -Z Ｏ ｎ It may also be 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 such as an acid halide compound, an acid anhydride, or a carboxylic acid with a hydroxy group of a polyol to form an ester bond. Alternatively, a modified polyol can be produced by reacting a modifying agent such as a halide or an epoxy compound with a hydroxy group of a polyol to form an ether bond. Those skilled in the art can appropriately design the reaction conditions between the polyol 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.

[0258] [Polycarboxylic Acid Modified Compound] As an example of a liquid-repellent compound, a polycarboxylic acid modified compound will be described. 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 modified polycarboxylic acid may be a low molecular weight (for example, a weight average molecular weight of less than 1500, less than 1000, or 500 or less) and / or a high molecular weight. The weight average molecular weight of the polycarboxylic acid modified product may be 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1,000 or more, 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more; and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 9,000 or less, 8,000 or less, 7,000 or less, 6,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,000 or less, or 500 or less.

[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 a standard sample with the following equipment and conditions: Separation column: SB-806M (8 mm x 30 mm, Shodex) Column temperature: 40°C Mobile phase solvent: ion-exchanged water Mobile phase flow rate: 1.0 mL / min Sample concentration: 0.5 wt% Injection volume: 50 μL Detector: RI detector (Waters 2414, Waters Corporation)

[0261] The weight average molecular weight (Mw), number average molecular weight (Mn) and polydispersity index (Mw / Mn) of the polycarboxylic acid modified product, calculated 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 hydroxy groups for carboxyl groups in the modified polycarboxylic acid may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%, and is preferably 10% or more, for example, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, particularly 80% or more, and may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, for example, 95% or less. Here, the "substitution rate" refers to the proportion (mol %) of hydroxy groups in 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 from 1 to 40 carbon atoms, or a monovalent polysiloxane group, which may have a substituent.

[0263] The residual rate of hydroxy groups in carboxyl groups in the modified polycarboxylic acid may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, for example, 5% or more, and may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, or 5% or less, for example, 50% or less, 30% or less, or 10% or less. Here, the "residual rate" refers to the proportion (mol %) of hydroxy groups in carboxyl groups derived from polycarboxylic acid that are not modified.

[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. This is the value obtained by dividing the weight average molecular weight of the polycarboxylic acid modified product by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent.

[0266] In the polycarboxylic acid modified product, one or more hydroxy groups of the polycarboxylic acid are substituted with a modifying group. The modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent. From the viewpoint of improving liquid repellency, the polycarboxylic acid modified product may have 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 descriptions of the (monovalent hydrocarbon group which may have a substituent) and (monovalent polysiloxane group) are incorporated herein by reference.

[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 represented by the following formula: -Y Ｃ -Z Ｃ ｎ [In the formula, Y Ｃ Is Y Ｃ１ and Y Ｃ２ Y is a 1+n valent group consisting of one or more groups selected from the group consisting of Ｃ１ represents 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), and Y Ｃ２ is a group consisting of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles, Ｃ is a monovalent hydrocarbon group having from 1 to 40 carbon atoms which may have a substituent, or a monovalent polysiloxane group, and n is an integer of from 1 to 3.

[0269] (Y Ｃ ) Y Ｃ Is Y Ｃ１ and Y Ｃ２ Y is a 1+n valent group consisting of one or more groups selected from the group consisting of Ｃ１ represents 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), and Y Ｃ２ is a group composed of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles.

[0270] n is Y Ｃ Z combines with Ｃ and may be an integer of 1 or more and 3 or less. n may be 1 or more, 2 or more, or 3 or more. n may be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

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

[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. Ｃ is -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO ２ It may be NR'-. Ｃ By including these groups, the liquid repellency can be improved.

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

[0274] Y Ｃ１is a direct bond or a divalent or higher valent group. Ｃ１ The valence of Y may be 2 to 4, 2 to 3, or 2. Ｃ１ is preferably not only a direct bond.

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

[0276] Y Ｃ１ represents a direct bond, —O—, —C(═O)—, —S(═O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) Ｃ１ Examples of include a direct bond, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′-C(═O)—O—, —NR′-C(═O)—NR′—, —C(═O)—, —C(═O)—O—, —C(═O)—NR′—, —SO ２ -, -SO ２ NR'-, -C(OR')R'-, -C(OR')(-) ２ and the like (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (eg, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[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. Ｃ１ is -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO ２ NR'- may be included.Ｃ１ By including these groups, the liquid repellency can be improved.

[0278] ○ Y Ｃ２ Y Ｃ２ is a linker of a hydrocarbon ring which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, or a heterocyclic ring 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 valent group. Ｃ２ The valency of may be, for example, 2-4, 2-3, 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 carbon atoms, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

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

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

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

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

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

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

[0290] Y Ｃ２ Specific examples of -(CH ２ ) 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, -(CH ２ ) ｑ -Cy-(CH ２ ) ｒ -(q and r each independently represent a number from 0 to 20, for example, from 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle), and the like.

[0291] (Y ＣExample: 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 When is divalent, -Y Ｃ１ -, -Y Ｃ１ -Y Ｃ２ -, -Y Ｃ１ -Y Ｃ２ -Y Ｃ１ -, -Y Ｃ１ -Y Ｃ２ -Y Ｃ１ -Y Ｃ２ -, -Y Ｃ２ -, -Y Ｃ２ -Y Ｃ１ -, -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 When is trivalent, -Y Ｃ１ (-) ２ , -Y Ｃ１ -Y Ｃ２ (-) ２ , -Y Ｃ１ -(Y Ｃ２ -) ２ , -Y Ｃ１ -Y Ｃ２ -Y Ｃ１ (-) ２ , -Y Ｃ１ -Y Ｃ２ (-Y Ｃ１ -) ２ , -Y Ｃ１ -(Y Ｃ２ -Y Ｃ１ -) ２ , -Y Ｃ１ -Y Ｃ２ -Y Ｃ１ -Y Ｃ２ (-) ２ , -Y Ｃ１ -Y Ｃ２ -Y Ｃ１ -(YＣ２ - ) 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 and so on.

[0294] Y Ｃ Examples of Y Ｃ When Y is tetravalent, - Y Ｃ１ (-) ３ , - Y Ｃ１ - Y Ｃ２ (-) ３ , - Y Ｃ１ - (Y Ｃ２ - ) ３、-Y Ｃ１ -Y Ｃ２ -Y Ｃ１ (-) ３ 、-Y Ｃ１ -Y Ｃ２ (-Y Ｃ１ -) ３ 、-Y Ｃ１ -(Y Ｃ２ -Y Ｃ１ -) ３ 、-Y Ｃ１ -Y Ｃ２ -Y Ｃ１ -Y Ｃ２ (-) ３ 、-Y Ｃ１ -Y Ｃ２ -Y Ｃ１ -(Y Ｃ２ -) ３、 -Y Ｃ１ -Y Ｃ２ -(Y Ｃ１ -Y Ｃ２ -) ３、 -Y Ｃ１ -(Y Ｃ２ -Y Ｃ１ -Y Ｃ２ -) ３ ; -Y Ｃ２ (-) ３ 、-Y Ｃ２ -Y Ｃ１ (-) ３ 、-Y Ｃ２ -(Y Ｃ１ -) ３ 、-Y Ｃ２ -Y Ｃ１ -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 -(YＣ２ -Y Ｃ１ -) ３、 -Y Ｃ２ -(Y Ｃ１ -Y Ｃ２ -Y Ｃ１ -) ３ ; etc.

[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 Preferably, Y Ｃ is -Y Ｃ１１ - or -Y Ｃ１１ -Y Ｃ２１ -Y Ｃ１２ wherein each symbol represents independently at each occurrence: Y Ｃ１１ is —O— or —NR′—, and Y Ｃ２１ is a hydrocarbon group having 1 to 40 carbon atoms, and 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'-, -SO ２ -, -SO ２ NR'-, -C(OR')R'-, or -C(OR')(-) ２ ], or

[0297] Y Ｃ１１is a non-hydrocarbon linker, which is a direct bond or a divalent or higher valent 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 carbon atoms, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[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 Specific examples of -(CH ２ ) 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, -(CH ２ ) ｑ -Cy-(CH ２ ) ｒ -(q and r each independently represent a number from 0 to 20, for example, from 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle), and the like.

[0304] Y Ｃ１２-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'-, -SO ２ -, -SO ２ NR'-, -C(OR')R'-, or -C(OR')(-) ２ It may be.

[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. Ｃ１２ is -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO ２ It may be NR'-. Ｃ１２ By including these groups, the liquid repellency can be improved.

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

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

[0308] [Production Method] The modified polycarboxylic acid may be produced by reacting a modifying agent having a modifying group (or a precursor structure of the modifying group) with a hydroxy group of a polycarboxylic acid.

[0309] (Polycarboxylic Acid) Polycarboxylic acid is a compound having two or more carboxyl groups and is a compound that can be used as a raw material for a modified polycarboxylic acid. 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 low molecular weight (e.g., weight average molecular weight less than 1,000, 500 or less) and / or high molecular weight. The weight average molecular weight of the polycarboxylic acid may be 100 or more, 300 or more, 500 or more, 1,000 or more, 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more; or 1,000,000 or less, 7,500,000 or less, 500,000 or less, 3,000,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,000 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 natural product also includes 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, and examples thereof include citric acid, tricarballylic acid, t-aconitic acid, trimellitic acid, and salts thereof.

[0317] The tetracarboxylic acid is a compound having four carboxyl groups, and examples thereof include 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] (Modifying Agent) The modifying agent is a compound 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 modifiers are: Epoxy (CH ２ OCH)CH ２ O-Z Ｃ Amine H ２ N-Z Ｃ Hydroxy HO-Z Ｃ [In the formula, Z Ｃ is as described above.]

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

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

[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 particularly be a (meth)acrylic polymer.

[0324] [Characteristics, etc.] The vinyl polymer is preferably a compound containing carbon of biobased origin. The biobased content is measured in accordance with ASTM D6866. The biobased content 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 biobased content means that the amount of fossil resource-based materials, such as petroleum, used is reduced. From this perspective, the higher the biobased content of the vinyl polymer, the better.

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

[0326] [Structure etc.] The weight average molecular weight of the vinyl polymer may be 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more, and may be 5,000,000 or less, 3,000,000 or less, 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, or 5,000 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 contained in 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 may be 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-based monomer may be a combination of a hydrocarbon-based monomer having an amide group, a urea group, or a urethane group and a hydrocarbon-based monomer not having an amide group, a urea group, or a urethane group. When the monomer (a) contains such a group, the effects of the present disclosure can be effectively achieved.

[0330] The monomer (a) having a hydrocarbon group having 6 to 40 carbon atoms is represented by the 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, ａ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ represents a divalent to tetravalent hydrocarbon group having one carbon atom (particularly, —CH ２ -, -CH(-) ２ ), -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ - or -NH-, and k is an integer of 1 to 3.

[0331] X ａ 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. ａ is preferably a divalent group. ａ represents a hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２It is preferable that Y is a group constituted by at least one selected from - and -NH-. ａ is preferably not a hydrocarbon group. Examples of hydrocarbon groups having one carbon atom include -CH ２ -, -CH(-) ２ or -C(-) ３ The hydrocarbon group having one carbon atom is repeated, and -(CH ２ ) m A hydrocarbon group having two or more carbon atoms may be formed, such as Y - (where 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 - and R' is -(CH ２ ) m - (m is an integer of 1 to 5) or -C ６ H ４ -(phenylene group).

[0334] Y ａ Specific examples of are -O-, -NH-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C ６ H ４ -, -O-(CH ２ ) m -O-, -NH-(CH ２ ) m -NH-, -O-(CH ２ ) m -NH-, -NH-(CH ２ ) m -O-, -O-(CH ２ ) m -O-C(=O)-, -O-(CH ２ ) m-C(=O)-O-、-NH-(CH ２ ) m -O-C(=O)-、-NH-(CH ２ ) m -C(=O)-O-、-O-(CH ２ ) m -O-C(=O)-NH-、-O-(CH ２ ) m -NH-C(=O)-O-、-O-(CH ２ ) m -C(=O)-NH-、-O-(CH ２ ) m -NH-C(=O)-、-O-(CH ２ ) m -NH-C(=O)-NH-、-O-(CH ２ ) m -O-C ６ H ４ -、-O-(CH ２ ) m -NH-S(=O) ２ -、-O-(CH ２ ) m -S(=O) ２ -NH-、-NH-(CH ２ ) m -O-C(=O)-NH-、-NH-(CH ２ ) m -NH-C(=O)-O-、-NH-(CH ２ ) m -C(=O)-NH-、-NH-(CH ２ ) m -NH-C(=O)-、-NH-(CH ２ ) m -NH-C(=O)-NH-、-NH-(CH ２ ) m -O-C ６ H ４ -、-NH-(CH ２ ) m -NH-C ６ H ４ -、-NH-(CH ２ ) m -NH-S(=O) ２ -、or -NH-(CH ２ ) m -S(=O) ２-NH-, wherein m is 1 to 5, particularly 2 or 4.

[0335] Y ａ is -O-, -NH-, -O-(CH ２ ) m -O-C(=O)-, -O-(CH ２ ) m -NH-C(=O)-, -O-(CH ２ ) m -OC(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-O-, -O-(CH ２ ) m -NH-C(=O)-NH-, -O-(CH ２ ) m -NH-S(=O) ２ -, -O-(CH ２ ) m -S(=O) ２ -NH-, -NH-(CH ２ ) m -NH-S(=O) ２ -, or -NH-(CH ２ ) m -S(=O) ２ -NH- [wherein m is an integer of 1 to 5, particularly 2 or 4] is preferred. ａ is -O- or -O-(CH ２ ) m —NH—C(═O)—, particularly —O—(CH ２ ) 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 hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 or 15 to 26, particularly 18 to 22 or 17 to 22 carbon atoms.

[0337] Examples of the monomer (a) are: (a1) a monomer of the formula: CH2=C(-X ａ１ )-C(=O)-Y ａ１ -Rａ１ [In the formula, R ａ１ is a hydrocarbon group having 6 to 40 carbon atoms, ａ１ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ１ is —O— or —NH—.], and (a2) a monomer represented by the formula: CH═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; ａ２ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ２１ is —O— or —NH—, and Y ａ２２ are each independently a direct bond, or —O—, —C(═O)—, —S(═O) ２ -, -NH- or -CH ２ -, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2.

[0338] (a1) Monomer The monomer (a1) is a monomer represented by 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, ａ１ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ１ is —O— or —NH—.]

[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 R is —NH—. ａ１ is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. ａ１In the formula (I), the number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example, 16 to 26, and particularly preferably 18 to 22. 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 examples of the long-chain acrylate ester monomer include lauryl (meth)acrylate, stearyl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, icosyl α-chloroacrylate, and behenyl α-chloroacrylate. Preferred examples of the long-chain acrylamide monomer include stearyl (meth)acrylamide, icosyl (meth)acrylamide, and behenyl (meth)acrylamide.

[0341] Monomer (a2) Monomer (a2) is a monomer different from monomer (a1). Monomer (a2) is a monomer having —O—, —C(═O)—, —S(═O) ２ -, -NH- or -CH ２ The monomer (a2) is a (meth)acrylate or (meth)acrylamide having a group consisting of at least one selected from 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; ａ２ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ２１ is —O— or —NH—, and Y ａ２２ are each independently a direct bond, or —O—, —C(═O)—, —S(═O) ２ -, -NH- or -CH ２ -, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2.ａ２２ and / or Z may not be a direct bond. ａ２２ and Z may not be a direct bond at the same time.

[0342] R ａ２ is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. ａ２ In the formula (I), 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 represents -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'-, wherein each Y' independently represents a direct bond, -O-, -NH-, or -S(=O) ２ - and R' is -(CH ２ ) 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 of 1 to 5 carbon atoms, or -(CH ２ ) ｌ -C ６ H ４ -(CH ２ ) ｌ - (each l is independently an integer of 0 to 5; -C ６ H ４ - is a phenylene group.

[0345] Y ａ２２ Specific examples include direct bond, -O-, -NH-, -OC(=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-C ６ H ４ -、-NH-C ６ H ４ -、-O-(CH ２ ) m -O-、-NH-(CH ２ ) m -NH-、-O-(CH ２ ) m -NH-、-NH-(CH ２ ) m -O-、-O-(CH ２ ) m -O-C(=O)-、-O-(CH ２ ) m -C(=O)-O-,-NH-(CH ２ ) m -O-C(=O)-,-NH-(CH ２ ) m -C(=O)-O-、-O-(CH ２ ) m -O-C(=O)-NH-,-O-(CH ２ ) m -NH-C(=O)-O-,-O-(CH ２ ) m -C(=O)-NH-,-O-(CH ２ ) m -NH-C(=O)-,-O-(CH ２ ) m -NH-C(=O)-NH-,-O-(CH ２ ) m -O-C ６ H ４ -、-NH-(CH ２ ) m -O-C(=O)-NH-,-NH-(CH ２ ) m -NH-C(=O)-O-,-NH-(CH ２ ) m -C(=O)-NH-,-NH-(CH ２ ) m -NH-C(=O)-,-NH-(CH ２ ) m -NH-C(=O)-NH-,-NH-(CH ２ ) m -O-C６ H ４ -, -NH-(CH ２ ) m -NH-C ６ H ４ wherein m is an integer of 1 to 5.

[0346] Y ａ２２ is -O-, -NH-, -O-C(=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-, -OC ６ H ４ - is preferred. ａ２２ is more preferably —NH—C(═O)—, —C(═O)—NH—, —O—C(═O)—NH—, —NH—C(═O)—O— or —NH—C(═O)—NH—. ａ２２ may not 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 linear or branched structure. Z preferably has 2 to 4 carbon atoms, and particularly preferably 2. Specific examples of Z include a direct bond, -CH ２ -, -CH ２ CH ２ -, -CH ２ CH ２ CH ２ -, -CH ２ CH ２ CH ２ CH ２ -, -CH ２ CH ２ CH ２ CH ２ CH ２ -, -CH ２ CH(-) ２ , -CH ２ (CH-)CH ２ -, -CH ２ CH ２ CH(-) ２ , -CH ２ CH２ CH ２ CH ２ CH(-) ２ , -CH ２ CH ２ (CH-)CH ２ -, -CH ２ CH ２ CH ２ CH(-) ２ Z does not have to be a direct bond.

[0348] Monomer (a2) is CH2=C(-X ａ２ )-C(=O)-O-(CH ２ ) m -NH-C(=O)-R ａ２ , C.H. ２ =C(-X ａ２ )-C(=O)-O-(CH ２ ) ｍ -OC(=O)-NH-R ａ２ , C.H. ２ =C(-X ａ２ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-OR ａ２ , C.H. ２ =C(-X ａ２ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-NH-R ａ２ Preferably, R ａ２ and X ａ２ has the same meaning as above.]. The monomer (a2) is CH2=C(-X ａ２ )-C(=O)-O-(CH ２ ) m -NH-C(=O)-R ａ２ It is particularly preferred that:

[0349] Monomer (a2) can be produced by reacting a hydroxyalkyl (meth)acrylate or hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate. Examples of long-chain alkyl isocyanates include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, and behenyl isocyanate. Alternatively, 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 α-chloroacrylate, behenyl α-chloroacrylate; stearyl (meth)acrylamide, behenyl (meth)acrylamide;

[0351]

[0352]

[0353]

[0354]

[0355]

[0356] [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 chemical formula is an acrylic compound having a hydrogen atom at the α-position, but specific examples may be a methacryl compound having a methyl group at the α-position and an α-chloroacrylic compound having a chlorine atom at the α-position.

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

[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 =CH ２ , -CHR ａ２１１ =CH ２ , -CH ２ CHR ａ２１１ =CH ２ and the like. ａ２１１ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ２１ R may have various organic groups in addition to the ethylenically unsaturated polymerizable group, such as organic groups of chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, and polysiloxane groups, and these organic groups may be substituted with various substituents. ａ２１ is -C(=O)CR ａ２１１ =CH ２ It is preferable that:

[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 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. ａ２３The number of carbon atoms in R is preferably 2 to 4, and particularly preferably 2. ａ２３ is preferably an alkylene group.

[0361] The amide group-containing monomer is R ａ２２ is one type (for example, R ａ２２ is only a compound having 17 carbon atoms), or R ａ２２ A combination of multiple ａ２２ a compound having 17 carbon atoms, and R ａ２２ and a compound having 15 carbon atoms.

[0362] An example of the amide group-containing monomer is carboxylic acid amide alkyl (meth)acrylate.Specific examples of the amide group-containing monomer include palmitic acid amide ethyl (meth)acrylate, stearic acid amide ethyl (meth)acrylate, behenic acid amide ethyl (meth)acrylate, myristate amide ethyl (meth)acrylate, laurate amide ethyl (meth)acrylate, isostearate ethyl amide (meth)acrylate, oleic acid ethyl amide (meth)acrylate, tertiary butylcyclohexyl caproate amide ethyl (meth)acrylate, adamantanecarboxylic acid ethyl amide (meth)acrylate, naphthalenecarboxylic acid amide ethyl (meth)acrylate, anthracenecarboxylic acid amide ethyl (meth)acrylate, palmitic acid amide propyl (meth)acrylate, stearic acid amide propyl (meth)acrylate, palmitic acid amide ethyl vinyl ether, stearic acid amide ethyl vinyl ether, palmitic acid amide ethyl allyl ether, stearic acid amide ethyl allyl ether, and 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 wt% or more, 50 wt% or more, 60 wt% or more, or 70 wt% or more, and may be 90 wt% or less, 80 wt% or less, or 70 wt% or less, based on the total weight of the amide group-containing monomers. The remaining monomer may be, for example, palmitamidoethyl (meth)acrylate.

[0364] The amount of monomer (a2) in monomer (a) 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). Monomer (b) is a monomer other than monomer (a) that 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, 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] Monomer (b) has the formula: CH ２ =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, and Y ｂ is —O— or —NH—, R ｂ are each independently an alkylene group having 2 to 6 carbon atoms,ｂ represents a hydrogen atom, an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, or CH ２ =CX ｂ C(═O)—, and n is an integer of 1 to 90.

[0367] Examples of monomer (b) are those of the formula: CH ２ =CX ｂ C(=O)-O-(R ｂ O) ｎ -A ｂｉ (b1) and CH ２ =CX ｂ C(=O)-O-(R ｂ O) ｎ -C(=O)CX ｂ =CH ２ (b2), CH ２ =CX ｂ C(=O)-NH-(R ｂ O) ｎ -A ｂｉ (b3) wherein X ｂ are each independently a hydrogen atom or a methyl group; ｂｉ are each independently a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, ｂ are each independently an alkylene group having 2 to 6 carbon atoms, and n is an integer of 1 to 90.

[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, a group of the formula -(CH ２ ) ｘ - or - (CH ２ ) ｘ１ -(CH(CH ３ )) ｘ２ - [wherein x1 and x2 are 0 to 6, for example, 2 to 5, and the sum of x1 and x2 is 1 to 6. -(CH ２ ) ｘ１ - and - (CH (CH ３ ))ｘ２ The order of - is not limited to the illustrated formula and may be random. 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 is particularly preferably an ethylene group, a propylene group or a butylene group, and particularly preferably a butylene group. ｂ R may be a combination of two or more alkylene groups. In this 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 a combination of an ethylene group / propylene group, a combination of an ethylene group / butylene group, and a combination of a propylene group / butylene group. The monomer (b) may be a mixture of two or more types. In this case, at least one of the monomers (b) is a mixture of R in formula (b1), (b2), or (b3). ｂ is preferably an ethylene group, a propylene group, or a butylene group. When a polyalkylene glycol di(meth)acrylate represented by formula (b2) is used, 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 content of the compound represented by formula (b2) to less than 30% by weight of the monomer (b) used.

[0370] Specific examples of the monomer (b) can be exemplified by, for example, the following, but are not limited thereto. CH2=CHCOO-CH2CH2O-H CH2=CHCOO-CH2CH2CH2O-H CH2=CHCOO-CH2CH(CH3)O-H CH2=CHCOO-CH(CH3)CH2O-H CH2=CHCOO-CH2CH2CH2CH2O-H CH2=CHCOO-CH2CH2CH(CH3)O-H CH2=CHCOO-CH2CH(CH3)CH2O-H CH2=CHCOO-CH(CH3)CH2CH2O-H CH2=CHCOO-CH2CH(CH2CH3)O-H CH2=CHCOO-CH2C(CH3)2O-H CH2=CHCOO-CH(CH2CH3)CH2O-H CH2=CHCOO-C(CH3)2CH2O-H CH2=CHCOO-CH(CH3)CH(CH3)O-H CH2=CHCOO-C(CH3)(CH2CH3)O-H CH2=CHCOO-(CH2CH2O)2-H CH2=CHCOO-(CH2CH2O)4-H CH2=CHCOO-(CH2CH2O)5-H CH2=CHCOO-(CH2CH2O)6-H CH2=CHCOO-(CH2CH2O)5-CH3 CH2=CHCOO-(CH2CH2O)9-CH3 CH2=CHCOO-(CH2CH2O) 23 -CH3 CH2=CHCOO-(CH2CH2O) 90 -CH3

[0371] CH2=CHCOO-(CH2CH(CH3)O)9-H CH2=CHCOO-(CH2CH(CH3)O)9-CH3 CH2=CHCOO-(CH2CH(CH3)O) 12 -CH3 CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=CHCOO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9 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)OH CH2=CH-C(=O)-NH-CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH(CH3)CH2O-H 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-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] The monomer (b) may be 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-tertiarybutylsulfonic acid, and salts thereof.

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

[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, two groups bonded to the nitrogen atom may be the same or different and may be 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 aromatic aliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example a benzyl group (C ６ H ５ -CH ２ In the quaternary amino group, the three groups bonded to the nitrogen atom are 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 aromatic aliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example a benzyl group (C ６ H ５ -CH ２ 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 in the form of a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, such as carboxylic acids having 1 to 20 carbon atoms (particularly monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid), are preferred. 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) 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 Monomer The vinyl polymer may have a repeating unit derived from a halogenated olefin monomer (d). The halogenated olefin monomer (d) may not contain fluorine atoms. The halogenated olefin monomer (d) is preferably an olefin having 2 to 20 carbon atoms and 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 examples of the halogenated olefin monomer (d) include 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 the durability of water repellency). The presence of repeating units derived from the halogenated olefin monomer (d) provides the vinyl polymer with enhanced wash durability.

[0387] (e) Crosslinkable Monomer The crosslinkable monomer of the vinyl polymer has 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 also be a compound that does not contain fluorine atoms. The crosslinkable monomer (e) may be a compound that has at least two ethylenically unsaturated double bonds (preferably, (meth)acrylate groups), or a compound that has 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, etc.

[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 have, for example, 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 linear 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 the cyclic hydrocarbon group include a cyclohexyl group, a t-butylcyclohexyl group, an adamantyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group, a bornyl group, an isobornyl group, a norbornyl group, a dicyclopentanyl group, a dicyclopentenyl group, a benzyl group, a phenyl group, a naphthyl group, a 2-t-butylphenyl group, residues obtained by removing one or more hydrogen atoms from these groups (for example, a cyclohexylene group, an adamantylene group, a phenylene group, a naphthylene group, 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 monomers (a) to (g) constituting the repeating units of the vinyl polymer is not particularly limited, but examples are as follows (brackets 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 Furthermore, another monomer (g) may be used in combination with the above combinations. In the case of pulp products, it is preferable to use the monomer (a), monomer (b), and monomer (c) in combination.

[0399] The amount of repeating units derived from 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 repeating units derived from 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 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, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0401] The amount of repeating units derived from 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 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, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0402] The amount of repeating units derived from 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 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, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0403] The amount of repeating units derived from 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 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, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0404] The amount of repeating units derived from 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 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, relative to 100 parts by weight of the repeating units derived from monomer (a).

[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 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, relative to 100 parts by weight of the amount of the repeating units derived from monomer (a).

[0406] [Polymerization Method] Vinyl polymers can be produced by known polymerization methods, 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 employed in which monomers are dissolved in an organic solvent in the presence of a polymerization initiator, and after purging with nitrogen, the mixture is heated and stirred at a temperature in the range of 30 to 120°C for 1 to 10 hours. Examples of polymerization initiators 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, per 100 parts by weight of the monomers.

[0408] The organic solvent is inert 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, and trichlorotrifluoroethane. The organic solvent is used in an amount of 10 to 3,000 parts by weight, for example, 50 to 2,000 parts by weight, per 100 parts by weight of the total of the monomers.

[0409] Emulsion polymerization involves emulsifying monomers in water in the presence of a polymerization initiator and an emulsifier, purging with nitrogen, and then polymerizing the mixture at a temperature ranging from 50 to 80°C for 1 to 20 hours with stirring. Examples of polymerization initiators that can be used include 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, as well as oil-soluble initiators such as 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 ranging from 0.01 to 10 parts by weight per 100 parts by weight of the monomer.

[0410] To obtain a polymer aqueous dispersion with excellent shelf stability, it is desirable to polymerize the monomer by microparticulating it in water using an emulsifying device capable of applying powerful crushing energy, such as a high-pressure homogenizer or ultrasonic homogenizer. Furthermore, various anionic, cationic, or nonionic emulsifiers can be used as emulsifiers, and are used in a range of 0.5 to 20 parts by weight per 100 parts by weight of monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. If the monomers are not completely compatible, it is preferable to add a compatibilizer, such as a water-soluble organic solvent or a low-molecular-weight monomer, that will fully compatibilize these monomers. Addition of a compatibilizer can improve emulsification and copolymerization properties.

[0411] The water-soluble organic solvent may be any of the organic solvents described above. Examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol. These may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of water. Examples of low-molecular-weight monomers include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate. These may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of the total amount of monomers.

[0412] A chain transfer agent may be used in the polymerization. The molecular weight of the polymer can be changed depending on the amount of chain transfer agent used. Examples of chain transfer agents 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 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, per 100 parts by weight of the total amount of monomers.

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

[0414] As the dispersant, an organic dispersant and an inorganic dispersant may be used individually, or a combination of an organic dispersant and an inorganic dispersant may be used.

[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 refer to a surfactant.

[0416] The dispersant may be fluorine-free.

[0417] [Nonionic Dispersant] The dispersant may contain a nonionic dispersant, which may be a nonionic surfactant.

[0418] The nonionic dispersant may be a low molecular weight or a high molecular weight dispersant, and may have a molecular weight of 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may 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 mono- to trio-hydric (particularly di- to deca-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0422] An example of an ester ether is a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. An example of an alcohol is a mono- to trio-hydric (particularly di- to deca-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0423] Examples of alkanolamides are those formed from fatty acids and alkanolamines. The alkanolamides may be monoalkanolamides or dialkanolamines. Examples of fatty acids include saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamines may be alkanols having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, and 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 (for example, 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, or the like. Among these, those in which the alkylene oxide adduct moiety and the polyalkylene glycol moiety have a structure of polyoxyethylene (POE), polyoxypropylene (POP), or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Furthermore, the nonionic dispersant does not have to contain an aromatic group.

[0428] The nonionic dispersant has the formula: １ O-(CH ２ CH ２ O) 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, ２ are independently the same or different and are alkylene groups having 3 or more carbon atoms (e.g., 3 to 10), ３ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, and q is a number of 0 or 1 or more.

[0429] R １ R preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. １Preferred specific examples of R include an octyl group, a nonyl group, a trimethylnonyl group, a lauryl group, a tridecyl group, an oleyl group, and a stearyl group. ２ Examples of the nonionic dispersant 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) at the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, with the oxypropylene chain being preferred.

[0430] Specific examples of nonionic dispersants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkanes (C １２ -C １６ ) thiol, sorbitan mono fatty acid (C ７ -C １９ ) or alkyl(C １２ -C １８ ) condensation products with amines, etc., sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lecithin derivatives, etc. Examples of nonionic dispersants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycol, polyethyleneimine ethoxylate, etc.

[0431] The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example 30 to 75% by weight, and 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 Dispersant] The dispersant may contain a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a compound having no amide group.

[0433] The cationic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the cationic dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

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

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

[0436] Specifically, the low molecular weight cationic dispersant is represented by the formula: １ ｐ -N ＋ R ２ ｑ X － [In the formula, R １ is C12 or more (e.g. C １２ ~C ５０) is a linear and / or branched aliphatic (saturated and / or unsaturated) group of the formula R ２ is H or a C1-4 alkyl group, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50) (CH ３ , C ２ H ５ is particularly preferred), and X is a halogen atom (e.g., chlorine), or C １ ~C ４ or a fatty acid salt of C １ ~C ４ where p is 1 or 2, q is 2 or 3, and p+q=4. １ may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0437] Examples of 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 natural products (particularly cationic sugars) such as cationic starch, cationic cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propylhydroxyethylcellulose chloride), cationic guar gum, cationic xanthan gum, and chitosan; and polymers of cationic group-containing monomers such as aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternized dimethylammonium ethyl methacrylate, diallyldimethylammonium chloride, dimethylaminopropylamine, and quaternized vinylimidazole.

[0439] [Anionic Dispersant] The dispersant may contain an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may not contain an anionic dispersant.

[0440] The anionic dispersant may be a low molecular weight or a high molecular weight dispersant, and may have a molecular weight of 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may have a molecular weight of 100,000 or less, 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, phosphate mono- or diester type dispersants, and sulfosuccinate esters. An example of an anionic dispersant is a carboxylate (e.g., a fatty acid salt).

[0442] [Amphoteric Dispersant] The dispersant may contain 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, and may have a molecular weight of 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may have a molecular weight of 100,000 or less, 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 acetic acid betaine, and specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetic acid betaine, and fatty acid amidopropyl dimethylamino acetic acid betaine.

[0445] [Inorganic Dispersant] The dispersant may contain 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 hydrophilic particles.

[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 dispersant may be 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, relative to 100 parts by weight of the liquid repellent compound, 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 agent of the present disclosure may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The repellent agent may be a dispersion or a solution. The repellent agent of the present disclosure may contain at least water.

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

[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 agent according to 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 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the liquid repellent compound, 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 agent according to the present disclosure may contain wax. By including 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 wax, particularly paraffin wax, is 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, and 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, and 1-hexatriacontene). The number of carbon atoms in the compounds 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 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the liquid repellent compound, 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. Known organic acids can be used. Preferred organic acids include carboxylic acids, sulfonic acids, sulfinic acids, etc., with carboxylic acids being particularly preferred. Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., with formic acid or acetic acid being particularly preferred. In the present disclosure, one type of organic acid may be used, or two or more types may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0463] [Amount of Organic Acid] The amount of organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the liquid-repellent compound, 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. The amount of 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 contain a hardening agent (active hydrogen-reactive compound or 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 include isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of the active hydrogen-containing compound include 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 contain an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound functions as a crosslinking agent. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (for example, a blocked polyisocyanate compound). The blocked isocyanate compound is a compound in which the isocyanate group of an isocyanate compound is masked with a blocking agent to inhibit reaction.

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

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

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

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

[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 a polyisocyanate compound is blocked with a blocking agent. It is preferable to use a blocked polyisocyanate compound because it is relatively stable in 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, e.g., 130°C or higher, the isocyanate groups are regenerated and can easily react with hydroxyl groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. The polyisocyanate compounds can be used alone or in combination of two or more.

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

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

[0476] [Amount of Curing Agent] The amount of the curing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the liquid repellent compound, 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 Components] The repellent may contain other components in addition to the above components. Examples of other components include polysaccharides, paper strength agents, flocculants, retention aids, coagulants, binder resins, anti-slip agents, sizing agents, paper strength agents, fillers, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorizers, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above components, other components include other water and / or oil repellents, dispersants, texture adjusters, softeners, flame retardants, paint fixatives, wrinkle inhibitors, drying speed adjusters, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity adjusters, UV absorbers, antioxidants, pH adjusters, insect repellents, antifoaming agents, shrinkage inhibitors, anti-wrinkle agents after washing, shape retention agents, drape retention agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, dye transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain release agents, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Tinopal CBS-X manufactured by Ciba Specialty Chemicals), dye fixatives, and anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine. The following may be blended: stain removers, enzymes such as cellulase, amylase, protease, lipase, keratinase, etc. as fiber surface modifiers; foam inhibitors; silk protein powder, surface-modified products thereof, or emulsified dispersions thereof (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk liquid (Jomo), Silkgen G Soluble S (Ichimaru Falcos)); stain inhibitors (e.g., nonionic polymer compounds composed 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.) that can impart silk texture and functionality such as moisture absorption and release. 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, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, chitin nanofiber, cellulose nanofiber, pullulan, etc. The polysaccharide may be a substituted modified polysaccharide (excluding the above-mentioned liquid repellent compounds), and 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 agents, flocculants, retention aids, 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 polyalkylenepolyamines, dicyandiamide-formalin condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0480] Sizing Agents 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 acrylate.

[0481] [Antistatic Agent] Examples of antistatic agents 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, sulfate ester salts, phosphonates, and phosphate ester salts; amphoteric antistatic agents such as alkylbetaine and its derivatives, imidazoline and its derivatives, alanine and its derivatives, and nonionic antistatic agents such as aminoalcohols and its derivatives, glycerin and its derivatives, and polyethylene glycol and its derivatives. Ion-conductive polymers obtained by polymerizing or copolymerizing monomers having these cationic, anionic, or amphoteric ionic conductive groups may also be used. These may be used alone or in combination of two or more.

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

[0483] [Ultraviolet Absorber] An ultraviolet absorber is a chemical agent that has the effect of protecting against ultraviolet rays, and is a component that absorbs ultraviolet rays and converts them into infrared rays, visible light, etc. Examples of ultraviolet absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, and 4-t-butyl-4'-methoxybenzoylmethane.

[0484] [Antibacterial Agent] An antibacterial agent is a component that has the effect of suppressing the growth of bacteria on fibers and further suppressing the generation of unpleasant odors resulting from microbial decomposition products. Examples of the antibacterial agent include cationic disinfectants such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide)zinc, polyhexamethylenebiguanidine hydrochloride, 8-oxyquinoline, and polylysine.

[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 (e.g., zinc complex of trisodium methylglycine diacetate described in WO 2012 / 090580).

[0486] [Amount of Other Components] The amount of each or the total amount of the other components may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the liquid repellent compound, 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 can be made without departing from the spirit and scope of the claims.

[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 under conditions of 23°C and 50% humidity for 12 hours. 100 ml of corn oil at 65°C was poured into the mold, and after leaving it at room temperature for 45 minutes, the corn oil was removed from the mold and the degree of oil staining on the mold was evaluated. The following evaluation values ​​were set depending on the degree of staining: 5: No staining on the inside. 4: Stained on the inside. No staining on the back. 3: Stained on the inside. Slight seepage on the back. 2: Stained on the inside. Staining on the back took up less than 50% of the area. 1: Stained on the inside. Staining on the back took up 50% or more but less than 100% of the area. 0: Stained on the entire back.

[0491] [Practical Water Resistance Test] The mold was pretreated by storing it under conditions of 23°C and 50% humidity for 12 hours. 100 ml of water at 100°C was poured into the mold, and after leaving it at room temperature for 30 minutes, the water was removed from the mold and the degree of staining on the mold was evaluated. The following evaluation values ​​were set depending on the degree of staining: 5: No staining on the inside 4: Stained on the inside. No staining on the backside 3: Stained on the inside. Slight staining on the backside 2: Stained on the inside. Staining on the backside was less than 50% of the area 1: Stained on the inside. Staining on the backside was 50% or more but less than 100% of the area 0: Stained on the entire backside

[0492] [Evaluation of Adhesion Amount] The amount of liquid-repellent compound attached to the pulp mold will be less than the amount of liquid-repellent compound added. The amount of adhesion can be calculated using the following procedure. In the first step, the paper plate of the pulp mold is weighed. In the second step, an internal standard (e.g., toluene or DMF) is added to a solvent (e.g., chloroform) in which the liquid-repellent compound dissolves to create an evaluation solvent. In the third step, the evaluation solvent is measured, and the weighed paper plate is immersed in the solvent, heated as necessary to extract the liquid-repellent compound. In the fourth step, a portion of the solution from which the liquid-repellent compound has been extracted is taken out, diluted with a heavy solvent, and subjected to 1H-NMR measurement. If a heavy solvent is used as the evaluation solvent, the solution from which the liquid-repellent compound has been extracted is measured directly 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 Agent 2 g of decaglycerol dodecabehenyl ester (degree of polymerization: 10, hydroxy group substitution rate: 12 / 12*100 [100%], biobased ratio: 100%, melting point: 69°C) as a liquid-repellent compound, 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 agent. This precursor A of a water-dispersed repellent agent was heated to 80°C and then allowed to cool while stirring with a magnetic stirrer, thereby obtaining a precursor B of a water-dispersed repellent agent. A water-dispersed repellent agent was obtained by treating precursor B of a water-dispersed repellent agent twice in a high-pressure wet microparticulation device under conditions of 80 MPa. The volumetric ratio of particles of 100 μm or larger in the obtained water-dispersed repellent agent 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 wt % 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). While stirring, the water-dispersible repellent obtained above and a liquid-repellent compound were added in an amount of 3 parts by weight (solids concentration) per pulp weight to prepare a pulp composition.

[0495] [Preparation of Pulp Mold] A pulp mold was formed using an automatic molding machine. A mesh-like body was placed on a metal pulp mold mold with multiple suction holes at the bottom, and a metal tank was placed on the top, with the pulp composition placed in the upper metal tank. The pulp composition was sucked and dehydrated through the pulp mold mold and mesh-like body using a vacuum pump from the side opposite the side where the mesh-like body was placed in the pulp mold mold, and the solid content (pulp, etc.) contained in the pulp composition was deposited on the mesh-like body to obtain a pulp mold intermediate. Next, the obtained pulp mold intermediate was heated from above and below in a heated male-female metal mold at a pressure of 0.3 MPa at 80°C for 10 seconds (preheating), followed by first heating at the temperature and time shown in the table below, and heated and dried until the amount of liquid medium reached 10% by weight, obtaining 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 second heating under the conditions shown in the table below. After the obtained pulp mold after the second heating was returned to room temperature (after second cooling), the above test was carried out. The results are shown in the table below.

[0496]

[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 Agent] As a liquid repellent compound, a compound having the following formula: A water-dispersible repellent was obtained by mixing 2 g of dry-ground ethylene bisstearic acid amide powder (biobased content: 97%, melting point: 143°C) represented by the formula (1), 0.2 g of polyethylene glycol trimethyl nonyl ether (HLB 13), and 17.8 g of water (volume proportion of particles of 100 μm or more: 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 wt % 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). While stirring, the water-dispersible repellent obtained above and a liquid-repellent compound were added in an amount of 1 part by weight in solids concentration per pulp weight to prepare a pulp composition.

[0500] [Preparation of Pulp Mold] Pulp molds were prepared and tested in the same manner as in Example 1-1, except that the above pulp composition was subjected to heating and cooling treatment under the conditions shown in the table below. The results are shown in the table below.

Claims

1. A method for producing a pulp product, comprising: 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 adheres 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.

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

3. The method for producing a pulp product according to claim 1 or 2, wherein the first heating temperature is equal to or higher than the melting point of the liquid repellent compound, and the first cooling temperature is lower than 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 at least the first cooling temperature +30°C and at least the melting point of the liquid repellent compound -50°C.

6. A method for producing a pulp product according to any one of claims 1 to 5, wherein 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, and the second heating temperature is equal to or higher than the melting point of the liquid repellent compound -50°C and equal to or higher than the melting point of the liquid repellent compound +100°C.

7. A method for producing a pulp product according to any one of claims 1 to 6, wherein the pulp composition contains a liquid medium, and in the first heating step, the amount of the liquid medium in the pulp composition is removed until it is 10% by weight or less.

8. A method for producing a pulp product according to any one of claims 1 to 7, wherein in the first heating step, the pulp composition is molded, and the precursor product is a pulp mold.

9. A method for producing a pulp product according to any one of claims 1 to 8, wherein the bio-based content of the liquid repellent compound is 30% or more.

10. A method for producing a pulp product according to any one of claims 1 to 9, wherein the liquid-repellent compound is a compound having a hydrocarbon group having 6 to 40 carbon atoms.

11. A method for producing a pulp product according to any one of claims 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.

12. A method for producing a pulp product according to any one of claims 1 to 11, wherein the pulp composition comprises 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, and the repellent comprises the liquid-repellent compound.

13. The method for producing a pulp product according to any one of claims 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. A method for producing a pulp product according to any one of claims 12 or 13, wherein the repellent agent comprises a dispersant and water.

15. A method for producing a pulp product according to any one of claims 1 to 14, wherein the pulp product has the liquid repellent compound added thereto.

16. A method for producing a pulp product according to any one of claims 1 to 15, 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, and the polyol modified compound is a compound in which a hydroxy group of a polyglycerin having a polymerization degree of 1 to 15 is converted into a compound 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. In the polyol modified product, the hydroxy group substitution rate is 50% or more, and the amine modified product is a compound substituted with a group represented by 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 is independently in each occurrence an integer of 1 to 2, q is independently in each occurrence 0 or 1, and p+q is each N(-C(=O)-Z N ) p (-H) q In the formula, r is 2, r is, independently at each occurrence, 0 or 1, s is, independently at each occurrence, 0 or 1, and r+s is each N(-C(=O)-Z N ) r (-H) s The method for producing a pulp product according to any one of claims 1 to 16, wherein the compound is represented by the formula:

Images