Method for manufacturing pulp products

Abstract

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

Description

Technical Field

[0001] The present disclosure relates to a method for manufacturing a pulp product.

Background Art

[0002] In Patent Document 1, a method for manufacturing a pulp molded product is disclosed, which is characterized in that, immediately after the pulp is formed, a coating agent is applied to the surface before or while sucking in a vacuum from the back surface of the pulp molded body, so that the effect (waterproofness, strength, etc.) of the coating agent can be enhanced and it can be made economical.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In Patent Document 1, there is no description or suggestion regarding providing heating multiple times or providing a cooling step in the manufacturing process. Also, in Patent Document 1, the oil resistance of the product has not been studied.

[0005] An object of the present disclosure is to provide a novel method for manufacturing a pulp product provided with liquid repellency.

Means for Solving the Problems

[0006] The present disclosure includes the following aspects: [Item 1] A first heating step of heating a pulp composition containing pulp and a liquid repellent compound to a first heating temperature to obtain a precursor product in which the liquid repellent compound 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 pre-cooling product to a second heating temperature to obtain a pulp product A method for manufacturing a pulp product, comprising: [Item 2] The first heating temperature is 40 °C or higher, The first cooling temperature is less than 40 °C, The method for manufacturing a pulp product according to Item 1, wherein the second heating temperature is 40 °C or higher. [Item 3] The first heating temperature is equal to or higher than the melting point of the liquid-repellent compound, The method for manufacturing a pulp product according to Item 1 or 2, wherein the first cooling temperature is less than the melting point of the liquid-repellent compound. [Item 4] The method for manufacturing 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 manufacturing a pulp product according to Item 3, wherein the second heating temperature is equal to or higher than the first cooling temperature + 30 °C and equal to or higher than the melting point of the liquid-repellent compound - 50 °C. [Item 6] The first heating temperature is equal to or higher than the melting point of the liquid-repellent compound, The first cooling temperature is less than 40 °C, The method for manufacturing a pulp product according to any one of Items 1 to 5, wherein the second heating temperature is equal to or higher than the melting point of the liquid-repellent compound - 50 °C and equal to or lower than the melting point of the liquid-repellent compound + 100 °C. [Item 7] The pulp composition contains a liquid medium, The method for manufacturing a pulp product according to any one of Items 1 to 6, wherein in the first heating step, the amount of the liquid medium in the pulp composition is removed until it becomes 10% by weight or less. [Item 8] In the first heating step, the pulp composition is formed, The method for manufacturing a pulp product according to any one of Items 1 to 7, wherein the pre-product is a pulp mold. [Item 9] The method for manufacturing a pulp product according to any one of Items 1 to 8, wherein the bio-based degree of the liquid-repellent compound is 30% or higher. [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 with 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 pulp composition contains at least one repellent selected from the group consisting of a water repellent, an oil repellent, a water repellent, an oil repellent, and an antifouling agent, The method for producing a pulp product according to any one of Items 1 to 11, wherein 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 repellent and an oil repellent. [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 pulp product is internally added with the liquid-repellent compound. [Item 16] The method for producing a pulp product according to any one of Items 1 to 15, wherein the adhesion amount of the liquid-repellent compound in the pulp product is 3.0% by weight or less. [Item 17] The liquid-repellent compound is a polyol-modified product or an amine-modified product, The polyol-modified product is a compound in which the hydroxy group of polyglycerin having a polymerization degree of 1 or more and 15 or less is substituted with a group represented by the following formula: -O-C(=O)-Z O [wherein, Z O is an alkyl group having 14 to 24 carbon atoms.] is a compound substituted with a group represented by and the hydroxy group substitution rate in the polyol-modified product is 50% or more. The amine-modified product has the following formula: N(-C(=O)-Z N ) p (-H) q -L 1 -[N(-C(=O)-Z N ) r (-H) s -L 1 -] t -N(-C(=O)-Z N ) p (-H) q [In the formula, Z N is, in each occurrence, independently an alkyl group having 14 to 24 carbon atoms, L 1 is, in each occurrence, independently a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, p is, in each occurrence, independently an integer of 1 or more and 2 or less, q is, in each occurrence, independently 0 or 1, p + q is 2 in each N(-C(=O)-Z N ) p (-H) q , r is, in each occurrence, independently 0 or 1, s is, in each occurrence, independently 0 or 1, r + s is 1 in each N(-C(=O)-Z N ) r (-H) s , and t is an integer of 0 or more and 3 or less.] The method for producing a pulp product according to any one of items 1 to 16, which is a compound represented by .

Advantages of the Invention

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

Modes for Carrying Out the Invention

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

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

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

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

[0012] <Method for manufacturing pulp product> The method for manufacturing a pulp product in the present disclosure is 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 are included.

[0013] In one aspect of the present disclosure, a pulp product with good liquid repellency (especially high-temperature oil resistance) can be produced. In one aspect of the present disclosure, the amount of the liquid repellent (especially the liquid repellent compound) used can be reduced. It is presumed that the arrangement and rearrangement of the molecular structure (for example, the hydrocarbon group of the hydrocarbon-based liquid repellent) of the liquid repellent compound attached to the pulp during heating and cooling contribute 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 liquid repellent, adheres to the inside and / or surface of the pulp by heating. Here, the adhesion may be physical adhesion or chemical adhesion. For example, the liquid repellent compound may be physically or (reactively) chemically modified to the hydroxyl group of the pulp.

[0016] When the pulp composition contains a liquid medium, in the first heating step, the liquid medium contained in the pulp composition may be removed from the pulp composition. That is, drying may be performed in the first heating step. In the first heating step, the amount of the liquid medium in the pulp composition may be removed until it becomes 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 pressurizing the pulp composition, or may be performed without pressurization. The pressure during pressurization 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 pressurization 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 pressurizing to 0.1 - 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 the molding is as follows: (1) Preparation of pulp mold intermediate Place a net-like body on a metal pulp mold forming die provided with a suction hole for the slurry, and put the pulp slurry therein. Here, a liquid-repellent compound may be added to the pulp slurry. The pulp mold intermediate is prepared by sucking and dehydrating the pulp slurry through the pulp mold forming die and the net-like body. (2) Drying of the pulp mold intermediate The obtained pulp mold intermediate is dried from above and below with a metal osmese forming die heated to a predetermined temperature (the first heating temperature, for example, 60 - 200 °C) under a predetermined pressure (for example, 0.1 - 1 MPa). Thereby, a molded body (pulp mold) formed in the shape of a container can be manufactured.

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

[0020] The first 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, preferably 40°C or higher, 80°C or higher, 100°C or higher, 120°C or higher, or 150°C or higher, and may also 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, or 120°C or lower, preferably 250°C or lower, or 200°C or lower. 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 with respect to the melting point of the liquid-repellent compound, 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 also 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 with respect to the melting point of the liquid-repellent compound, preferably 0.7 times or more, 1.0 times or more, or 1.2 times or more, particularly 1.0 times or more with respect to the melting point of the liquid-repellent compound, and may also be 4.0 times or less, 3.5 times or less, 3.0 times or less, 2.5 times or less, 2.0 times or less, 1.5 times or less, 1.2 times or less, or 1.0 times or less, preferably 3.0 times or less, or 2.0 times or less.

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

[0024] The time for maintaining the first heating temperature is not particularly limited, but may be 10 seconds or more, 30 seconds or more, 60 seconds or more, 90 seconds or more, or 120 seconds or more, preferably 30 seconds or more. Also, from the perspective of productivity, the time for maintaining the first heating temperature may preferably be within 1 hour, within 30 minutes, within 10 minutes, or within 5 minutes.

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

[0026] The first cooling step may be performed while pressurizing the precursor product (e.g., 0.1 to 1 MPa), or may be performed without pressurization. Preferably, it is not pressurized. For example, when cooling the precursor product, the precursor product may be cooled in the mold used in the previous step, or may be taken out of the mold and cooled. Preferably, it is taken out of the mold and cooled.

[0027] The method of cooling in the first cooling step is not limited, and examples include press cooling, heat dissipation, air cooling, etc.

[0028] The first cooling temperature may be -10°C or higher, 0°C or higher, 10°C or higher, 20°C or higher, 25°C or higher, 30°C or higher, 40°C or higher, 50°C or higher, 60°C or higher, 70°C or higher, 80°C or higher, or 90°C or higher, and may also 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, it is 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 with respect to the melting point of the liquid-repellent compound, preferably -150°C or higher, -100°C or higher, or -50°C or higher, and may also be +25°C or lower, +15°C or lower, +5°C or lower, 0°C or lower, -5°C or lower, -10°C or lower, -15°C or lower, -20°C or lower, -25°C or lower, -30°C or lower, -35°C or lower, -40°C or lower, -50°C or lower, -75°C or lower, -100°C or lower, -125°C or lower, or -150°C or lower, preferably 0°C or lower, -15°C or lower, -30°C or lower, -50°C or lower, or -75°C or lower.

[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 with respect to the melting point of the liquid-repellent compound, and may also be 2.0 times or less, 1.75 times or less, 1.5 times or less, 1.25 times or less, 1.0 times (melting point) or less, 0.9 times or less, 0.8 times or less, 0.7 times or less, 0.6 times or less, 0.5 times or less, 0.4 times or less, 0.3 times or less, 0.2 times or less, or 0.1 times or less.

[0031] The first cooling temperature may be -300°C or 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 with respect to the first heating temperature, and may also 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, preferably -75°C or lower, or -150°C or lower.

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

[0033] The time for maintaining the first cooling temperature 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, still more preferably 10 minutes or more, and may be 1 hour or more. Also, from the viewpoint of productivity, the time for maintaining the first cooling temperature is preferably within 48 hours, within 24 hours, or within 12 hours.

[0034] 〔Second Heating Step〕 In the second heating step, the pre-cooled product is heated to the second heating temperature to obtain a pulp product.

[0035] The second heating step may be performed while pressurizing the pre-cooled product (for example, 0.1 to 1 MPa), or may be performed without pressurization. Preferably, it is not pressurized. For example, when heating the pre-cooled product, the pre-cooled product may be heated in the mold used in the previous step, or may be taken out of the mold and heated. Preferably, it is taken out of the mold and heated.

[0036] The heating method in the second heating step is not limited, and examples include hot press, hot air drying, oven heating, etc. 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, preferably 40°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 also 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, 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 with respect to the melting point of the liquid-repellent compound, preferably -50°C or higher, -30°C or higher, or 0°C (melting point) or higher, and may also 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, preferably +75°C or lower, +50°C or lower, +10°C or lower, 0 (melting point)°C or lower, -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 with respect to the melting point of the liquid-repellent compound, preferably 0.7 times or more, 0.8 times or more, 1.0 times or more, or 1.2 times or more, particularly 0.7 times or more with respect to the melting point of the liquid-repellent compound, and may also be 4.0 times or less, 3.5 times or less, 3.0 times or less, 2.5 times or less, 2.0 times or less, 1.5 times or less, 1.2 times or less, or 1.0 times or less, preferably 2.0 times or less, 1.5 times or less, or 1.2 times or less.

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

[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 with respect to the first cooling temperature, and may also 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 performed in one stage or in multiple stages, but heating is performed at least until the pre-cooled product reaches the second heating temperature.

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

[0044] A pulp product is obtained through the second heating step. The amount of the liquid-repellent compound adhered to the pulp product after the second heating step may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and may also be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, and is preferably 3.0% by weight 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 manufacturing the pulp product in the present disclosure may include a step of treating a pulp base material with a sizing agent to obtain a pulp composition.

[0046] As a method for treating the pulp base material, an internal addition treatment method of adding a sizing agent to pulp before papermaking (for example, pulp slurry) or an external addition treatment method of applying a sizing agent to pulp after papermaking (for example, a pulp product) can be used. Examples of the internal addition treatment include mixing, dipping, etc., and may include a step of adding a sizing agent to the pulp slurry and stirring and mixing.

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

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

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

[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 the sizing agent.

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

[0052] [Sizing agent] The sizing agent contains a liquid-repellent compound. The sizing agent will be described in detail separately in <Sizing agent> below. The addition amount of the sizing agent added to the pulp base material may be adjusted so that the amount of the liquid-repellent compound becomes a desired amount.

[0053] The amount of the liquid-repellent compound may be 0.1 part by weight or more, 0.3 part by weight or more, 0.5 part by weight or more, 0.75 part by weight or more, 1.0 part by weight or more, 2.0 part by weight or more, or 3.0 part by weight or more per 100 parts by weight of the pulp, and may also 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 part by weight or less, 0.75 part by weight or less, or 0.5 part 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 that is a fatty acid ester may be 0.1 part by weight or more, 0.3 part by weight or more, 0.5 part by weight or more, 0.75 part by weight or more, 1.0 part by weight or more, 2.0 part by weight or more, or 3.0 part by weight or more per 100 parts by weight of the pulp, and may also 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 part by weight or less, 0.75 part by weight or less, or 0.5 part by weight or less, preferably 5.0 parts by weight or less, more preferably 3.0 parts by weight or less.

[0055] The amount of the liquid-repellent compound that is a fatty acid amide may be 0.1 part by weight or more, 0.3 part by weight or more, 0.5 part by weight or more, 0.75 part by weight or more, 1.0 part by weight or more, 2.0 parts by weight or more, or 3.0 parts by weight or more, per 100 parts by weight of the pulp, and may also 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 part by weight or less, 0.75 part by weight or less, or 0.5 part 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 that is a linear hydrocarbon may be 0.1 part by weight or more, 0.3 part by weight or more, 0.5 part by weight or more, 0.75 part by weight or more, 1.0 part by weight or more, 2.0 parts by weight or more, or 3.0 parts by weight or more, per 100 parts by weight of the pulp, and may also 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 part by weight or less, 0.75 part by weight or less, or 0.5 part 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 liquid-repellent compound that is an amine-modified product may be 0.1 part by weight or more, 0.3 part by weight or more, 0.5 part by weight or more, 0.75 part by weight or more, 1.0 part by weight or more, 2.0 parts by weight or more, or 3.0 parts by weight or more, per 100 parts by weight of the pulp, and may also 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 part by weight or less, 0.75 part by weight or less, or 0.5 part 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 liquid-repellent compound which is a polyol-modified product may be 0.1 part by weight or more, 0.3 part by weight or more, 0.5 part by weight or more, 0.75 part by weight or more, 1.0 part by weight or more, 2.0 part by weight or more, or 3.0 part by weight or more, and may also 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 part by weight or less, 0.75 part by weight or less, or 0.5 part by weight or less, preferably 5.0 parts by weight or less, more preferably 3 parts by weight or less, based on 100 parts by weight of the pulp.

[0059] The amount of the liquid-repellent compound which is a polycarboxylic acid-modified product may be 0.1 part by weight or more, 0.3 part by weight or more, 0.5 part by weight or more, 0.75 part by weight or more, 1.0 part by weight or more, 2.0 part by weight or more, or 3.0 part by weight or more, and may also 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 part by weight or less, 0.75 part by weight or less, or 0.5 part by weight or less, preferably 5.0 parts by weight or less, more preferably 3.0 parts by weight or less, based on 100 parts by weight of the pulp.

[0060] The amount of the liquid-repellent compound which is a vinyl polymer may be 0.1 part by weight or more, 0.3 part by weight or more, 0.5 part by weight or more, 0.75 part by weight or more, 1.0 part by weight or more, 2.0 part by weight or more, or 3.0 part by weight or more, and may also 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 part by weight or less, 0.75 part by weight or less, or 0.5 part by weight or less, preferably 5.0 parts by weight or less, more preferably 3.0 parts by weight or less, still more preferably 2.0 parts by weight or less, based on 100 parts by weight of the pulp.

[0061] In the external addition treatment, the amount of the liquid-repellent compound contained in the coating layer is 0.01 g / m 2 or more, 0.03 g / m 2 or more, 0.05 g / m 2 or more, 0.1 g / m 2 or more, 0.3 g / m 2 or more, 0.5 g / m 2 or more, or 1.0 g / m2 may be the above, and also 5.0 g / m 2 or less, 4.0 g / m 2 or less, 3.0 g / m 2 or less, 2.0 g / m 2 or less, 1.0 g / m 2 or less, 0.5 g / m 2 or less, 0.3 g / m 2 or less, or 0.1 g / m 2 or less may be acceptable.

[0062] [Additive] In addition to pulp and a sizing agent (sizing liquid compound), the pulp composition may contain sizing agents (e.g., cationic sizing agents, anionic sizing agents, rosin sizing agents (e.g., acidic rosin sizing agents, neutral rosin sizing agents)), paper strength enhancers, flocculants, fixing agents, yield improvers, dyes, fluorescent dyes, slime control agents, defoaming agents, and other additives used in the production of pulp products. Specific examples of the additives include alkyl ketene dimer, alkenyl succinic anhydride, styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, starch, modified starch, carboxymethyl cellulose, polyamideamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichloride and polyalkylene polyamines, dicyandiamide-formalin condensates, dimethyldiallylammonium chloride polymers, olefin / maleic anhydride polymers, and the like. The pulp composition contains components derived from the sizing agent, and each component contained in the sizing agent may be separately added to the pulp composition as an additive.

[0063] The additive may be nonionic, cationic, anionic, or amphoteric. The ionic charge density of the additive may be 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. In the case of a paper base material containing a cationic additive with respect to the pulp, the sizing agent may be anionic, and in the case of a paper base material containing an anionic additive, the sizing agent may be cationic.

[0064] The amount of the above additive may be 0.1 part by weight or more, 1 part by weight or more, 3 part by weight or more, 5 part by weight or more, respectively, based on 100 parts by weight of the pulp, and may also 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.

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

[0066] <Sizing agent> The sizing agent in the present disclosure can adhere to a base material (especially a pulp base material) and impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance to the base material, and can also function as a water repellent, oil repellent, water repellent, oil repellent, and / or stain repellent. The sizing agent of the present disclosure contains a liquid repellent compound. The liquid repellent compound itself may be used as the sizing agent, or may be used as the sizing agent in combination with other components as described below.

[0067] The repellent agent in the present disclosure may not have any selected from the group consisting of a compound having a fluoroalkyl group with 8 or more carbon atoms, a compound having a perfluoroalkyl group with 8 or more carbon atoms, a compound having a fluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The repellent agent in the present disclosure can impart liquid repellency to the substrate even without containing these fluorine compounds.

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

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

[0070] [Liquid repellent compound] The liquid repellent compound in the present disclosure can adhere to a substrate (especially a pulp substrate) and impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or antifouling property, to the substrate.

[0071] [Properties, etc.] The properties that a liquid-repellent compound may have are shown below. Such properties may vary depending on the type of compound.

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

[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 also be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. By having a water contact angle of the liquid-repellent compound equal to or greater than the above lower limit, good liquid-repellent properties (especially water-repellent properties) can be imparted to the substrate. The water contact angle refers to the static contact angle of the liquid-repellent compound with respect to the spin-coated film, and is obtained by dropping 2 μL of water onto the spin-coated film and measuring the contact angle 1 second after droplet landing.

[0074] The liquid-repellent compound is preferably a bio-based compound having carbon of bio-based origin. The bio-based content is measured in accordance with ASTM D6866. The bio-based content may be 20% or more, preferably 30% or more, more preferably 50% or more, still more preferably 60% or more, still more preferably 70% or more, most preferably 80% or more or 90% or more, for example 100%. A high bio-based content means a small amount of use of fossil resource-based materials represented by petroleum and the like. From this perspective, it can be said that the higher the bio-based content of the liquid-repellent compound, the more preferable.

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

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

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

[0078] The liquid-repellent compound may be a compound having a monovalent hydrocarbon group or a monovalent polysiloxane group having 1 to 40 carbon atoms, which may have a substituent. 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] (A monovalent hydrocarbon group which may have a substituent) The liquid-repellent compound may have a monovalent hydrocarbon group which may have a substituent.

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

[0081] The number of carbon atoms of the hydrocarbon group may be 1 or more, 3 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 6 or more, 10 or more, 12 or more, or 16 or more, and may also 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’, -N(R’)2, -COOR’, and a halogen atom, etc. (wherein R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, the hydrocarbon group may have 1 to 3 (e.g., 1) -OR’ (especially -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. Similar to the (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 at each occurrence, a hydrocarbon group having 1 to 40 carbon atoms or a reactive group, a is an integer of 5 or more and 10000 or less.] It may also be represented by

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

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

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

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

[0089] Examples of the reactive group are groups having a functional group (for example, hydroxy group, amino group, mercapto group, epoxy group, carboxyl group, halogen-substituted alkyl group, vinyl group, (meth)acrylic group, (meth)acryloyloxy group, and (meth)acrylamide group, hydrogen atom directly bonded to a silicon atom, etc.). These functional groups may be directly bonded to the silicon atom or may be bonded to an organic group directly bonded to the silicon atom. The organic group may be a hydrocarbon group, for example, an alkylene group or a divalent aromatic group. The hydrocarbon group may have 2 to 12 carbon atoms, and as the alkylene group, those having 2 to 10 carbon atoms are preferred. As the divalent aromatic group, those having 6 to 12 carbon atoms are preferred. The reactive group may be a group selected from the group consisting of a hydroxy group, an epoxy ring, a carboxyl group, a (meth)acrylic group, and an amino group, and may be, for example, at least one selected from the group consisting of an epoxy ring, a hydroxy group, a (meth)acrylic group, and a carboxyl group.

[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, preferably 10 or more, and may be 10000 or less, 7500 or less, 5000 or less, 3000 or less, 1500 or less, 1000 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less, preferably 500 or less.

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

[0092] R, which is a hydrocarbon group having 6 to 40 carbon atoms in the polysiloxane group s The amount of s R may be 3 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more, based on the total of R, and may be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less.

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

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

[0095] The terminal structure of the polysiloxane group described above is not limited, but is -OR s , -Si(R s)It may be 3 or the like. R of the terminal structure s It may have one or more reactive groups. Examples of the reactive group are as described above, and for example, it may be 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 includes, but is not limited to, a hydrocarbon group having 1 to 40 carbon atoms (for example, 1 to 20 carbon atoms) which may be interrupted by an oxygen atom, for example, a (poly)oxyalkylene group having 1 to 40 carbon atoms (for example, 1 to 20 carbon atoms).

[0097] Examples of the polysiloxane group include -[-Si(R s )2-O-] a -Si(R s )3 -L s1 -[-Si(R s )2-O-] a -Si(R s )3 -L s1 -O-L s1 -[-Si(R s )2-O-] a -R s -L s1 -[-Si(R s )2-O-] a -Si(R s )3 -L s1 -O-L s1 -[-Si(R s )2-O-] a -R s -L s1 -[-Si(R s )2-O-] a -Si(R s ) 3、 -L s1 -[-Si(R s )2-O-] a -R s [Wherein, R s is, independently at each occurrence, a hydrocarbon group or a reactive group having 1 to 40 carbon atoms, and the terminal R s has one or more reactive groups, R s more than 50 mol% of the total of the groups is a methyl group, L s1 is a hydrocarbon group having 1 to 20 carbon atoms, a is 5 or more and 10,000 or less. ], TIFF0007701661000001.tif2169[Wherein, a represents an integer from 0 to 150, b represents an integer from 1 to 150, (a + b) is from 5 to 200, and n is an integer from 0 to 36. ] etc. may be mentioned.

[0098] [Examples of liquid-repellent compounds] As an example of the liquid-repellent compound, a compound having a hydrocarbon group with 6 or more and 40 or less carbon atoms can be mentioned. Examples and preferred ranges of the hydrocarbon group are as described above.

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

[0100] As an example of the liquid-repellent compound, at least one selected from the group consisting of amine-modified products, polyol-modified products, polycarboxylic acid-modified products, and vinyl polymers can be mentioned (detailed below).

[0101] The liquid-repellent compound may contain an ester group, an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfonylurea group, a sulfonylurethane group, or a sulfonimide group (for example, an ester group, an amide group, a urethane group, a urea group, an imide group). For example, the liquid-repellent compound may contain -C(=O)-O-, -O-C(=O)-, -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'- (R' is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms)). The liquid-repellent compound may be a compound in which a raw material compound and a modifying group (in particular, a monovalent hydrocarbon group which may have the above-described substituents) are bonded via at least one of these groups. The liquid-repellent compound may contain an amide structure. By the liquid-repellent compound containing 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 (acid amide) groups, urethane groups, urea groups, imide groups, thioamide groups, thiourethane groups, thiourea groups, thioimide groups, sulfonamide groups, sulfonylurethane groups, sulfonylurea groups, sulfonimide groups, etc. The amide structure may be an amide structure selected from the group consisting of -(C=O)N(-)2, -(C=S)N(-)2, and -S(=O)2N(-)2 (note that each group may be in a direction reversed left and right). Here, at least one of the bonds possessed by N of the amide structure may be bonded to a hydrogen atom. The amide structure is preferably -(C=O)N(-)2, and may be an amide structure in a group selected from the group consisting of an amide group, a urethane group, a urea group, and an imide group).

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

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

[0104] In terms of its structure, the amine-modified product in the present disclosure is excellent in dispersibility in a liquid medium, and the repellent of the present disclosure can have stable performance. In the case of a repellent using a polymer-type compound as an active ingredient, the molecular weight distribution is wide and it tends to contain a relatively large amount of impurity components. On the other hand, the amine-modified product can be made low molecular weight and the molecular weight distribution can be narrowed (unified), and the performance can be improved.

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

[0107] The amine-modified product in the present disclosure may be a polyamide having a plurality of amide structures. For example, a plurality of modifying groups (e.g., Z N ) described below may be modified to the amine (raw material amine compound, for example, polyamine) 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 material amine compound) with a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group, which may have a substituent.

[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 alkyl group having 6 to 40 carbon atoms is modified to the amine.

[0110] For details of the monovalent hydrocarbon group and the monovalent polysiloxane group, which may have a substituent, the descriptions of the above-mentioned (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 having a predetermined number of bonds (valences), which are obtained by removing a predetermined number of atoms or atomic groups (e.g., hydrogen) from an amine compound. The amino group in the amine skeleton means a group selected from the group consisting of -NH2, -NH-, and -N(-)2, and also includes an amino group adjacent to a carbonyl group contained in an amide group, a urethane group, a urea group, an imide, or the like. Note that the amine skeleton may be an aliphatic group or an aromatic group having one or more amino groups, and the presence of heteroatoms other than nitrogen is not excluded.

[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 also be 2800 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 600 or less, 450 or less, 300 or less, or 250 or less.

[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 also be 100 or less, 80 or less, 60 or less, 40 or less, 30 or less, 20 or less, 10 or less, or 5 or less, preferably 50 or less, particularly 30 or less.

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

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

[0116] The amine skeleton may be composed of a 1- to 3-valent amino group and a chain-like saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group that may be interrupted by an oxygen atom and / or a sulfur atom.

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

[0118] (-Y N -Z N n ) The amine-modified product in the present disclosure has the following formula: -Y N -Z N n [wherein, Y N is a direct bond or a (1 + n)-valent group, Z N is a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group, and n is an integer of 1 or more and 3 or less.] having one or more groups represented by, at least one -Y N -Z N n is bonded to the nitrogen atom of the amine skeleton.

[0119] -Y N -Z N n The number of -Y

[0120] -Z N -Z N n in the amine-modified product is bonded to the nitrogen atom of the amine skeleton. All -Y N -Z N n -Y N -Z N n in the amine-modified product may be 10% or more, 30% or more, 60% or more, 80% or more, or 100%, and may also be 75% or less, 50% or less, or 25% or less. -Y N -Z N n not bonded to the nitrogen atom of the amine skeleton is bonded to another group (e.g., hydrocarbon group) of the amine skeleton.

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

[0122] n is the number of Z that binds to Y N and may be an integer of 1 or more and 3 or less. n may be 1 or more, 2 or more, or 3 or more, and may also be 3 or less, 2 or less, or 1 or less, for example 2 or less. N n is the number of Z that binds to Y and may be an integer of 1 or more and 3 or less. n may be 1 or more, 2 or more, or 3 or more, and may also be 3 or less, 2 or less, or 1 or less, for example 2 or less.

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

[0124] Y N The molecular weight of Y may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more, and may also be 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. Y N Y 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 Y may form one or more selected from the group consisting of an amide group, a urea group, a urethane group, and an imide together with the amino group in the amine skeleton. Examples of such amide groups, urea groups, urethane groups, and imide groups include -O-C(=O)-NR'- -NR'-C(=O)- -NR'-C(=O)-O- -NR'-C(=O)-NR'- -C(=O)-NR'- -C(=O)-NR'-C(=O)- [wherein, R' is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms).] are exemplified. Y N is preferably bonded to the nitrogen atom in the amine skeleton via a -(C=O)- group.

[0126] Y Nis a 1+n-valent group composed of one or more selected from the group consisting of direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -C(=S)-, -NR’-, -C(OR’)R’-, -C(OR’)(-)2, -N(-)2, a 2- to 4-valent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a 2- to 4-valent hydrocarbon aromatic ring, and a 2- to 4-valent heterocyclic ring [In the formula, R’ is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).] and may be a 1+n-valent group composed of one or more selected from the group consisting of

[0127] Y N is Y N1 and Y N2 and is a 1+n-valent group composed of one or more selected from the group consisting of Y N1 is a group composed of one or more selected from the group consisting of direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -C(=S)-, -NR’-, -C(OR’)R’-, -C(OR’)(-)2, and -N(-)2 (wherein, in each occurrence, R’ is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) Y N2 is a group composed of one or more selected from the group consisting of a 2- to 4-valent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a 2- to 4-valent hydrocarbon aromatic ring, and a 2- to 4-valent heterocyclic ring and may be a 1+n-valent group composed of one or more selected from the group consisting of. In the present specification, Y N The group described as is bonded to the amine skeleton on the left side and Z N on the right side.

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

[0129] Y N1 is a direct bond or a polyvalent group. The valence of Y N1 may be 2 to 4, 2 to 3, or 2. YN1 is preferably not only a direct bond.

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

[0131] Y N1 may be composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -C(=S)-, -NR’-, -C(OR’)R’-, -C(OR’)(-)2, and -N(-)2 (wherein R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms)). Y N1 Examples of a direct bond, -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=O)-NR’-, -NR’-, -NR’-C(=O)-, -NR’-C(=O)-O-, -NR’-C(=O)-NR’-, -C(=O)-, -C(=O)-O-, -C(=O)-NR’-, -C(=O)-NR’-C(=O)-, -C(=NR’)-, -S-, -SO2-, -SO2NR’-, -C(OR’)R’-, -C(OR’)(-)2, -N(-)2, etc. [wherein R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms).] are included. Note that Y N1When it is bonded to the nitrogen atom of the amine skeleton, the nitrogen atom is regarded as a part of the amine skeleton (amino group).

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

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

[0134] Y N2 is a group with a valence of two or more. Y N2 The valence of may be, for example, 2 to 4, 2 to 3, or 2.

[0135] Y N2 The number of carbon atoms of may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0136] Y N2 is composed of one or more selected from the group consisting of a 2- to 4-valent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a 2- to 4-valent hydrocarbon aromatic ring which may have a substituent, and a 2- to 4-valent heterocycle which may have a substituent.

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

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

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

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

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

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

[0143] Y N2 Examples of -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali(-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- [wherein Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring.] etc. are included.

[0144] Y N2 Specific examples of -(CH2) p -(p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(q and r are each independently 0 to 20, for example 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring) and the like can be mentioned.

[0145] ·Y N Examples of Y N Examples of Y will be described. In the following, R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[0146] Y N Examples of Y include, when Y N is divalent, -Y N1 -, -Y N1 -Y N2 -, -Y N1 -Y N2 -Y N1 -, -Y N1 -Y N2 -Y N1 -Y N2 -, -Y N2 -, -Y N2 -Y N1 -, -Y N2 -Y N1 -Y N2 -, -Y N2 -Y N1 -Y N2 -Y N1 -, etc. can be mentioned.

[0147] Y N Examples of Y include, when Y N is trivalent, -Y N1 (-), -Y N1 -Y N2 (-), -Y N1 -(Y N2 -), -Y N1 -Y N2 -Y N1 (-), -Y N1 -Y N2 (-Y N1 (-), -Y N1 -(Y N2 -YN1 -)2, -Y N1 -Y N2 -Y N1 -Y N2 (-)2, -Y N1 -Y N2 -Y N1 -(Y N2 -) 2、 -Y N1 -Y N2 -(Y N1 -Y N2 -) 2、 -Y N1 -(Y N2 -Y N1 -Y N2 -)2; -Y N2 (-)2, -Y N2 -Y N1 (-)2, -Y N2 -(Y N1 -)2, -Y N2 -Y N1 -Y N2 (-)2, -Y N2 -Y N1 (-Y N2 -)2, -Y N2 -(Y N1 -Y N2 -)2, -Y N2 -Y N1 -Y N2 -Y N1 (-)2, -Y N2 -Y N1 -Y N2 -(Y N1 -) 2、 -Y N2 -Y N1 -(Y N2 -Y N1 -) 2、 -Y N2 -(Y N1 -Y N2 -Y N1 Examples include -)2, etc.

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

[0149] Y N Preferred examples of -Y N1 -,-Y N1 -Y N2 -,-Y N1 -Y N2 -Y N1 -,-Y N1 -Y N2 (-)2, -Y N2 -,-Y N2 -Y N1 -,-Y N2 -Y N1 -Y N2 -,-Y N2 -Y N1 (-)2, etc. In the amine-modified product, one or more Ys N preferably have an amine backbone side terminal of -(C=O)- and are bonded to the nitrogen atom in the amine backbone.

[0150] Y N is preferably -Y N1 -,-Y N1 -Y N2 -,-Y N1 -Y N2 -Y N1 -,-Y N1 -Y N2 (-)2, -Y N2 -,-Y N2 -Y N1 -,-Y N2 -Y N1 -Y N2 -,-Y N2 -Y N1 (-)2, [In the formula, Y N1 is, in each occurrence, independently a direct bond, -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=O)-NR’-, -NR’-, -NR’-C(=O)-, -NR’-C(=O)-O-、 -NR’-C(=O)-NR’-、 -C(=O)-、 -C(=O)-O-、 or -C(=O)-NR’- -C(=O)-NR’-C(=O)- (In the formula, R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms).) and Y N2 is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a divalent aromatic group (for example, a divalent phenyl group, a divalent triazole group).] is a group represented by this. Thereby, liquid repellency can be imparted to the substrate favorably.

[0151] Y N As further specific examples of *-(C=O)- -O-(C=O)-NR’- [In the formula, * means being bonded to the nitrogen atom of the amine skeleton, R’ is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms).] etc. can be mentioned.

[0152] (Z N ) Z N is a monovalent hydrocarbon group having 1 or more and 40 or less carbon atoms which may have a substituent, or a monovalent polysiloxane group, and the descriptions in the above (monovalent hydrocarbon group which may have a substituent) and (monovalent polysiloxane group) are incorporated herein.

[0153] [Examples of amine-modified products] (Example 1 of amine-modified product) As an example of the amine-modified product, the following formula: N(-Y N -Z N n ) p (-H) q -L1 -[N(-Y N -Z N n ) r (-H) s -L 1 -] t -N(-Y N -Z N n ) p (-H) q [In the formula, Y N is, independently at each occurrence, a direct bond or a 1 + n-valent group, Z N is, independently at each occurrence, a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, L 1 is, independently at each occurrence, a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by an oxygen atom and / or a sulfur atom, n is, independently at each occurrence, an integer of 1 or more and 3 or less, p is, independently at each occurrence, an integer of 0 or more and 2 or less, q is, independently at each occurrence, an integer of 0 or more and 2 or less, p + q is 2 in each N(-Y N -Z N n ) p (-H) q and is 2, r is, independently at each occurrence, 0 or 1, s is, independently at each occurrence, 0 or 1, r + s is 1 in each N(-Y N -Z N n ) r (-H) s and is 1, the sum of all p and all r is 1 or more, t is an integer of 0 or more and 10 or less.] Examples include compounds (amine-modified example 1) represented by .

[0154] In amine modification form 1, Y N , Z N , and for the details of n, refer to the above description.

[0155] In amine modification form 1, L 1 is a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be interrupted by an oxygen atom and / or a sulfur atom, and may be a cyclic, branched, or linear hydrocarbon group, preferably a chain hydrocarbon group or an aromatic hydrocarbon. L 1 may refer to the hydrocarbon groups in the description of the [amine skeleton] mentioned above. The hydrocarbon group may be interrupted by an oxygen atom and / or a sulfur atom, or may consist only of carbon atoms, nitrogen atoms, and hydrogen atoms. L 1 is, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings. L 1 is preferably a cyclic group having both a ring (e.g., aromatic ring) and a chain structure (e.g., linear structure, ether oxygen, thioether sulfur). Specific examples include 1,3-phenylenebisalkylene group, 1,4-phenylenebisalkylene group, diphenyl ether diyl group, diphenyl thioether diyl group, etc. L 1 The number of carbon atoms of L may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and may also be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less.

[0156] In amine modification form 1, p is, independently at each occurrence, an integer of 0 or more and 2 or less, q is, independently at each occurrence, an integer of 0 or more and 2 or less, and p + q is 2 in each N(-Y N -Z N n ). p (-H) q In, it is 2. Preferably, p may be 1 or more, for example 2, independently at each occurrence.

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

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

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

[0160] (Amine modification form 2) As an example of another amine modification form, the following formula: N(-Y N -Z N n ) p (-H) q -L 2 (-Y N -Z N n ) u [wherein, Y N is, independently at each occurrence, a direct bond or a 1 + n-valent group, Z N is, independently at each occurrence, a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, L2 is an aliphatic hydrocarbon group or aromatic hydrocarbon group with 1+u valence and 2 to 20 carbon atoms, which may be interrupted by oxygen atoms and / or sulfur atoms, n is, independently in each occurrence, an integer of 1 or more and 3 or less, p is an integer of 0 or more and 2 or less, q is an integer of 0 or more and 2 or less, p + q is 2, u is an integer of 1 or more and 3 or less, The sum of p and u is 1 or more.] Examples include compounds represented by (amine modification example 2).

[0161] In amine modification example 2, Y N , Z N For details of and n, refer to the above description.

[0162] In amine modification example 2, L 2 is an aliphatic hydrocarbon group or aromatic hydrocarbon group with 1+u valence and 2 to 20 carbon atoms, which may be interrupted by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched, or linear hydrocarbon group, preferably a chain hydrocarbon group or an aromatic hydrocarbon. L 2 As L, the hydrocarbon groups described in the above description of [amine skeleton] may be referred to. The hydrocarbon group may be interrupted by oxygen atoms and / or sulfur atoms, or may consist only of carbon atoms, nitrogen atoms, and hydrogen atoms. L 2 For example, it may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings. L 2 is preferably a cyclic group having a ring (e.g., aromatic ring) and a chain structure (e.g., linear structure, ether oxygen, thioether sulfur). Specific examples include 1,3-phenylenebisalkylene group, 1,4-phenylenebisalkylene group, diphenyl ether diyl group, diphenyl thioether diyl group, etc. L 2The number of carbon atoms may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and may also be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less.

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

[0164] In amine modification form 2, u is an integer of 1 or more and 3 or less. u is 1, 2, or 3, for example, 2 or 3.

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

[0166] (Specific example) As a specific example of the amine-modified body, a compound represented by the following formula can be mentioned. In the following formula, Y N , Z N , and the details of n are referred to the above description.

[0167] TIFF0007701661000002.tif35154

[0168] TIFF0007701661000003.tif28160

[0169] TIFF0007701661000004.tif31167

[0170] TIFF0007701661000005.tif18157

[0171] TIFF0007701661000006.tif18165

[0172] TIFF0007701661000007.tif18166

[0173] TIFF0007701661000008.tif18158

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

[0175] [Manufacturing method] The manufacturing method of the amine-modified product is not limited, but for various amines (raw material amines), in the presence of a condensing agent if necessary, Z N A method of synthesizing by reacting a carboxylic acid containing a group, a method of synthesizing by reacting an acid chloride, acid anhydride, isocyanate, etc. of a carboxylic acid containing a Z N group with various amines, etc. may be mentioned. The condensing agent may be a known condensing agent, and examples thereof include DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA, Py-Bop, etc.

[0176] (Amine (raw material amine)) Examples of amines (raw material amines) that are precursors of the amine skeleton include alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine that can form the amine skeleton; alkylene diamines such as ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine, cyclohexanediamine, and methylenebiscyclohexylamine; polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tris(2-aminoethyl)amine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tris(2-aminopropyl)amine, tetrapropylenetetramine, pentapropylenehexamine, iminobispropylamine, dibutylenetriamine, bis(2-aminoethoxy)ethane, bis(2-aminoethyl)ether, bis[2-(2-aminoethoxy)ethyl]ether, bis[2-(3-aminopropoxy)ethyl]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-aminophenanthrene, 2-, 3-, or 4-aminobiphenyl, etc.; monocyclic aromatic polyamines such as o-, m-, or p-phenylenediamine, o-, m-, or p-xylylenediamine, diaminotoluene, 2,3-, 2,4-, or 2,5-tolylenediamine, etc.;Polycyclic aromatic polyamines such as diaminobiphenyl, bisaminophenoxyphenylpropane, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl sulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenylphenylethane, bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, aminophenoxybiphenyl, aminophenoxyphenyl ketone, bisaminoditrifluoromethylbenzylbenzene, aminophenoxyphenyl sulfone, aminophenoxyphenyl ether, aminophenoxyphenylpropane, bis(aminophenoxybenzoyl)benzene, bis(aminophenoxy-α,α-dimethylbenzyl)benzene, bis[(aminoaryloxy)benzoyl]diphenyl ether, bis(amino-α,α-dimethylbenzylphenoxy)benzophenone, aminophenoxyphenyl sulfide, bis[amino-α,α-dimethylbenzylphenoxy]diphenyl sulfone, 4,4'-bis[aminophenoxyphenoxy]diphenyl sulfone, diaminodiaryloxybenzophenone, diaminoaryloxybenzophenone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminotriphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenebisaniline, 4,4'-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 4,4'-diaminodiphenyl ether, 4,4′-bis(aminophenyl)amine; oxygen- or sulfur-containing polycyclic aromatic polyamines such as 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, etc.;2-Hydroxyethyl ethylenediamine, 2-hydroxyethyl propylenediamine, di-2-hydroxyethyl ethylenediamine, di-2-hydroxyethyl propylenediamine, 2-hydroxypropyl ethylenediamine, di-2-hydroxypropyl ethylenediamine, and other hydroxyl group-containing polyamines such as these may be mentioned. The polyamine may be one obtained by polymerizing a polymerizable compound such as allylamine.;

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

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

[0179] The polymerization degree in the present disclosure means the average polymerization degree. The average polymerization degree in the present disclosure means the polymerization obtained by measuring under the following conditions. When the polyol-modified product in the present disclosure is a polyglycerol-modified product obtained by modifying polyglycerol, the polymerization degree of the polyol-modified product means the average polymerization degree of the above polyglycerol. The average polymerization degree of polyglycerol is the average polymerization degree (n) calculated from the hydroxyl value by the end group analysis method. Specifically, the average polymerization degree 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 indicator of the number of hydroxyl groups contained in polyglycerin. The hydroxyl value is calculated from the amount of potassium hydroxide required to neutralize acetic acid necessary for acetylating the free hydroxyl groups contained in 1 g of polyglycerin, and is calculated in accordance with "Japanese Oil Chemists' Society Standard, Standard Oil Analysis Test Methods (I), 2003 Edition" compiled by the Society of Japanese Oil Chemists. The hydroxyl value of the raw material polyglycerin is actually measured in accordance with the above standard oil analysis test method, and the average degree of polymerization and average molecular weight of polyglycerin can be calculated from the above relational expression.

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

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

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

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

[0184] The residual ratio 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, it may be 5% or more. Also, it 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, it may be 50% or less, 30% or less, or 10% or less. Here, the "residual ratio" means the unmodified ratio (mol%) among the hydroxyl groups derived from the polyol.

[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. Also, it 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. Also, it may be 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 400 or less. It is the value obtained by dividing the weight average molecular weight of the polyol-modified product by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent.

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

[0188] For the details of the monovalent hydrocarbon group and the monovalent polysiloxane group which may have a substituent, the descriptions of the above-mentioned (monovalent hydrocarbon group which may have a substituent) and (monovalent polysiloxane group) are incorporated by reference.

[0189] (-Y O -Z O n ) In the polyol modified product in the present disclosure, one or more hydroxy groups of the polyol are represented by the following formula: -Y O -Z O n [wherein, Y O is a 1 + n-valent group composed of one or more selected from the group consisting of Y O1 and Y O2 , Y O1 is a group composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein, R' is independently, in each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms).). Y O2 is a group composed of one or more selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 2 to 4 carbon atoms and 1 to 40 carbon atoms, an optionally substituted hydrocarbon aromatic ring having 2 to 4 carbon atoms, and an optionally substituted heterocyclic ring having 2 to 4 carbon atoms. Z O is an optionally substituted monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group. n is an integer of 1 or more and 3 or less.] and may be substituted by a group represented by

[0190] (Y O ) Y O is Y O1 and Y O2a 1+n-valent group selected from the group consisting of one or more selected from the group consisting of Y O1 is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -C(=S)-, -NR’-, -C(OR’)R’-, -C(OR’)(-)2, and -N(-)2 (wherein R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).). Y O2 is a group consisting of one or more selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 2 to 4 valences and 1 to 40 carbon atoms, an optionally substituted hydrocarbon aromatic ring having 2 to 4 valences, and an optionally substituted heterocyclic ring having 2 to 4 valences.

[0191] n is the number of O Z bonded to Y 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 also 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 also be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[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 sulfourea group, a sulfourethane group, or a sulfonimide group. For example, Y O may contain -C(=O)-NR’-, -C(=S)-NR’-, -O-C(=O)-NR’-, -NR’-C(=O)-, -NR’-C(=O)-NR’- or -SO2NR’-. Y OBy including these groups, the liquid repellency can be improved.

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

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

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

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

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

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

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

[0201] Y O2 is a group having a valence of two or more. Y O2 The valence of may be, for example, 2 to 4, 2 to 3, or 2.

[0202] Y O2 The number of carbon atoms of may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0203] Y O2It is composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a divalent to tetravalent hydrocarbon aromatic ring which may have a substituent, and a divalent to tetravalent heterocyclic ring which may have a substituent.

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

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

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

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

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

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

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

[0211] Y O2 Specific examples of -(CH2) p -(p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(q and r are each independently 0 to 20, for example 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring) etc. can be mentioned.

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

[0213] Y O Examples of are, when Y O is divalent, -Y O1 -, -Y O1 -Y O2 -, -Y O1 -Y O2 -Y O1 -, -Y O1 -Y O2 -Y O1 -Y O2 -, -Y O2 -, -Y O2 -Y O1 -, -Y O2 -YO1 -Y O2 - and -Y O2 -Y O1 -Y O2 -Y O1 - etc. can be mentioned.

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

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

[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. can be mentioned.

[0217] (Preferred Y O example) Preferably, Y O is -O-Y O11 -, or -O-Y O11 -Y O21 -Y O12 - [Wherein, each symbol is independent at each occurrence, YO11 is a direct bond, -C(=O)-, -C(=O)-NR’-, or -C(=S)-NR’-, Y O21 is a hydrocarbon group having 1 to 40 carbon atoms, Y O12 is -O-, -O-C(=O)-, -O-C(=O)-O-, -C(=O)-NR’-, -O-C(=O)-NR’-, -NR’-, -NR’-C(=O)-, -NR’-C(=O)-O-, -NR’-C(=O)-NR’-, -C(=O)-, -C(=O)-O-, -C(=O)-NR’-, -SO2-, -SO2NR’-, -C(OR’)R’-, or -C(OR’)(-)2.], may be

[0218] Y O11 is a non-hydrocarbon linker, a direct bond or a polyvalent 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 also 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 and may be a hydrocarbon group having 1 to 40 carbon atoms.

[0222] Y O21 The number of carbon atoms of may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

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

[0224] Y O21 Specific examples of -(CH2) p -(where p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(where q and r are each independently 0 to 20, for example 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring) and the like can be mentioned.

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

[0226] Y O12 may at least contain 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 sulfourea group, a sulfourethane group, or a sulfonimide group. For example, Y O12 may be -C(=O)-NR’-, -O-C(=O)-NR’-, -NR’-C(=O)-, -NR’-C(=O)-NR’- or -SO2NR’-. Y C12 By Y containing these groups, the liquid repellency can be improved.

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

[0228] [Other modifying groups] The hydroxy group of the polyol is -Y O -Z O n may be substituted with a modifying group other than the above. Examples of the modifying group are an anionic group and / or a cationic group.

[0229] Examples of the anionic group include monomers having a carboxyl group, a sulfonic acid group or a phosphoric acid group.

[0230] Examples of the salt of the anionic group include an alkali metal salt, an alkaline earth metal salt, or an ammonium salt, such as a methylammonium salt, an ethanolammonium salt, a triethanolammonium salt, and the like.

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

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

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

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

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

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

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

[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 also be 3000 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.

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

[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. Compounds converted from microorganisms are also included among the above natural products. Examples of polyols include monosaccharides, oligosaccharides, polysaccharides, sugar alcohols (reducing sugars), hydroxy acids, amino acids, vitamins, flavonols, hydroxy hydrocarbons, hydroxy group-containing compound polymers, polyether polyols, polymer polyols, polyester polyols, and other polyols.

[0241] Examples of monosaccharides include glucose, fructose, galactose, xylose, etc.

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

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

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

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

[0246] Examples of amino acids include glucosamine and the like.

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

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

[0249] Examples of hydroxyhydrocarbons include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerin, trimethylolpropane, trimethylolethane, and the like. Hydroxyhydrocarbon is a hydrocarbon having a hydroxy group, which may be aromatic or aliphatic, but is preferably aliphatic. When referring to hydroxyhydrocarbon, it may mean hydroxyhydrocarbons other than compounds included in other groups such as polysaccharides (other hydroxyhydrocarbons).

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

[0251] Examples of polyether polyols may be compounds obtained by addition polymerization of alkylene oxides to an initiator. Examples of the initiator include compounds having two or more hydroxyl groups. For example, the initiator includes propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, glycerin, polyglycerin, trimethylolpropane, triethanolamine, pentaerythritol, ethylenediamine, aromatic diamine, diethylenetriamine, sorbitol, and sucrose. Examples of the alkylene oxide include ethylene oxide and propylene oxide. The polyether polyol obtained by addition polymerization of the alkylene oxide to the initiator is also referred to as a polyoxyalkylene polyol or an oxyalkylene derivative of a polyol. Representative examples of the polyether polyol include polyoxypropylene triol obtained by addition polymerization of propylene oxide to glycerin, and polyoxypropylene polyglyceryl ether obtained by addition polymerization of propylene oxide to polyglycerin.

[0252] Examples of polymer polyols are compounds obtained by polymerizing at least a part of the polyether polyol with an ethylenically unsaturated monomer in the polyether polyol. Examples of the ethylenically unsaturated monomer include acrylonitrile and styrene.

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

[0254] (Modifier) The modifier is a compound having reactivity with the polyol, and is preferably a compound having a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group as described above.

[0255] Examples of the modifier are as follows. Acid halide G(O=)C-Z O Acid anhydride O(C(=O)-Z O )2 Carboxylic acid HO(O=)C-Z O Isocyanate O=C=N-Z O Thiocyanate S=C=N-Z O Epoxy (CH2OCH)CH2O-Z O Halide G-Z O Amine H2N-Z O Hydroxy HO-Z O [In the formula, Z O is as described above, and G is a halogen atom (for example, F, Cl, Br, or I).]

[0256] Z in the structure of the above modifier O may be replaced with any group constituting the modifying group. For example, Z O may be a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a group having a monovalent polysiloxane group. For example, Z O may be -Y O -Z O n and so on.

[0257] The polyol modified product may be synthesized by reacting a polyol with a modifier. For example, a modifier which is an acid halide compound, an acid anhydride, or a carboxylic acid is reacted with the hydroxy group of the polyol to form an ester bond, thereby synthesizing a polyol modified product. Further, a modifier which is a halide or an epoxy compound is reacted with the hydroxy group of the polyol to form an ether bond, thereby generating a polyol modified product. Those skilled in the art can appropriately design the reaction conditions between the polyol and the modifier, such as the use of a catalyst (for example, an acid catalyst or a base catalyst) and the use of a condensing agent, according to the target product.

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

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

[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 under the following apparatus and conditions. Separation column: SB-806M (8 mm×30 mm, Shodex) Column temperature: 40 °C Mobile phase solvent: Ion-exchanged water Mobile phase flow rate: 1.0 mL / min Sample concentration: 0.5 wt% Injection volume: 50 μL Detector: RI detector (Waters2414, Waters)

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

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

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

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

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

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

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

[0268] (-Y C -Z C n ) In the polycarboxylic acid modifier in the present disclosure, the hydroxy groups of one or more carboxyl groups of the polycarboxylic acid are represented by the following formula: -Y C -Z C n [wherein, Y C is a 1 + n-valent group composed of one or more selected from the group consisting of Y C1 and Y C2 ; Y C1is a group composed of one or more selected from the group consisting of direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -C(=S)-, -NR’-, -C(OR’)R’-, -C(OR’)(-)2, and -N(-)2 (wherein R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).), Y C2 is a group composed of one or more selected from the group consisting of a 2- to 4-valent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, and a heterocyclic ring which may have a substituent, Z C is a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group, n is an integer of 1 or more and 3 or less.] may be substituted by a group represented by

[0269] (Y C ) Y C is the same as Y C1 and Y C2 is a (1 + n)-valent group composed of one or more selected from the group consisting of Y C1 is a group composed of one or more selected from the group consisting of direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -C(=S)-, -NR’-, -C(OR’)R’-, -C(OR’)(-)2, and -N(-)2 (wherein R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).), Y C2 is a group composed of one or more selected from the group consisting of a 2- to 4-valent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, and a heterocyclic ring which may have a substituent.

[0270] n is the Z that binds to Y C ​C is a number and may be an integer of 1 or more and 3 or less. n may be 1 or more, 2 or more, or 3 or more. 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 Y may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more, and may also be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[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 sulfourea group, a sulfourethane group, or a sulfonimide group. For example, Y C may be -C(=O)-NR’-, -O-C(=O)-NR’-, -NR’-C(=O)-, -NR’-C(=O)-NR’- or -SO2NR’-. Y C By containing these groups, the liquid repellency can be improved.

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

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

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

[0276] Y C1may be composed of one or more selected from the group consisting of direct bond, -O-, -C(=O)-, -S(=O)2-, -NR’-, -C(OR’)R’-, and -C(OR’)(-)2 (wherein R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms)). Y C1 Examples of direct bond, -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=O)-NR’-, -NR’-, -NR’-C(=O)-, -NR’-C(=O)-O-, -NR’-C(=O)-NR’-, -C(=O)-, -C(=O)-O-, -C(=O)-NR’-, -SO2-, -SO2NR’-, -C(OR’)R’-, -C(OR’)(-)2 etc. (wherein R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms).) are included.

[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 sulfourea group, a sulfourethane group, or a sulfonimide group. For example, Y C1 may contain -C(=O)-NR’-, -O-C(=O)-NR’-, -NR’-C(=O)-, -NR’-C(=O)-NR’- or -SO2NR’-. Y C1 By Y containing these groups, the liquid repellency can be improved.

[0278] ○ Y C2 YC2 is a linker of a hydrocarbon 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 may be a hydrocarbon group or a non-hydrocarbon group (including a heteroatom). Y C2 may be aliphatic or aromatic. Y C2 may be linear, branched, or cyclic.

[0280] Y C2 is a group with a valence of two or more. Y C2 The valence of may be, for example, 2 to 4, 2 to 3, or 2.

[0281] Y C2 The number of carbon atoms of may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0282] Y C2 is composed of one or more selected from the group consisting of a 2- to 4-valent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a 2- to 4-valent hydrocarbon aromatic ring which may have a substituent, and a 2- to 4-valent heterocyclic ring which may have a substituent.

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

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

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

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

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

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

[0290] Y C2 Specific examples of -(CH2) p -(p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(q and r are each independently 0 to 20, for example 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring) etc. can be mentioned.

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

[0292] Y C 's example includes, when Y C is divalent, -Y C1 -, -Y C1 -Y C2 -, -Y C1 -Y C2 -Y C1 -, -Y C1 -Y C2 -Y C1 -Y C2 -, -Y C2 -, -Y C2 -Y C1 -, -Y C2 -Y C1 -Y C2 -, -Y C2 -Y C1 -Y C2 -Y C1 -etc. can be mentioned.

[0293] Y C 's example includes, when Y C is trivalent, -Y C1 (-)2, -Y C1 -Y C2 (-)2, -Y C1 -(Y C2 -)2, -Y C1 -Y C2 -Y C1 (-)2, -Y C1 -Y C2 (-Y C1 -)2, -Y C1 -(Y C2 -YC1 -), 2, -Y C1 -Y C2 -Y C1 -Y C2 (-), 2, -Y C1 -Y C2 -Y C1 -(Y C2 -) 2、 -Y C1 -Y C2 -(Y C1 -Y C2 -) 2、 -Y C1 -(Y C2 -Y C1 -Y C2 -), 2; -Y C2 (-), 2, -Y C2 -Y C1 (-), 2, -Y C2 -(Y C1 (-), 2, -Y C2 -Y C1 -Y C2 (-), 2, -Y C2 -Y C1 (-Y C2 (-), 2, -Y C2 -(Y C1 -Y C2 (-), 2, -Y C2 -Y C1 -Y C2 -Y C1 (-), 2, -Y C2 -Y C1 -Y C2 -(Y C1 -) 2、 -Y C2 -Y C1 -(Y C2 -Y C1 -) 2、 -Y C2 -(Y C1 -Y C2 -Y C1 -), 2, etc. can be mentioned.

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

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

[0296] (Preferred Y C example) Preferably, Y C is -Y C11 - or -Y C11 -Y C21 -Y C12 - [Wherein, each symbol is independent at each occurrence, Y C11 is -O- or -NR'- and Y C21 is a hydrocarbon group having 1 to 40 carbon atoms, Y C12 is -O-, -O-C(=O)-, -O-C(=O)-O-, -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'- or -C(OR')(-)2.], may be.

[0297] Y C11 is a non-hydrocarbon linker, a direct bond or a group having a valence of two or more.

[0298] Y C11 The molecular weight of Y may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less, and may also 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 and may be a hydrocarbon group having 1 to 40 carbon atoms.

[0301] Y C21 The number of carbon atoms of Y may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[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 (for example, saturated) aliphatic hydrocarbon group.

[0303] Y C21 Specific examples of Y include -(CH2) p -(where p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(where q and r are each independently 0 to 20, for example 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring) and the like.

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

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

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

[0307] [Other modifying groups] The hydroxy group of the polycarboxylic acid may be substituted with a modifying group other than -Y C -Z C n Examples of the modifying group are an anionic group and / or a cationic group. For the anionic group and / or the cationic group, the description of [Other modifying groups] in the above polyol is incorporated herein by reference.

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

[0309] (Polycarboxylic acid) Polycarboxylic acid is a compound having two or more carboxyl groups and is a compound serving as a raw material for a polycarboxylic acid modified product. 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] Polycarboxylic acid may be low molecular weight (for example, weight average molecular weight less than 1000, 500 or less) and / or high molecular weight. The weight average molecular weight of polycarboxylic acid may be 100 or more, 300 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may also be 1000000 or less, 7500000 or less, 500000 or less, 3000000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 5000 or less, 3000 or less, 2000 or less, 1000 or less, or 500 or less.

[0311] The number of carboxyl groups possessed by 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 also be 3000 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.

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

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

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

[0315] The dicarboxylic acid is a compound having two carboxyl groups, and examples thereof include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid, terephthalic acid, malic acid, tartaric acid, aldic acid, and salts thereof.

[0316] The tricarboxylic acid is a compound having three carboxyl groups, and examples thereof include citric acid, tricarballylic acid, t-aconitic acid, trimellitic acid, and salts thereof.

[0317] The tetracarboxylic acid is a compound having four carboxyl groups, and examples thereof include pyromellitic acid and salts thereof.

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

[0319] (Modifier) The modifier is a compound having reactivity with the polycarboxylic acid, and is preferably a compound having a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent as described above.

[0320] Examples of the modifier are as follows. Epoxy (CH2OCH)CH2O-Z C Amine H2N-Z C Hydroxy HO-Z C [wherein, Z C is as described above.]

[0321] Z in the structure of the above-mentioned modifier C may be replaced with any group constituting a modifying group. For example, Z C may be a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent. For example, Z C may be -Y C -Z C n and the like.

[0322] The polycarboxylic acid modified product may be synthesized by reacting a polycarboxylic acid with a modifier. For example, a modifier which is an epoxy compound is reacted with the carboxy group of a polycarboxylic acid to form an ester bond, thereby generating a polycarboxylic acid modified product. Those skilled in the art can appropriately design the reaction conditions between the polycarboxylic acid and the modifier, such as the use of a catalyst (for example, an acid catalyst or a base catalyst) and the use of a condensing agent, according to the target product.

[0323] [Vinyl polymer] As an example of the 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] [Properties, etc.] The vinyl polymer preferably contains a compound having 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, still more preferably 60% or more, still more preferably 70% or more, most preferably 80% or more or 90% or more, for example, 100%. A high biobased content means a small amount of use of fossil resource-based materials typified by petroleum and the like. From this perspective, it can be said that the higher the biobased content of the vinyl polymer, the more preferable.

[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 also be 250°C or lower, 225°C or lower, 200°C or lower, 150°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, 80°C or lower, or 50°C or lower.

[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 also 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 the 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 with 6 to 40 carbon atoms.

[0328] The hydrocarbon group of 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, 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 of 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 also 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.

[0329] Monomer (a) may contain an amide group, a urea group or a urethane group. The hydrocarbon monomer may be a combination of a hydrocarbon monomer having an amide group, a urea group or a urethane group and a hydrocarbon monomer having no amide group, urea group or urethane group. By including such a group in monomer (a), the effects of the present disclosure can be achieved well.

[0330] The monomer (a) having a hydrocarbon group with 6 to 40 carbon atoms is Formula: CH2=C(-X a )-C(=O)-Y a (R a ) k [In the formula, R a are each independently a hydrocarbon group having 6 to 40 carbon atoms, X a is a hydrogen atom, a monovalent organic group or a halogen atom, Y a is a divalent to tetravalent hydrocarbon group having 1 carbon atom (particularly, -CH2-, -CH(-)2), -C6H4-, -O-, -C(=O)-, -S(=O)2- or -NH- and is a group composed of at least one or more selected therefrom, k is 1 to 3.] It is preferably a monomer represented by

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

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

[0333] Y a is -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 Y’ is a direct bond, -O-, -NH-, or -S(=O)2-, R’ is -(CH2) m -(where m is an integer of 1 to 5) or -C6H4- (a phenylene group).] may be.

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

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

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

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

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

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

[0340] Preferred specific examples of the long-chain acrylate 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 specific examples of the long-chain acrylamide monomer include stearyl (meth)acrylamide, icosyl (meth)acrylamide, and behenyl (meth)acrylamide.

[0341] (a2) monomer The monomer (a2) is a monomer different from the monomer (a1). The monomer (a2) is a (meth)acrylate or (meth)acrylamide having a group composed of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, or -CH2-. The monomer (a2) has the formula: CH2=C(-X a2 )-C(=O)-Y a21 -Z(-Y a22 -R a2 ) n [In the formula, R a2 are each independently a hydrocarbon group having 6 to 40 carbon atoms, X a2 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y a21 is -O- or -NH-, Y a22 are each independently a direct bond, or a group composed of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, or -CH2-, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2.] It may be a compound represented by. Y a22 And / or Z may not be a direct bond. Y 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. R a2 In, the number of carbon atoms of the hydrocarbon group is preferably 12 to 30, for example 16 to 26 or 15 to 26, particularly 18 to 22 or 17 to 22.

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

[0344] Y a22 is -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' is independently a direct bond, -O-, -NH- or -S(=O)2-, R' is -(CH2) m -(m is an integer from 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 -(CH2) l -C6H4-(CH2) l -(l is independently an integer from 0 to 5 each and -C6H4- is a phenylene group).] It may be.

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

[0346] Y a22is preferably -O-, -NH-, -O-C(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O)2-, -S(=O)2-NH-, -O-C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4. Y a22 is more preferably -NH-C(=O)-, -C(=O)-NH-, -O-C(=O)-NH-, -NH-C(=O)-O- or -NH-C(=O)-NH-. Y a22 does not have to be a direct bond. Y 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 structure or a branched structure. The number of carbon atoms of Z is preferably 2 to 4, particularly preferably 2. Specific examples of Z are a direct bond, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH(-)2, -CH2(CH-)CH2-, -CH2CH2CH(-)2, -CH2CH2CH2CH2CH(-)2, -CH2CH2(CH-)CH2-, -CH2CH2CH2CH(-)2. Z does not have to be a direct bond.

[0348] The monomer (a2) is CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-R a2 , CH2=C(-X a2 )-C(=O)-O-(CH2) m -O-C(=O)-NH-R a2 , CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-O-R a2 , CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-NH-R a2 is preferably [where R a2 and X a2 are as defined above.]. The monomer (a2) is CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-R a2 is particularly preferred.

[0349] The monomer (a2) can be produced by reacting a hydroxyalkyl (meth) acrylate or hydroxyalkyl (meth) acrylamide with a long-chain alkyl isocyanate. Examples of the long-chain alkyl isocyanate include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, behenyl isocyanate, and the like. Alternatively, the monomer (a2) can also 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 long-chain alkyl alcohol. Examples of the long-chain alkylamine include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, behenylamine, and the like. Examples of the long-chain alkyl alcohol include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, and the like.

[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] TIFF0007701661000009.tif2453

[0352] TIFF0007701661000010.tif2253 TIFF0007701661000011.tif2152 TIFF0007701661000012.tif2155

[0353] TIFF0007701661000013.tif2357 TIFF0007701661000014.tif2256 TIFF0007701661000015.tif2156

[0354] TIFF0007701661000016.tif2051 TIFF0007701661000017.tif2054 TIFF0007701661000018.tif2352 TIFF0007701661000019.tif2659

[0355] TIFF0007701661000020.tif2046

[0356] TIFF0007701661000021.tif2249 [In the above formula, n is a number from 6 to 40, and m is a number from 1 to 5.] The compound of the above chemical formula is an acrylic compound with a hydrogen atom at the α-position. Specific examples may be a methacrylic compound with a methyl group at the α-position and an α-chloroacrylic compound with a chlorine atom at the α-position.

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

[0358] R a21 is an organic residue having an ethylenically unsaturated polymerizable group and is not particularly limited as long as there is a double bond between carbons. Specifically, -C(=O)CR a211 =CH2, -CHR a211 =CH2, -CH2CHR a211 =CH2 and other organic residues having an ethylenically unsaturated polymerizable group are exemplified, and R a211 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Also, R 21 may have various organic groups other than the ethylenically unsaturated polymerizable group. For example, organic groups such as chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, and polysiloxane groups are exemplified, and these organic groups may be substituted with various substituents. R a21 is preferably -C(=O)CR a211 =CH2.

[0359] R a22 is a hydrocarbon group having 6 to 40 carbon atoms, preferably an alkyl group, and examples include a chain hydrocarbon group and a cyclic hydrocarbon group. Among them, a chain hydrocarbon group is preferable, and a linear saturated hydrocarbon group is particularly preferable. The carbon number of R a22 is 6 to 40, 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 preferably it is linear. The carbon number of R a23 is preferably 2 to 4, and particularly preferably 2. R a23 is preferably an alkylene group.

[0361] The amide group-containing monomer is one in which R a22 is of one type (for example, only a compound in which R a22 has 17 carbon atoms), or one in which R a22 is a combination of a plurality (for example, a compound in which the carbon number of R a22 is 17 and a compound in which the carbon number of Ra22 It may be a mixture with a compound having 15 carbon atoms.

[0362] Examples of the amide group-containing monomer are carboxylic acid amide alkyl (meth)acrylates. 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, myristic acid amide ethyl (meth)acrylate, lauric acid amide ethyl (meth)acrylate, isostearic acid ethyl amide (meth)acrylate, oleic acid ethyl amide (meth)acrylate, tertiary butyl cyclohexyl caproic acid amide ethyl (meth)acrylate, adamantane carboxylic acid ethyl amide (meth)acrylate, naphthalene carboxylic acid amide ethyl (meth)acrylate, anthracene carboxylic 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, or a mixture thereof.

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

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

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

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

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

[0368] n may be, for example, 1 to 50, particularly 1 to 30, 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, the formula -(CH2) x - or -(CH2) x1 -(CH(CH3)) 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. -(CH2) x1 - and -(CH(CH3)) x2 - are not limited to the order in the described formula and may be random.].] -(R b O) n - in which R may be two or more (for example, 2 to 4, particularly 2) 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. It may be a combination of].

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

[0370] Specific examples of monomer (b) can be exemplified, for example, by 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)O-H CH2=CH-C(=O)-NH-CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH(CH3)O-H CH2=CH-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH(CH3)CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH(CH2CH3)O-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)O-H CH2=CH-C(=O)-NH-C(CH3)(CH2CH3)O-H 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)O-H CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH(CH3)O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH2CH3)O-H 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)O-H CH2=C(CH3)-C(=O)-NH-C(CH3)(CH2CH3)O-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)2-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)4-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)6-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 23 -CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 90 -CH3

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

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

[0379] (c) Monomer containing an ionic group The vinyl polymer may contain a monomer (c) containing an ionic group. 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 monomers 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, phosphoric acid (meth)acrylate, vinylbenzenesulfonic acid, acrylamidotertiarybutylsulfonic acid, etc., or salts thereof.

[0381] Examples of the salt of the anionic group include an alkali metal salt, an alkaline earth metal salt, or an ammonium salt, such as a methylammonium salt, an ethanolammonium salt, a triethanolammonium salt, etc.

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

[0383] The cationic group which is a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, such as carboxylic acids having 1 to 20 carbon atoms (especially monocarboxylic acids such as acetic acid, propionic acid, butyric acid, stearic acid, etc.) 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 (for example, acetate) CH2=CHCOO-CH2CH2-N(CH2CH3)2 and its salts (for example, acetate) CH2=C(CH3)COO-CH2CH2-N(CH3)2 and its salts (for example, acetate) CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2 and its salts (for example, acetate) CH2=CHC(O)N(H)-CH2CH2CH2-N(CH3)2 and its salts (for example, acetate) CH2=CHCOO-CH2CH2-N(-CH3)(-CH2-C6H5) and its salts (for example, acetate) CH2=C(CH3)COO-CH2CH2-N(-CH2CH3)(-CH2-C6H5) and its salts (for example, 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] As the ionic group-containing monomer (c), methacrylic acid, acrylic acid, or dimethylaminoethyl methacrylate is preferable, and methacrylic acid or dimethylaminoethyl methacrylate is more preferable.

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

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

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

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

[0390] Examples of the crosslinkable monomer include, but are not limited to, diacetone (meth)acrylamide, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoxyacetoxyethyl (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, neopentyl glycol di(meth)acrylate, and the like.

[0391] (f) Monomer containing a cyclic hydrocarbon group The vinyl polymer may have a repeating unit derived from the 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 an 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, and is preferably alicyclic. The cyclic hydrocarbon group may be saturated or unsaturated, and is preferably saturated. The cyclic hydrocarbon group may be a monocyclic group, a polycyclic group, or a bridged cyclic group, and a bridged cyclic group is preferred. The cyclic hydrocarbon group may have a chain group (for example, a linear or branched hydrocarbon group).

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

[0395] Specific examples of the cyclic hydrocarbon group include cyclohexyl group, t-butylcyclohexyl group, adamantyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, bornyl group, isobornyl group, norbornyl group, dicyclopentanyl group, dicyclopentenyl group, benzyl group, phenyl group, naphthyl group, 2-t-butylphenyl group, residues obtained by removing one or more hydrogen atoms from these groups (for example, cyclohexylene group, adamantylene group, phenylene group, naphthylene group, etc.), and groups which are substituents of these.

[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 obtained by substituting these acrylates with acrylamide. These may be used alone or in combination of two or more.

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

[0398] [Composition of polymer] The combination of monomers (a) to (g) constituting the repeating unit of the vinyl polymer is not particularly limited, and for example, it is as follows (parentheses are omitted). a a + b a + b + c a + c a + d a + b + c + d a + b + c + d + e a + b + c + d + e + f Furthermore, other monomer (g) may be used in combination with the above combinations. In the case of pulp products, it is preferable to use monomer (a), monomer (b), and monomer (c) in combination.

[0399] The amount of the repeating unit 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, with respect to the vinyl polymer, and may also 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.

[0400] The amount of the repeating unit 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, with respect to the vinyl polymer, and may also 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. The amount of the repeating unit derived from monomer (b) may be 0.01 part by weight or more, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 1000 parts by weight or more, with respect to 100 parts by weight of the repeating unit derived from monomer (a), and may also be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less.

[0401] The amount of the repeating unit 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 with respect to the vinyl polymer, and may also 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. The amount of the repeating unit derived from monomer (c) may be 0.01 part by weight or more, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more with respect to 100 parts by weight of the repeating unit derived from monomer (a), and may also be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less.

[0402] The amount of the repeating unit 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 with respect to the vinyl polymer, and may also 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. The amount of the repeating unit derived from monomer (d) may be 0.01 part by weight or more, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, based on 100 parts by weight of the repeating unit derived from monomer (a), and may also be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less.

[0403] The amount of the repeating unit 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, based on the vinyl polymer, and may also 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. The amount of the repeating unit derived from monomer (e) may be 0.01 part by weight or more, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, based on 100 parts by weight of the repeating unit derived from monomer (a), and may also be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less.

[0404] The amount of the repeating unit 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 with respect to the vinyl polymer, and may also 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. The amount of the repeating unit derived from monomer (f) may be 0.01 part by weight or more, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more with respect to 100 parts by weight of the repeating unit derived from monomer (a), and may also be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less.

[0405] The amount of the repeating unit 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 with respect to the vinyl polymer, and may also 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. The amount of the repeating unit derived from the monomer (g) may be 0.01 part by weight or more, 0.1 part by weight or more, 1 part by weight or more, 3 part by weight or more, 5 part by weight or more, 10 part by weight or more, 15 part by weight or more, 20 part by weight or more, 50 part by weight or more, 75 part by weight or more, 100 part by weight or more, 300 part by weight or more, 500 part by weight or more, 1000 part by weight or more, based on 100 parts by weight of the repeating unit derived from the monomer (a), and may also be 3000 part by weight or less, 2000 part by weight or less, 1000 part by weight or less, 750 part by weight or less, 500 part by weight or less, 300 part by weight or less, 200 part by weight or less, 100 part by weight or less, 50 part by weight or less, 30 part by weight or less, 10 part by weight or less, or 1 part by weight or less.

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

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

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

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

[0410] In order to obtain a polymer aqueous dispersion with excellent storage stability, it is desirable to polymerize by micronizing monomers in water using an emulsifying device capable of imparting strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. As the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and they are used in the range of 0.5 to 20 parts by weight based on 100 parts by weight of the monomers. It is preferable to use an anionic and / or nonionic and / or cationic emulsifier. When 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 can be sufficiently compatible with these monomers. By adding the compatibilizer, it is possible to improve the emulsifying property and copolymerizability.

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

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

[0413] 〔Dispersant〕 The release agent 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] The dispersant may use each of an organic dispersant and an inorganic dispersant, or may be a combination of an organic dispersant and an inorganic dispersant.

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

[0416] The dispersant may be non-fluorine.

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

[0418] The nonionic dispersant may be a low molecular type or a high molecular type. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0419] Examples of the nonionic dispersant include ether, ester, ester ether, alkanolamide, polyol, and amine oxide.

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

[0421] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are alcohols having 1 to 30 valences (particularly 2 to 10 valences) and 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0422] Examples of ester ethers are compounds in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. Examples of alcohols are alcohols having 1 to 30 valences (particularly 2 to 10 valences) and 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

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

[0424] The polyol may be an alcohol having 2 to 5 valences and 10 to 30 carbon atoms. The amine oxide may be an oxide of an amine (secondary amine or preferably tertiary amine) (for example, having 5 to 50 carbon atoms).

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

[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, etc. Among these, those in which the structure of the alkylene oxide addition part and the polyalkylene glycol part is polyoxyethylene (POE) or polyoxypropylene (POP) or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Also, the nonionic dispersant may not contain an aromatic group.

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

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

[0430] Specific examples of the nonionic dispersant include ethylene oxide and hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkane (C 12 -C 16 ) thiol, sorbitan monofatty acid (C7-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. are included. As an example of a nonionic dispersant, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycols, polyethyleneimine ethoxylates, etc. may be mentioned.

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

[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 of low molecular weight (for example, with a molecular weight of 2000 or less, particularly 10000 or less), or may be of high molecular weight (for example, with a molecular weight of 2000 or more). The molecular weight of the cationic dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 1000000 or less, 750000 or less, 500000 or less, 250000 or less, 100000 or less, 50000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0434] The cationic dispersant may be aliphatic or aromatic, and examples include ammonium salts (such as quaternary ammonium salts). The cationic dispersant may also be an oxyethylene-added type ammonium salt. Specifically, amine salt type dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline; quaternary ammonium salt type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, benzethonium chloride, etc.; high molecular weight cationic dispersants such as polyquaternium-1 to 47, etc. Examples of the cationic dispersant include alkylamine salts, quaternary ammonium salts, etc.

[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 are hydrogen, or a hydrocarbon group having 1 to 40 carbon atoms, and X is an anionic group.] It may be a compound represented by. R 21 , R 22 , R23 and -R 24 Specific examples of 24 are alkyl groups (for example, methyl group, butyl group, stearyl group, palmitoyl group). Specific examples of X are halogen (for example, chlorine), acid (for example, hydrochloric acid, acetic acid). The cationic dispersant may be a monoalkyltrimethylammonium salt (alkyl having 4 to 40 carbon atoms).

[0436] Specifically, the low-molecular-weight cationic dispersant has the formula: R 1 p -N + R 2 q X - [wherein R 1 is a linear and / or branched aliphatic (saturated and / or unsaturated) group having 12 or more carbon atoms (for example, C 12 ~C 50 ), R 2 is H or an alkyl group having 1 to 4 carbon atoms, benzyl group, polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (especially 2, particularly 3) to 50) (CH3 and C2H5 are particularly preferred), X is a halogen atom (for example, chlorine), or a fatty acid salt having 1 to 4 carbon atoms, or a sulfonate having 1 to 4 carbon atoms, p is 1 or 2, q is 2 or 3, and p + q = 4.] and may be an ammonium salt represented by . The number of carbon atoms of R 1 may be 12 to 50, for example, 12 to 30.

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

[0438] The high-molecular cationic dispersant may be various polymers having cationic groups (e.g., ammonium group, quaternary ammonium group) (e.g., polyquaternium-1 to 47). Examples of the high-molecular cationic dispersant include cationized starch, cationized cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propyl)hydroxyethylcellulose chloride), cationized guar gum, cationized xanthan gum, cationized natural products such as chitosan (especially cationized saccharides); polymers of cationic group-containing monomers such as aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternized dimethylammonium ethyl methacrylate, diallyldimethylammonium chloride, dimethylaminopropylamine, quaternized vinylimidazole, and the like.

[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 of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 100,000 or less, 10,000 or less, 7500 or less, 5000 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, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonated fatty acid salts, N-acyl amino acid type dispersants, phosphoric acid mono- or diester type dispersants, and sulfosuccinic acid esters. As an example of an anionic dispersant, carboxylate salts (e.g., fatty acid salts) and the like can be mentioned.

[0442] [Amphoteric Dispersant] The dispersant may contain an amphoteric dispersant. The amphoteric dispersant may be an amphoteric surfactant.

[0443] The amphoteric dispersant may be of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 100,000 or less, 10,000 or less, 7500 or less, 5000 or less, 25,000 or less, 750 or less, or 250 or less.

[0444] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amide betaines, betaine acetates, etc. Specifically, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetate betaine, fatty acid amide propyl dimethylaminoacetate betaine, etc. can be mentioned.

[0445] [Inorganic Dispersant] The dispersant may contain an inorganic dispersant.

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

[0447] Examples of the inorganic dispersant 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; hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

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

[0449] [Liquid medium] The liquid-repellent agent in the present disclosure may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The liquid-repellent agent may be a dispersion or a solution. The liquid-repellent agent in 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., alcohols, polyols such as glycol solvents, ether forms of polyols (e.g., monoether forms), etc.). These may be used alone or in combination of two or more.

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

[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, per 1 part by weight of the liquid-repellent compound, and may also be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less.

[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 with respect to 1 part by weight of the liquid-repellent compound, and may also be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less.

[0454] 〔Silicone〕 The liquid repellent agent in the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, in addition to good liquid repellency, it can also have good texture and durability.

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

[0456] The weight average molecular weight of the silicone may be 1000 or more, 10000 or more, or 50000 or more, and may also be 500000 or less, 2500000 or less, 100000 or less, or 50000 or less.

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

[0458] 〔Wax〕 The repellent agent in the present disclosure may contain wax. By containing wax, liquid repellency can be favorably imparted to the substrate.

[0459] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin waxes (such as polyethylene wax and polypropylene wax), oxidized polyolefin waxes, silicone waxes, animal and plant waxes, and mineral waxes. Hydrocarbon waxes, particularly paraffin wax, are preferred. Specific examples of the compounds constituting the wax are normal alkanes (for example, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane), normal alkenes (for example, 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene, 1-hentriacontene, 1-dotriacontene, 1-tritriacontene, 1-tetratriacontene, 1-pentatriacontene, 1-hexatriacontene). The number of carbon atoms of the compounds constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be 200 to 2000, for example, 250 to 1500, 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 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, based on 100 parts by weight of the liquid-repellent compound.

[0462] [Organic acid] The liquid-repellent agent of the present disclosure may contain an organic acid. Known organic acids can be used. Preferred examples of the organic acid include carboxylic acids, sulfonic acids, sulfinic acids, etc., and carboxylic acids are particularly preferred. Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., and formic acid or acetic acid is particularly preferred. In the present disclosure, one kind of organic acid may be used, or two or more kinds may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0463] [Amount of organic acid] The amount of the organic acid may be 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, based on 100 parts by weight of the liquid-repellent compound. Also, it may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of the organic acid may be adjusted so that the pH of the 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 hardening agent (crosslinking agent) in the repellent can cure the liquid-repellent compound well. The hardening agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen-reactive group of the liquid-repellent compound. Examples of the active hydrogen-reactive compound are isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of the active hydrogen-containing compound are hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

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

[0467] Examples of the aliphatic polyisocyanate include aliphatic diisocyanates such as 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-diisocyanatomethyl caproate, and lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane and other aliphatic triisocyanates. These may be used alone or in combination of two or more.

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

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

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

[0471] Derivatives of polyisocyanates include, for example, various derivatives such as dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, uretoimines, isocyanurates, iminooxadiazinediones, etc. of the above-mentioned polyisocyanate compounds. These may be used alone or in combination of two or more.

[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 obtained by blocking the isocyanate groups of the polyisocyanate compound with a blocking agent. It is preferable to use the blocked polyisocyanate compound because it is relatively stable in solution and can be used even in the same solution as the sizing agent.

[0473] The blocking agent blocks the free isocyanate groups. The blocked polyisocyanate compound can regenerate the isocyanate groups and easily react with hydroxyl groups, for example, by heating to 100 °C or higher, for example, 130 °C or higher. Examples of the blocking agent are phenolic compounds, lactam compounds, aliphatic alcohol compounds, oxime compounds, etc. The polyisocyanate compounds can be used alone or in combination of two or more.

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

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

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

[0477] [Other components] The liquid repellent may contain other components in addition to the above components. Examples of other components include polysaccharides, paper strength enhancers, flocculants, yield improvers, coagulants, binder resins, anti-slip agents, sizing agents, paper strength enhancers, fillers, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, fragrances, and the like. These may be used alone or in combination of two or more. In addition to the above components, as other components, other water and / or oil repellents, dispersants, hand modifiers, softeners, flame retardants, paint fixatives, anti-wrinkle agents, drying rate adjusters, crosslinking agents, film-forming aids, compatibilizers, anti-freezing agents, viscosity adjusters, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage preventers, anti-washing wrinkle agents, shape retainers, drape retainers, ironing property improvers, brighteners, whitening agents, fabric softening clay, migration inhibitors such as polyvinylpyrrolidone, polymer dispersants, soil release agents, scum dispersants, fluorescent brighteners such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Tinopal CBS-X manufactured by Ciba Specialty Chemicals), dye fixatives, anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine, stain removers, enzymes such as cellulase, amylase, protease, lipase, keratinase, etc. as fiber surface modifiers, anti-foaming agents, silk protein powder, their surface modified products or emulsion dispersions (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical Co., Ltd.), hydrolyzed silk solution (Jomo), Silkgen G Soluble S (Ichimaru Pharcos)) that can impart silk-like hand and functions such as moisture absorption and release, anti-pollution agents (e.g., nonionic polymer compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by Gohou Chemical Industry Co., Ltd.), SRC-1 manufactured by Clariant Japan, etc.) can be blended. These may be used alone or in combination of two or more.

[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 nanofibers, cellulose nanofibers, and pullulan. The polysaccharides may be substituted modified polysaccharides (excluding the above-mentioned liquid repellent compounds), and in particular, modified polysaccharides into which a hydroxyl group or a cationic group has been introduced.

[0479] [Paper strength enhancer, flocculant, yield improver or coagulant] Examples of paper strength enhancers, flocculants, yield improvers or coagulants include styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide-based polymers, polyamine-based polymers, polydiallyldimethylammonium chloride, alkylamine·epichlorohydrin condensates, condensates of alkylene dichloride and polyalkylene polyamines, dicyandiamide·formalin condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers, etc.

[0480] [Sizing agent] Examples of sizing agents include cellulose-reactive sizing agents, rosin-based sizing agents such as rosin soaps, rosin-based emulsions / dispersions, cellulose-reactive sizing agents, emulsions / dispersions of acid anhydrides such as alkyl and alkenyl succinic anhydrides (ASA), alkenyl and alkyl ketene dimers (AKD) and multimers, and anionic, cationic and amphoteric polymers of ethylenically unsaturated monomers such as 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, primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate esters, phosphonates, and phosphate esters; amphoteric antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, alanine and its derivatives; and nonionic antistatic agents such as amino alcohols and their derivatives, glycerin and its derivatives, polyethylene glycol and its derivatives. These may also be ion conductive polymers obtained by polymerizing or copolymerizing monomers having cationic, anionic, or zwitterionic conductive groups. These may be used alone or in combination of two or more.

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

[0483] [UV Absorbent] UV absorbers are agents that have the effect of protecting against ultraviolet rays and are components that absorb ultraviolet rays and convert them into and emit infrared rays, visible light, etc. Examples of UV absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole-based compounds, 4-t-butyl-4'-methoxybenzoylmethane, and the like.

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

[0485] [Deodorant] Examples of the deodorant include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, aminocarboxylic acid-based metal complexes (zinc complex of trisodium methylglycinediacetate described in International Publication No. 2012 / 090580), and the like.

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

[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.

Examples

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

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

[0490] [Practical oil resistance test] The mold was pretreated by storing it at 23°C and 50% humidity for 12 hours. 100 ml of corn oil at 65°C was poured into the mold, and after leaving it at room temperature for 45 minutes, the corn oil was taken out from the mold, and the degree of oil stain on the mold was evaluated. Evaluation values were set as follows according to the degree of penetration. 5: No stain on the inside. 4: Stain on the inside. No stain on the back side. 3: There is penetration on the inside. There is a slight penetration on the back side. 2: There is penetration on the inside. The penetration to the back side is less than 50% of the area. 1: There is penetration on the inside. The penetration to the back side is 50% or more and less than 100% of the area. 0: The entire back side is penetrated.

[0491] [Practical water resistance test] Pretreatment was carried out by storing the mold at 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 taken out from the mold, and the degree of penetration of the mold was evaluated. Evaluation values were set as follows according to the degree of penetration. 5: There is no penetration on the inside. 4: There is penetration on the inside. There is no penetration on the back side. 3: There is penetration on the inside. There is a slight penetration on the back side. 2: There is penetration on the inside. The penetration to the back side is less than 50% of the area. 1: There is penetration on the inside. The penetration to the back side is 50% or more and less than 100% of the area. 0: The entire back side is penetrated.

[0492] [Adhesion amount evaluation] The adhesion amount of the liquid repellent compound in the pulp mold is less than the addition amount of the liquid repellent compound. The adhesion amount can be calculated by the following procedure. As the first step, measure the paper dish of the pulp mold. As the second step, add an internal standard (for example, toluene, DMF) to a solvent (for example, chloroform) in which the liquid repellent compound dissolves to prepare an evaluation solvent. As the third step, weigh the evaluation solvent, immerse the weighed paper dish, and heat if necessary to extract the liquid repellent compound. As the fourth step, extract a part of the solution from which the liquid repellent compound has been extracted, dilute it with a heavy solvent, and perform 1H-NMR measurement. When a heavy solvent is used as the evaluation solvent, it is not diluted, and the solution from which the liquid repellent compound has been extracted is measured as it is. Calculate the liquid repellent compound attached to the mold from the obtained 1H-NMR measurement results.

[0493] [Examples 1-1 to 1-5, Comparative Example 1-1] [Preparation of repellent] As a liquid-repellent compound, 2 g of decaglycerol dodecabenzenesulfonate (degree of polymerization: 10, substitution rate of hydroxy groups: 12 / 12 * 100 [100%], bio-based ratio: 100%, melting point: 69 °C), 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 - 16, HLB: 7), and 17.8 g of water were mixed to obtain a precursor A of a water-dispersible liquid-repellent agent. After heating the precursor A of this water-dispersible liquid-repellent agent to 80 °C, it was allowed to cool while stirring with a magnetic stirrer to obtain a precursor B of the water-dispersible liquid-repellent agent. The precursor B of the water-dispersible liquid-repellent agent was treated twice under the condition of 80 MPa using a high-pressure wet micronization device to obtain a water-dispersible liquid-repellent agent. The volume occupancy ratio of particles of 100 μm or more in the obtained water-dispersible liquid-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 hardwood bleached kraft pulp and 30 parts of softwood bleached kraft pulp that had been beaten to a Canadian freeness of 550 cc. While stirring, 3 parts by weight of the liquid-repellent compound in solid content was added per unit weight of the pulp to the water-dispersible liquid-repellent agent obtained above to prepare a pulp composition.

[0495] [Production of pulp mold] A pulp mold was molded using an automatic mold forming machine. A net-like body was placed on a metal pulp mold forming die provided with a large number of suction holes at the bottom, and a metal tank was placed at the top. The pulp composition was placed in the upper metal tank. The pulp composition was suctioned and dehydrated through the pulp mold forming die and the net-like body from the side opposite to the side where the net-like body of the pulp mold forming die was placed using a vacuum pump, and the solid content (such as pulp) contained in the pulp composition was deposited on the net-like body to obtain a pulp mold intermediate. Next, the obtained pulp mold intermediate was preheated by heating it from above and below with a heated male and female metal molding die at 80°C for 10 seconds under a pressure of 0.3 MPa, followed by first heating at the temperatures and times shown in the following table until the amount of the liquid medium reached 10% by weight, and then heating and drying to obtain a pulp mold (a deep-dish-shaped paper plate). Thereafter, it was left at room temperature (15 to 40°C) until the temperature of the pulp mold reached room temperature (first cooling). Subsequently, the pulp mold after the first cooling was second-heated under the conditions shown in the following table. After returning the obtained pulp mold after the second heating to room temperature (after the second cooling), the above test was conducted. The results are shown in the following table.

[0496] TIFF0007701661000022.tif130164

[0497] The adhesion amount of the liquid-repellent compound in Examples 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 water-repellent agent] As the liquid-repellent compound, 2 g of powder of ethylene bisstearamide (bio-based degree: 97%, melting point: 143°C) subjected to dry grinding treatment represented by the following formula: TIFF0007701661000023.tif1863, 0.2 g of polyethylene glycol trimethyl nonyl ether (HLB 13), and 17.8 g of water were mixed to obtain a water-dispersed water-repellent agent (volume occupancy ratio of particles of 100 μm or more: 4.5%, volume median diameter: 19.2 μm).

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

[0500] [Production of Pulp Mold] A pulp mold was produced and tested in the same manner as in Example 1-1, except that the above pulp composition was subjected to heat and cooling treatments under the conditions shown in the following table. The results are shown in the following table. TIFF0007701661000024.tif82164

Claims

1. a first heating step of heating a pulp composition containing pulp and a liquid repellent compound to a first heating temperature to obtain a precursor product in which the liquid repellent compound is adhered to the pulp; a first cooling step of cooling the precursor product to a first cooling temperature to obtain a cooled precursor product; and a second heating step of heating the cooled precursor product to a second heating temperature to obtain a pulp product; The method for producing a pulp product comprises the steps of: ［１］ The first heating temperature is 40° C. or more, The first cooling temperature is below the melting point of the liquid repellent compound. ［２］ The first heating temperature is 40° C. or more, The first cooling temperature is less than 40° C., 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 plus 100° C.

2. A method for producing a pulp product as described in claim 1, wherein the first heating temperature is equal to or higher than the melting point of the liquid-repellent compound.

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

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

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

6. The method for producing a pulp product according to claim 4, wherein the second heating temperature is equal to or higher than the first cooling temperature +30°C and equal to or higher than the melting point of the liquid repellent compound -50°C.

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

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

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

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

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

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

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

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

15. The method of claim 13 , wherein the repellent agent comprises a dispersant and water.

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

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

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

Images