copolymer

Abstract

To provide a new composition capable of imparting liquid-repellent property to a substrate.SOLUTION: A copolymer includes a repeating unit derived from a hydrophobic monomer (A), and a repeating unit derived from a hydrophilic monomer (B). The copolymer is such that: an amount of the repeating unit derived from the hydrophilic monomer (B) is 51-99 wt.% based on the total amount of the repeating unit derived from the hydrophobic monomer (A), and the repeating unit derived from the hydrophilic monomer (B); a reflection peak is shown in a region at 2θ of 5° or less in an X-ray diffraction method (XRD); and an intensity of the reflection peak at 2θ of 5° or less is 0.7 or more times of a peak intensity at 2θ of 15-25°.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to copolymers. [Background technology]

[0002] Conventionally, fluorine-based compounds have been used to achieve high liquid repellency (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-201866 Summary of the Invention [Problem to be solved by the invention]

[0004] In Patent Document 1, a fluorine-containing acrylate polymer is used to impart liquid repellency, but there is no description or suggestion of imparting liquid repellency without using a fluorine-containing acrylate polymer.

[0005] An object of the present disclosure is to provide a novel composition that can impart liquid repellency to a substrate. [Means for solving the problem]

[0006] The present disclosure includes the following aspects: [Section 1] A copolymer comprising a repeating unit derived from a hydrophobic monomer (A) and a repeating unit derived from a hydrophilic monomer (B), the amount of the repeating units derived from the hydrophilic monomer (B) is 51 to 99% by weight based on the total amount of the repeating units derived from the hydrophobic monomer (A) and the repeating units derived from the hydrophilic monomer (B); In X-ray diffraction (XRD) measurement, a reflection peak is observed in the region where 2θ is 5° or less. A copolymer, wherein the intensity of the reflection peak at 2θ of 5° or less is 0.7 times or more the intensity of the peak at 2θ of 15 to 25°. [Section 2] Item 2. The copolymer according to item 1, wherein, in X-ray diffraction (XRD) measurement, the peak intensity at 2θ of 5° or less is greater than the peak intensity at 2θ of 15 to 25°. [Section 3] When the static contact angle of water in air is CA(Air), and the contact angle of water obtained by measuring the static contact angle of an air bubble in water is CA(Water), Item 3. The copolymer according to item 1 or 2, wherein the difference in contact angle as defined by CA(Air)-CA(Water) is 20° or more. [Section 4] 4. The copolymer according to any one of items 1 to 3, wherein the hydrophobic monomer (A) is a monomer having a hydrocarbon group having 6 to 40 carbon atoms which may have a substituent. [Section 5] The hydrophobic monomer (A) is Formula A: CH2=C(-X V )-Y V -(R a ) k [In the formula, X V is a hydrogen atom, a monovalent organic group, or a halogen atom, Y V is Y V1 and Y V2 is a 1+k valent group consisting of one or more groups selected from the group consisting of Y V1 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-, -NR'-, -C(OR')R'-, and -C(OR')(-)2, -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms); Y V2is a group consisting of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles, R a are each independently a hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, k is 1 to 3. Item 5. The copolymer according to any one of items 1 to 4, comprising at least one monomer represented by the following formula: [Section 6] Y V teeth, -Y V11 -Y V21 - [In the formula, Y V11 is -O-, -OC(=O)-, -OC(=O)-O-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SON2NR'-, -C(OR')R'-, or -C(OR')(-)2; Y V21 is a direct bond, a divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a divalent to tetravalent hydrocarbon aromatic ring.] Item 6. The copolymer according to Item 5, [Section 7] Y V teeth, -Y V3 -Y V4 - [In the formula, Y V3 is -C(=O)-, -O-, or -OC(=O)-, Y V4 is a group consisting of at least one selected from a direct bond, a divalent to tetravalent hydrocarbon group having 1 to 4 carbon atoms, -CH-, -O-, -C(=O)-, -S(=O)-, or -NR'- (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms). Item 7. The copolymer according to item 5 or 6, [Section 8] The hydrophilic monomer (B) is Formula B: CH2=C(-X b )-Y b -Z b -(R b ) k [In the formula, X b is a hydrogen atom, a monovalent organic group, or a halogen atom, Y b 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-, -NR'-, -C(OR')R'-, and -C(OR')(-)2, -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms); Z b represents a direct bond, a divalent to tetravalent hydrocarbon group having 1 to 4 carbon atoms, or a trivalent or tetravalent hydrocarbon group having 1 to 6 carbon atoms, or -(Z b1 O) n -Z b2 - and Z b1 are each independently an alkylene group having 2 to 6 carbon atoms, Z b2 is an alkylene group having 1 to 4 carbon atoms, n is an integer from 0 to 90, R b are each independently a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, or a phosphate group, k is 1 to 3. 8. The copolymer according to any one of items 1 to 7, wherein the monomer is represented by the formula: [Section 9] Y bItem 9. The copolymer according to Item 8, wherein R' is a direct bond, —O—, —OC(═O)—, —OC(═O)—O—, —C(═O)—NR′—, —OC(═O)—NR′—, —NR′—C(═O)—, —NR′—C(═O)—O—, —NR′—C(═O)—NR′—, —C(═O)—O—, —C(═O)—NR′—, —C(OR′)R′—, or —C(OR′)(-)2 (wherein R′ in each occurrence is independently a hydrogen atom or a hydrocarbon having 1 to 4 carbon atoms). [Section 10] Y b Item 10. The copolymer according to item 8 or 9, wherein - is a direct bond, -C(=O)-O-, -C(=O)-NH-, -O-, or -OC(=O)-. [Section 11] The hydrophilic monomer (B) is formula: CH2=C(-X b )-C(=O)-Y b -(Z b1 O) n -Z b2 -OH [In the formula, X b is a hydrogen atom or a methyl group, Y b is —O— or —NH—, Z b1 are each independently an alkylene group having 1 to 6 carbon atoms, Z b2 is an alkylene group having 1 to 4 carbon atoms, n is an integer from 0 to 90. Item 11. The copolymer according to any one of items 1 to 10, wherein the oxyalkylene group-containing monomer is represented by the formula: [Section 12] Item 12. The copolymer according to any one of items 1 to 11, having a static contact angle of water in air [CA(Air)] of 80° or more. [Section 13] Item 13. The copolymer according to any one of items 1 to 12, wherein the copolymer has a number average molecular weight Mn of 5,000 or more. [Section 14] Item 14. The copolymer according to any one of items 1 to 13, wherein the total amount of the hydrophobic monomer (A) and the hydrophilic monomer (B) relative to the copolymer is 50% by weight to 100% by weight. [Section 15] The hydrophobic monomer (A) is formula: CH2=C(-X V )-C(=O)-Y V (R a ) k [In the formula, X V is a hydrogen atom, a monovalent organic group, or a halogen atom, Y V is a group consisting of at least one selected from divalent to tetravalent hydrocarbon groups having 1 to 4 carbon atoms, -CH-, -O-, -C(=O)-, -S(=O)-, and -NR'- (R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), R a are each independently a hydrocarbon group having 6 to 40 carbon atoms, and k is 1 to 3. The hydrophilic monomer (B) is formula: CH2=C(-X b )-C(=O)-Y b -(Z b1 O) n -Z b2 -OH [In the formula, X b is a hydrogen atom or a methyl group, Y b is —O— or —NH—, Z b1 is an alkylene group having 2 to 6 carbon atoms, Z b2 is an alkylene group having 1 to 4 carbon atoms, n is an integer from 0 to 90. is an oxyalkylene group-containing monomer represented by Item 15. The copolymer according to any one of items 1 to 14, wherein the total amount of the hydrophobic monomer (A) and the hydrophilic monomer (B) relative to the copolymer is 50% by weight to 100% by weight. [Section 16] 16. A repellent comprising the copolymer according to any one of claims 1 to 15 and a liquid medium. [Section 17] Item 17. The repellent according to item 16, which is for textile products, paper products, glass, or resin. [Section 18] Item 17. A product treated with the repellent according to item 16. [Section 19] Item 18. The product according to item 18, which is a textile product, a paper product, a glass product, or a resin product. [Effects of the Invention]

[0007] According to the present disclosure, it is possible to impart liquid repellency to a substrate in an excellent manner. In particular, according to the present disclosure, it is possible to impart water repellency to a substrate in an excellent manner. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 shows a schematic cross-sectional view of a copolymer according to one embodiment in air. [Figure 2] FIG. 2 is a schematic cross-sectional view of a copolymer according to one embodiment in air when a water droplet is dropped on the copolymer. [Figure 3] FIG. 3 is a schematic cross-sectional view of a copolymer according to one embodiment in water with bubbles formed therein. [Figure 4] FIG. 4 shows a schematic cross-sectional view of a conventional copolymer in water with bubbles introduced therein. DETAILED DESCRIPTION OF THE INVENTION

[0009] <Terminology> As used herein, an "n-valent group" refers to a group having n bonds, i.e., a group that forms n bonds. An "n-valent organic group" refers to an n-valent group containing carbon. Such organic groups are not particularly limited, but may be hydrocarbon groups or derivatives thereof. A hydrocarbon group derivative refers to a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc. at the end or molecular chain of the hydrocarbon group.

[0010] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, which is obtained by removing a hydrogen atom from a hydrocarbon. Such hydrocarbon groups include, but are not limited to, C 1-20 Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may contain one or more ring structures. The hydrocarbon group may be substituted with one or more substituents.

[0011] In this specification, when a term (symbol) that may appear multiple times in a chemical structure is defined, that definition applies independently at each occurrence, unless otherwise stated, regardless of whether "independently at each occurrence," "independently of each other," "independently of each other," or similar expressions are explicitly stated.

[0012] The chemical structures described herein should be understood not to encompass chemical structures that would be recognized by those skilled in the art as chemically impossible or extremely unstable.

[0013] <Copolymer> The copolymer of the present disclosure is a copolymer comprising a repeating unit derived from a hydrophobic monomer (A) and a repeating unit derived from a hydrophilic monomer (B), the amount of the repeating units derived from the hydrophilic monomer (B) is 51 to 99% by weight based on the total amount of the repeating units derived from the hydrophobic monomer (A) and the repeating units derived from the hydrophilic monomer (B); In X-ray diffraction (XRD) measurement, a reflection peak is observed in the region where 2θ is 5° or less. The intensity of the reflection peak at 2θ of 5° or less is at least 0.7 times the intensity of the peak at 2θ of 15 to 25°.

[0014] The copolymer of the present disclosure has a phase-separated structure derived from repeating units derived from a hydrophobic monomer (A) and repeating units derived from a hydrophilic monomer (B). Furthermore, the copolymer of the present disclosure has environmental responsiveness. The fact that a copolymer has environmental responsiveness means that the copolymer structure changes depending on the surrounding environment. More specifically, the copolymer of the present disclosure exhibits uneven distribution of hydrophobic and hydrophilic components constituting the copolymer depending on the surrounding environment, and the distribution of the hydrophobic and hydrophilic components in the copolymer can change.

[0015] The phase-separated structure and environmental responsiveness of the copolymer of the present disclosure will be described in detail below.

[0016] [Phase separation structure] The copolymer of the present disclosure contains repeating units derived from a hydrophobic monomer (A) and repeating units derived from a hydrophilic monomer (B). The copolymer of the present disclosure has a hydrophobic component derived from the hydrophobic monomer (A) and a hydrophilic component derived from the hydrophilic monomer (B).

[0017] When the copolymer of the present disclosure is provided on a substrate and left standing in air, the copolymer on the substrate forms a phase-separated structure of a hydrophobic component-rich layer and a hydrophilic component-rich layer. More specifically, as shown in Figure 1, the surface of copolymer 2 on substrate 1 is such that the side exposed to air forms hydrophobic component-rich layer 21, and the surface facing the substrate forms hydrophilic component-rich layer 22. Copolymer 2 of the present disclosure can particularly form a lamellar structure.

[0018] A layer rich in hydrophobic components is a layer that contains a relatively large amount of hydrophobic components and may also contain a hydrophilic component. Similarly, a layer rich in hydrophilic components is a layer that contains a relatively large amount of hydrophilic components and may also contain a hydrophobic component.

[0019] Since the hydrophobic component has a higher affinity for air than the hydrophilic component, it is thought that the hydrophobic component is distributed in greater amounts (i.e., unevenly distributed) on the side of the copolymer surface exposed to air, while the hydrophilic component is distributed in greater amounts on the substrate side.

[0020] The arrangement of the repeating units derived from the hydrophobic monomer (A) and the repeating units derived from the hydrophilic monomer (B) in the copolymer of the present disclosure may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer. From the viewpoint of forming a phase-separated structure and facilitating environmental responsiveness, the copolymer of the present disclosure may be a random copolymer.

[0021] [Environmental responsiveness] When water is dropped onto copolymer 2 in Figure 1, a water droplet having a static contact angle α of water in air is formed on copolymer 2, as shown in Figure 2. The area where copolymer 2 and water 3 are in contact is in an aqueous environment. In other words, when the state of Figure 1 changes to the state of Figure 2, the environment of the area where copolymer 2 and water 3 are in contact changes from "air" to "water."

[0022] Here, if the copolymer is environmentally responsive, when the surrounding environment changes from "air" to "water," the copolymer can change its structure in response to the change in the environment. Specifically, as shown in Figure 2, the surface portion of copolymer 2 that comes into contact with water 3 changes from a hydrophobic component-rich layer 21 to a hydrophilic component-rich layer 22, compared to Figure 1. Since hydrophilic components have a higher affinity for water than hydrophobic components, it is thought that the hydrophilic components are distributed in greater amounts on the side of the copolymer surface that is exposed to water.

[0023] In Figure 2, the surface portion of copolymer 2 in contact with water 3 forms hydrophilic component-rich layer 22, while the surface portion of copolymer 2 in contact with air maintains hydrophobic component-rich layer 21. Because hydrophilic component-rich layer 22 is highly hydrophilic, water droplets 3 can easily remain on hydrophilic component-rich layer 22. Because hydrophobic component-rich layer 21 is highly hydrophobic, water 3 does not easily wet hydrophobic component-rich layer 21. This is thought to be because the energy barrier of the three-phase interface at the boundary between the water droplet contact area and the water droplet non-contact area inhibits the water droplet from wetting and spreading.

[0024] Due to such a distribution of hydrophilic and hydrophobic components, the water droplet 3 is less likely to spread across the hydrophobic component-rich layer 21 on the copolymer surface from the state shown in Figure 2, and the contact angle α of the water droplet may become larger. Therefore, the copolymer of the present disclosure can impart water repellency to a substrate.

[0025] Furthermore, the fact that the copolymer of the present disclosure exhibits environmental responsiveness will be explained below from the perspective of the static contact angle γ of water calculated from the contact angle β of air bubbles.

[0026] FIG. 3 shows the state when a substrate 1 ( FIG. 1 ) provided with a copolymer 2 of the present disclosure is placed in an underwater environment and bubbles 5 are formed on the substrate in the water 4. In FIG. 3 , bubbles 5 are formed on the lower surface of the substrate 1 (i.e., the surface of the substrate 1 opposite to the surface closer to the water surface) to prevent the bubbles 5 from floating up and to keep them in the water 4. As shown in FIG. 3 , when bubbles 5 are formed on the copolymer 2 of the substrate 1 in the water 4, the bubbles 5 have a static contact angle β of bubbles in the water.

[0027] By measuring the static contact angle β of air bubbles in water, the "static contact angle γ of water calculated from the contact angle β of air bubbles" can be obtained from the formula for "contact angle β of air bubbles in 180°-copolymer in water." The presence or absence of environmental responsiveness can be determined from the difference between the static contact angle α of water in air (Figure 2) and the static contact angle γ of water calculated from the contact angle β of air bubbles.

[0028] If the copolymer does not have environmental responsiveness, the copolymer applied to the substrate in air (see FIG. 1) can maintain a hydrophobic component-rich layer 21 on the surface of the copolymer 2 even in water 4 (see FIG. 4). As shown in FIG. 4, when bubbles 5 are formed on the substrate 1 in water 4, the bubbles 5 and the hydrophobic component have a high affinity for each other, so the bubbles 5 tend to spread over the hydrophobic component-rich layer 21, and the static contact angle B of the bubbles tends to become small. Therefore, the static contact angle γ of water calculated from the bubble contact angle β tends to become large. When the static contact angle α in FIG. 2 is compared with the static contact angle γ in FIG. 4, the difference between the two becomes small or can be substantially the same.

[0029] When the copolymer is environmentally responsive, immersing a substrate provided with the copolymer in water (see FIG. 3) changes the surrounding environment from "air" to "water," and the surface portion of the copolymer in contact with water 5 changes from hydrophobic component-rich layer 21 to hydrophilic component-rich layer 22. On the other hand, the surface portion of the copolymer 2 in contact with bubbles 5 becomes hydrophobic component-rich layer 21 because the surrounding environment is "air" (see FIG. 3).

[0030] Because a layer rich in a hydrophobic component has strong hydrophobicity, bubbles tend to remain on the layer rich in a hydrophobic component. Because a layer rich in a hydrophilic component has strong hydrophilicity, bubbles tend to spread less on the layer rich in a hydrophilic component. From the state shown in Figure 3, bubbles 5 tend to spread less on the copolymer surface 2 across the hydrophilic component-rich layer 22, and therefore the contact angle γ of the bubbles may become smaller than the contact angle α.

[0031] As described above, the presence or absence of environmental responsiveness can be more clearly confirmed from the relationship between the static contact angle α of water in air and the static contact angle γ of water calculated from the contact angle β of an air bubble.

[0032] The copolymer of the present disclosure forms a phase-separated structure of hydrophilic and hydrophobic components, and thus can impart water repellency to a substrate even when the amount of repeating units derived from the hydrophilic monomer (B) is 51 to 99% by weight (in other words, the hydrophilic component is abundant) relative to the total amount of repeating units derived from the hydrophobic monomer (A) and the amount of repeating units derived from the hydrophilic monomer (B).

[0033] Furthermore, the copolymer of the present disclosure can surprisingly impart water repellency to a substrate even when the amount of repeating units derived from the hydrophilic monomer (B) is 51 to 99% by weight (in other words, the hydrophilic component is abundant) of the total amount of repeating units derived from the hydrophobic monomer (A) and the hydrophilic monomer (B) due to the formation of a phase-separated structure of the hydrophilic component and the hydrophobic component and the environmental responsiveness.

[0034] In the above description, "air" and "water" are exemplified as the surrounding environment, but the surrounding environment is not limited to these and may be other environments such as "organic solvents." In such cases, the copolymer of the present disclosure may have effects such as not only water repellency but also oil repellency, i.e., liquid repellency.

[0035] The copolymer of the present disclosure has the above characteristics, and when adhered to a substrate, can impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the substrate. Due to these properties, the copolymer of the present disclosure can also be referred to as a liquid repellent compound.

[0036] [XRD measurement] In X-ray diffraction (XRD) measurement, the copolymer of the present disclosure exhibits a reflection peak in a region where 2θ is equal to or less than 5°. The region where 2θ is equal to or less than 5° means, for example, a region where 2θ is from 1.5° to 4.9° or from 1.9° to 4.5°.

[0037] The reflection peak appearing in the region where 2θ is 5° or less is believed to be a peak derived from the phase-separated structure of the copolymer, more specifically, a peak derived from a lamellar structure. The lamellar structure of the copolymer of the present disclosure is believed to be formed by phase separation between the hydrophobic and hydrophilic components, and / or crystallization of the hydrophobic component and its interaction as the driving force. An example of crystallization of the hydrophobic component is the formation of a fine lamellar structure with a domain spacing of about 5 to 10 nm, which is caused by the crystallization of long-chain hydrocarbon groups (e.g., octadecyl groups, etc.), resulting in microphase separation between the long-chain hydrocarbon groups.

[0038] To obtain a copolymer that exhibits a reflection peak in the region where 2θ is 5° or less, as described above, the hydrophobic monomer and the hydrophilic monomer should be selected so that the copolymer forms a phase-separated structure, preferably a lamellar structure.

[0039] The reflection peak appearing in the region where 2θ is equal to or less than 5° may be stronger than the reflection peak appearing in the region where 2θ is greater than 5°. In other words, the reflection peak appearing in the region where 2θ is equal to or less than 5° may have the strongest intensity. The region where 2θ is greater than 5° may be, for example, greater than 5° and equal to or less than 30°.

[0040] The peaks at 2θ of 15 to 25° are due to the packing (crystallinity) of long-chain alkyl groups.

[0041] From the viewpoint of further improving liquid repellency, in X-ray diffraction (XRD) measurement, the peak intensity at a 2θ of 5° or less may be 0.7 times or more, 0.8 times or more, 0.9 times or more, 1.0 times or more, 1.2 times or more, 1.5 times or more, 2.0 times or more, 2.5 times or more, or 3.0 times or more of the peak intensity at a 2θ of 15 to 25°, and may be 6.0 times or less, 5.5 times or less, 5.0 times or less, 4.5 times or less, 4.0 times or less, or 3.5 times or less.

[0042] From the viewpoint of further improving the liquid repellency, the intensity of the peak at 2θ of 5° or less may be greater than the intensity of the peak at 2θ of 15 to 25° in X-ray diffraction (XRD) measurement.

[0043] XRD measurements are generally carried out at around room temperature of 25°C, but XRD measurements can also be carried out at a specified temperature using a temperature-variable XRD instrument such as an XRD-DSC.

[0044] [Static contact angle of water in air α] The static contact angle α (also referred to as CA(Air)) of the copolymer in air may be 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 80° or more, 85° or more, 90° or more, or 100° or more. The CA(Air) of the copolymer may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When the copolymer has a CA(Air) equal to or greater than the above lower limit, it can impart good liquid repellency (particularly water repellency) to the substrate. CA(Air) refers to the static contact angle of the copolymer with a spin-coated film, obtained by dropping 2 μL of water on the spin-coated film and measuring the contact angle 1 second after the drop lands.

[0045] [Static contact angle β of an air bubble in water] The static contact angle β of the copolymer in water 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. The static contact angle β of the copolymer in water may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When the copolymer has a static contact angle β of the copolymer in water that is equal to or greater than the above lower limit, it can impart good liquid repellency (particularly water repellency) to the substrate. The contact angle of the copolymer in water refers to the static contact angle of the air bubbles in water with a spin-coated film of the copolymer. Specifically, the polymer-treated silicon wafer was fixed so that the surface opposite to the polymer-treated surface was in contact with a jig. The polymer-treated silicon wafer was immersed in a glass container filled with pure water with the polymer-treated surface facing downwards and left for 5 minutes, after which a 2 μl air bubble was created with a syringe and attached to the polymer-treated silicon wafer surface, thereby measuring the contact angle of the air bubble in water. The contact angle of the air bubble thus obtained was taken as the static contact angle β of the air bubble in water.

[0046] [Static water contact angle γ calculated from bubble contact angle β] The static water contact angle γ (also referred to as CA(Water)), obtained by measuring the static contact angle of an air bubble in water, may be 10° or more, 15° 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, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more. The CA(Water) may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, 90° or less, 80° or less, 70° or less, or 60° or less. When the copolymer has a CA(Water) equal to or greater than the above lower limit, it can impart good liquid repellency (particularly water repellency) to the substrate. The static water contact angle, obtained by measuring the static contact angle of an air bubble in water of the copolymer, can be obtained by "180° - contact angle of an air bubble in water of the copolymer."

[0047] [CA(Air)-CA(Water)] When the static contact angle α of water in air is defined as CA(Air) and the contact angle γ of water obtained by measuring the static contact angle of an air bubble in water is defined as CA(Water), the contact angle difference defined as CA(Air)-CA(Water) may be 20° or more, 25° or more, 30° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, or 60° or more, or may be 100° or less, 90° or less, 80° or less, 70° or less, or 60° or less.

[0048] A copolymer has environmental responsiveness when the difference in contact angle, defined as CA(Air) - CA(Water), is 20° or more. The fact that a copolymer has environmental responsiveness means that the structure of the copolymer changes depending on the surrounding environment. More specifically, in the copolymer of the present disclosure, the hydrophobic and hydrophilic components constituting the copolymer are unevenly distributed depending on the surrounding environment, and the distribution of the hydrophobic and hydrophilic components in the copolymer can change.

[0049] [Other characteristics] The properties that the copolymer may have are listed below, and these properties may vary depending on the type of compound.

[0050] The HD (n-hexadecane) contact angle of the copolymer may be 5° or more, 10° or more, 20° or more, 25° or more, 30° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 60° or more, or 65° or more, preferably 25° or more, and more preferably 30° or more. The HD contact angle of the copolymer may be 100° or less, 90° or less, or 75° or less. When the copolymer has an HD contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (especially oil repellency) to the substrate. The HD contact angle is the static contact angle of the copolymer with a spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle 1 second after the drop has landed.

[0051] The copolymer is preferably a biobased compound containing carbon of biobased origin. The biobased content is measured in accordance with ASTM D6866. The biobased content may be 20% or more, preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example, 100%. A high biobased content means that a small amount of fossil resource-based materials, such as petroleum, is used. From this perspective, the higher the biobased content of the copolymer, the better.

[0052] The copolymer preferably has a biodegradability of 5% or more after 180 days. Higher biodegradability is preferable because it reduces the environmental impact. The copolymer's biodegradability after 180 days may be, for example, 10% or more, 20% or more, 30% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, preferably 30% or more, more preferably 50% or more, even more preferably 70% or more, and most preferably 80% or more. The copolymer preferably has a biodegradability of 5% or more after 60 days. Higher biodegradability is preferable because it reduces the environmental impact. The copolymer's biodegradability after 60 days may be, for example, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, or 45% or more, preferably 10% or more, and more preferably 30% or more. Such biodegradability may be the biodegradability specified in JIS K 6953-1 or ASTM D6400.

[0053] The weight average molecular weight (Mw) of the copolymer 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. The weight average molecular weight of the copolymer may be 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, or 5,000 or less.

[0054] The number average molecular weight (Mn) of the copolymer 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. The weight average molecular weight of the copolymer may be 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, or 5,000 or less.

[0055] The melting point of the copolymer 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. The melting point of the copolymer 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.

[0056] The copolymer according to the present disclosure does not necessarily have any group selected from the group consisting of a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, and a fluorine atom. Even if the copolymer does not contain these fluorine-containing groups, it can still impart liquid repellency to a substrate.

[0057] [(A) Hydrophobic Monomer] In the present disclosure, the hydrophobic monomer (A) is copolymerized with the hydrophilic monomer (B) to form a copolymer.

[0058] [Characteristics, etc.] The properties that the hydrophobic monomer (A) may have are shown below.

[0059] (solubility characteristics) The hydrophobic monomer (A) is hydrophobic and has low water solubility. The hydrophobic monomer (A) may have a water solubility at 25°C of 3.0 g / L or less, 1.0 g / L or less, 0.5 g / L or less, 0.1 g / L or less, or 0.01 g / L or less, for example, 1.0 g / L or less. The water solubility can be calculated by adding the compound in small amounts to a predetermined amount of water (25°C) and calculating the amount of dissolved compound at the point where the compound no longer dissolves (e.g., floating, precipitation, deposition, or cloudiness is observed). A compound that is highly water-soluble (e.g., a compound that is a water-miscible liquid) cannot be considered a hydrophobic compound.

[0060] The solubility parameter (SP value) of the hydrophobic monomer (A) may be 3.0 or more, 4.0 or more, 5.0 or more, 6.0 or more, 7.0 or more, 8.0 or more, 9.0 or more, 10.0 or more, or 11.0 or more, and may be 15.0 or less, 14.0 or less, 13.0 or less, 12.0 or less, 10.0 or less, 9.0 or less, or 8.0 or less, preferably 10.5 or less, particularly 10.0 or less. The SP value can be calculated using Fedors' formula (Polym. Eng. Sci., 14[2], 147(1974)).

[0061] The difference in SP value between the hydrophobic monomer (A) and the hydrophilic monomer (B) may be greater than 0, 0.1 or greater, 0.2 or greater, 0.3 or greater, 0.4 or greater, 0.5 or greater, 0.6 or greater, 0.7 or greater, 0.8 or greater, 0.9 or greater, 1.0 or greater, 2.0 or greater, 3.0 or greater, 4.0 or greater, or 5.0 or greater, or 6.0 or less, 5.0 or less, 4.0 or less, 3.0 or less, 2.0 or less, 1.5 or less, 1.0 or less, 0.8 or less, 0.6 or less, or 0.5 or less, preferably 5.0 or less, more preferably 3.0 or less. The SP value of the hydrophobic monomer (A) may be greater than that of the hydrophilic monomer (B). When multiple types of monomers are present in each of the hydrophobic monomer (A) and the hydrophilic monomer (B), a weighted average based on the weight ratio may be used to calculate each value. In this specification, unless otherwise stated, differences are absolute differences.

[0062] The octanol / water partition coefficient (logPow) of the hydrophobic monomer (A) may be 0 or more, 0.1 or more, 0.3 or more, 0.5 or more, 1 or more, 1.5 or more, 2.0 or more, 2.5 or more, 3.0 or more, 3.5 or more, 4.0 or more, 4.5 or more, 5.0 or more, 5.5 or more, or 6.0 or more, preferably 0.5 or more, 1.5 or more, 2.5 or more, or 3.5 or more, and may be 10.0 or less, 9.0 or less, 8.0 or less, 7.0 or less, 6.0 or less, 5.0 or less, 4.0 or less, 3.0 or less, 2.0 or less, or 1.0 or less.

[0063] The difference in octanol / water partition coefficient (logPow) between the hydrophobic monomer (A) and the hydrophilic monomer (B) may be greater than 0, 0.1 or greater, 0.3 or greater, 0.5 or greater, 1.0 or greater, 1.5 or greater, or 2.0 or greater, or 5.0 or less, 4.5 or less, 4.0 or less, 3.0 or less, 2.5 or less, 2.0 or less, 1.5 or less, 1.0 or less, 0.5 or less, 0.3 or less, or 0.1 or less, preferably 2.5 or less, more preferably 1.0 or less. The octanol / water partition coefficient (logPow) of the hydrophobic monomer (A) may be greater than that of the hydrophilic monomer (B). When multiple types of monomers are present in each of the hydrophobic monomer (A) and the hydrophilic monomer (B), a weighted average based on the weight ratio may be used to calculate each value.

[0064] (Other characteristics) The hydrophobic monomer (A) is preferably a biobased compound containing carbon of biobased origin. The biobased content is measured in accordance with ASTM D6866. The biobased content of each hydrophobic monomer (A) may be independently 20% or more, preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example, 100%. A high biobased content means that the amount of fossil resource-based materials, such as petroleum, used is reduced. From this perspective, the higher the biobased content of the hydrophobic monomer (A), the more preferable it is.

[0065] The biodegradability of the hydrophobic monomer (A) after 180 days is preferably 5% or more. Higher biodegradability is preferable because it reduces the environmental impact. The biodegradability of the hydrophobic monomer (A) after 180 days may be, for example, 10% or more, 20% or more, 30% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, preferably 30% or more, more preferably 50% or more, even more preferably 70% or more, and most preferably 80% or more. The biodegradability of the hydrophobic monomer (A) after 60 days is preferably 5% or more. Higher biodegradability is preferable because it reduces the environmental impact. The biodegradability of the hydrophobic monomer (A) after 60 days may be, for example, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, or 45% or more, preferably 10% or more, more preferably 30% or more. Such biodegradability may be the biodegradability specified in JIS K 6953-1 or ASTM D6400.

[0066] The melting point of the hydrophobic monomer (A) 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. The melting point of the hydrophobic monomer (A) 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.

[0067] [Structure, etc.] The hydrophobic monomer (A) may have a hydrocarbon group having 6 to 40 carbon atoms which may have a substituent.

[0068] The hydrocarbon group contained in the hydrophobic monomer (A) may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched or linear, and more preferably linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may have 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 carbon atoms, and preferably 10 or more, 12 or more, 14 or more, or 16 or more carbon atoms. The hydrocarbon group may have 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, and preferably 30 or less, 25 or less, or 20 or less.

[0069] 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 (wherein R', in each occurrence, is independently a hydrogen atom or an organic group (e.g., a hydrocarbon group, particularly an aliphatic 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 substituted hydrocarbon group, the ratio of carbon atoms to the total amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0070] The hydrophobic monomer (A) is preferably capable of forming a crystalline structure. Specifically, the hydrophobic monomer (A) preferably has a long-chain hydrocarbon group, and the long-chain hydrocarbon groups of multiple hydrophobic monomers (A) preferably interact with each other to aggregate and form a phase-separated structure in the copolymer.

[0071] The hydrophobic monomer (A) may contain an amide group, a urea group, or a urethane group. The hydrophobic monomer (A) may be a combination of a hydrophobic monomer having an amide group, a urea group, or a urethane group with a hydrophobic monomer not having an amide group, a urea group, or a urethane group. By including such a group in the hydrophobic monomer (A), the effects of the present disclosure can be effectively achieved.

[0072] The hydrophobic monomer (A) is Formula A: CH2=C(-X V )-Y V -(R a ) k [In the formula, X V is a hydrogen atom, a monovalent organic group, or a halogen atom, Y V is Y V1 and Y V2 is a 1+k valent group consisting of one or more groups selected from the group consisting of Y V1 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-, -NR'-, -C(OR')R'-, and -C(OR')(-)2, -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms); Y V2 is a group consisting of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles, R a are each independently a hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, k is 1 to 3. The copolymer may contain at least one monomer represented by the following formula:

[0073] (X V ) X VX may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. V Examples of X are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. V is preferably a hydrogen atom, a methyl group, or a chlorine atom. V is particularly preferably a hydrogen atom.

[0074] (Y V ) Y V is Y V1 and Y V2 is a 1+k valent group consisting of one or more groups selected from the group consisting of Y V1 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-, -NR'-, -C(OR')R'-, and -C(OR')(-)2, -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms); Y V2 is a group composed of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles.

[0075] k is Y V Combine with R a and may be an integer of 1 or more and 3 or less. k may be 1 or more, 2 or more, or 3 or more, and may be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0076] Y V The molecular weight of may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more, and may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[0077] ○ Y V1 Y V1 is a non-hydrocarbon linker.

[0078] Y V1 is a direct bond or a divalent or higher valent group. V1 The valence of Y may be 2 to 4, 2 to 3, or 2. V1 is preferably not only a direct bond.

[0079] Y V1 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0080] Y V1 may be 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', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)). Y V1 Examples include: direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, —C(═O)—NR′—, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2 etc. (In the formula, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) Examples include:

[0081] ○ Y V2 Y V2 is a linker of a hydrocarbon ring which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, or a heterocyclic ring which may have a substituent.

[0082] Y V2 Y may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). V2 Y may be aliphatic or aromatic. V2 may be linear, branched or cyclic.

[0083] Y V2 is a divalent or higher valent group. V2 The valence of may be, for example, 2 to 4, 2 to 3, or 2.

[0084] Y V2 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more carbon atoms, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0085] Y V2 is composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles.

[0086] The di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight-chain hydrocarbon group. The di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may be 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less. The valence of the aliphatic hydrocarbon group may be 2 or more, 3 or more, or 4 or less, 4 or less, 3 or less, or 2.

[0087] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (wherein R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have 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 substituted aliphatic hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0088] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0089] The hydrocarbon aromatic ring may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and a halogen atom (wherein R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have 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 substituted hydrocarbon aromatic ring, the ratio of carbon atoms to the total 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 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0090] The divalent to tetravalent heterocycle may be an aliphatic group or an aromatic group. Examples of divalent to tetravalent heterocycles include groups obtained by removing 2 to 4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring-constituting atoms of the heterocycle is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the heterocycle may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0091] The heterocycle may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and a halogen atom (wherein R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have 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 substituted heterocycle, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more, or 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0092] Y V2 Examples include: -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali(-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or heterocycle.] etc.

[0093] Y V2 Specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond; a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms; -(CH2) q -Cy-(CH2) r -(q and r each independently represent a number from 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0094] (Y V (Example) Y V In the following, R' is independently in each occurrence a hydrogen atom or an organic group (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group) having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[0095] Y V An example of this is Y V If is bivalent, -Y V1 -, -Y V1 -Y V2 -, -Y V1 -Y V2 -Y V1 -, -Y V1 -Y V2 -Y V1 -Y V2 -, -Y V2 -, -Y V2 -Y V1 -, -Y V2 -Y V1 -Y V2 -, -Y V2 -Y V1 -Y V2 -Y V1 -, etc.

[0096] For example, if Y is trivalent, -Y V1 (-)2, -Y V1 -Y V2 (-)2, -Y V1 -(Y V2 -)2, -Y V1 -Y V2 -Y V1 (-)2, -Y V1 -Y V2 (-Y V1 -)2, -Y V1 -(Y V2 -YV1 -), 2, -Y V1 -Y V2 -Y V1 -Y V2 (-), 2, -Y V1 -Y V2 -Y V1 -(Y V2 -) 2、 -Y V1 -Y V2 -(Y V1 -Y V2 -) 2、 -Y V1 -(Y V2 -Y V1 -Y V2 -), 2; -Y V2 (-), 2, -Y V2 -Y V1 (-), 2, -Y V2 -(Y V1 (-), 2, -Y V2 -Y V1 -Y V2 (-), 2, -Y V2 -Y V1 (-Y V2 (-), 2, -Y V2 -(Y V1 -Y V2 (-), 2, -Y V2 -Y V1 -Y[[ID=?]] V2 -Y V1 (-), 2, -Y V2 -Y V1 -Y V2 -(Y V1 -) 2、 -Y V2 -Y V1 -(Y V2 -Y V1 -) 2、 -Y V2 -(Y V1 -Y V2 -Y V1 -), 2; etc. can be mentioned.

[0097] As an example of Y, when Y is tetravalent, -Y V1 (-), 3, -Y V1 -Y V2 (-), 3, -Y V1 -(Y V2 (-), 3, -Y V1 It should be noted that there seems to be an unclear tag "? " in the original text at line 72 which is maintained as is in the translation. If this is an error in the original, it may need to be corrected for a more accurate translation.-Y V2 -Y V1 (-)3, -Y V1 -Y V2 (-Y V1 (-)3, -Y V1 -(Y V2 -Y V1 (-)3, -Y V1 -Y V2 -Y V1 -Y V2 (-)3, -Y V1 -Y V2 -Y V1 -(Y V2 -) 3、 -Y V1 -Y V2 -(Y V1 -Y V2 -) 3、 -Y V1 -(Y V2 -Y V1 -Y V2 -)3; [[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​Preferred examples of Y include -Y V1 -, -Y V1 -Y V2 -, -Y V1 -Y V2 -Y V1 -, -Y V1 -Y V2 (-)2, -Y V2 -, -Y V2 -Y V1 -, -Y V2 -Y V1 -Y V2 -, -Y V2 -Y V1 (-)2, etc.

[0099] (Preferred Y V (Example) Preferably, Y V teeth, -Y V11 -Y V21 - [In the formula, Y V11 is a direct bond, —O—, —OC(═O)—, —OC(═O)—O—, —C(═O)—NR′—, —OC(═O)—NR′—, —NR′—, —NR′—C(═O)—, —NR′—C(═O)—O—, —NR′—C(═O)—NR′—, —C(═O)—O—, —C(═O)—NR′—, —SO2—, —SO2NR′—, —C(OR′)R′—, or —C(OR′)(-)2; Y V21 is a direct bond, a divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a divalent to tetravalent hydrocarbon aromatic ring group.] It may be.

[0100] Y V11 is a non-hydrocarbon linker, which is a direct bond or a divalent or higher valent group.

[0101] Y O11 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0102] Y O11 may be -C(=O)-, -O-, or -OC(=O)-.

[0103] Y V21 is a linker that is a direct bond, an aliphatic hydrocarbon group, or a hydrocarbon aromatic ring.

[0104] Y V21 is a divalent or higher valent group. V21 The valence of may be, for example, 2 to 4, 2 to 3, or 2.

[0105] Y V21 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more carbon atoms, and may have 20 or less, 15 or less, 10 or less, or 5 or less carbon atoms.

[0106] Y V21 is a direct bond, a divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a divalent to tetravalent hydrocarbon aromatic ring.

[0107] The di- to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be a cyclic, branched, or straight-chain hydrocarbon group. The di- to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may be 20 or less, 15 or less, 10 or less, or 5 or less. The valence of the aliphatic hydrocarbon group may be 2 or more, 3 or more, or 4 or less, 4 or less, 3 or less, or 2.

[0108] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (wherein R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have 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 substituted aliphatic hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0109] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0110] The hydrocarbon aromatic ring may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and a halogen atom (wherein R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have 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 substituted hydrocarbon aromatic ring, the ratio of carbon atoms to the total 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 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0111] Y V teeth, -Y V3 -Y V4 - [In the formula, Y V3 is -C(=O)-, -O-, or -OC(=O)-, Y V4 is a group consisting of at least one selected from divalent to tetravalent hydrocarbon groups having 1 to 4 carbon atoms, -C6H4-, -O-, -C(=O)-, -S(=O)2-, and -NR'- (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms). It may be.

[0112] In other words, The hydrophobic monomer (A) is formula: CH2=C(-X V )-Y V3 -Y V4 -(R a ) k [In the formula, R a are each independently a hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, X V is a hydrogen atom, a monovalent organic group, or a halogen atom, YV3 is -C(=O)-, -O-, or -OC(=O)-, Y V4 represents a group (excluding hydrocarbon groups) consisting of at least one selected from a direct bond, a divalent to tetravalent hydrocarbon group having 1 to 4 carbon atoms (particularly, -CH-, -CH=), -CH-, -O-, -C(=O)-, -S(=O)-, and -NH-; k is 1 to 3. It is preferable that the monomer is a monomer represented by the following formula:

[0113] X V X may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. V Examples of X are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. V is preferably a hydrogen atom, a methyl group, or a chlorine atom. V is particularly preferably a hydrogen atom.

[0114] Y V3 is -C(=O)-, -O-, or -OC(=O)-. V3 may preferably be —C(═O)—.

[0115] Y V4 is a direct bond or a divalent to tetravalent group. V4 is preferably a direct bond or a divalent group. Y V4 is preferably a group (excluding hydrocarbon groups) composed of at least one selected from a direct bond, a hydrocarbon group having one carbon atom, -CH-, -O-, -C(=O)-, -S(=O)2-, and -NH-. Examples of hydrocarbon groups having one carbon atom include -CH2-, -CH= having a branched structure, and -C≡ having a branched structure.

[0116] Y V4-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)—; R' is -(CH2) m - (m is an integer of 1 to 5) or -C6H4- (phenylene group). It may be.

[0117] Y V4 Specific examples are -O-, -NH-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -OC(=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 -OC(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -OC(=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 -OC(=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).

[0118] Y V4 -O-, -NH-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -NH-S(=O)2- or -NH-(CH2) m -S(=O)2-NH- [In the formula, m is an integer of 1 to 5, particularly 2 or 4.] It is preferable that Y V4 is -O- or -O-(CH2) m -NH-C(=O)-, especially -O-(CH2) m It is more preferably -NH-C(=O)-.

[0119] R a is preferably a linear or branched hydrocarbon group. The hydrocarbon group may particularly be a linear hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. The hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 or 15 to 26, particularly 18 to 22 or 17 to 22 carbon atoms.

[0120] R a may be a hydrocarbon group which may have a substituent. 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 (wherein R', in each occurrence, is independently a hydrogen atom or an organic group (e.g., a hydrocarbon group, particularly an aliphatic 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 substituted hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0121] Examples of monomer (A) are: Formula (A1): CH2=C(-X a1 )-C(=O)-Y a1 -R a1 [In the formula, R a1 is a hydrocarbon group having 6 to 40 carbon atoms, X a1 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y a1 is —O— or —NH—.] A monomer represented by the formula: Formula (A2): CH2=C(-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 consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, and -CH2-, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms; n is 1 or 2. It is a monomer represented by the formula:

[0122] (A1) Monomer The monomer (A1) has the formula: CH2=C(-X a1 )-C(=O)-Y a1 -R a1 [In the formula, R a1 is a hydrocarbon group having 6 to 40 carbon atoms, X a1 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y a1 is —O— or —NH—.] It is a compound represented by the formula:

[0123] Monomer (A1) is Y a1 a long chain acrylate ester monomer in which Y is —O—; a1 is a long-chain acrylamide monomer in which is -NH-. R a1 is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. a1 In the formula (I), the hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 carbon atoms, and particularly preferably 18 to 22 carbon atoms. X a1 may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0124] Preferred specific examples of the long-chain acrylate ester monomer are lauryl (meth)acrylate, stearyl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl alpha chloroacrylate, icosyl alpha chloroacrylate, and behenyl alpha chloroacrylate. Specific preferred examples of the long-chain acrylamide monomer are stearyl (meth)acrylamide, icosyl (meth)acrylamide, and behenyl (meth)acrylamide.

[0125] (A2) Monomer Monomer (A2) is a monomer different from monomer (A1). Monomer (A2) is a (meth)acrylate or (meth)acrylamide having a group consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, and -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 consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, and -CH2-, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms; n is 1 or 2. The compound may be represented by the formula: Y a22 and / or Z may not be a direct bond. a22 and Z may not be a direct bond at the same time.

[0126] Ra2 is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. a2 In the formula (I), the hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 or 15 to 26, and particularly preferably 18 to 22 or 17 to 22 carbon atoms.

[0127] X a2 may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0128] Y a22 -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'- , -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- wherein each Y' independently represents a direct bond, -O-, -NH-, or -S(=O)2-; R' is -(CH2) m -(m is an integer of 1 to 5), a linear hydrocarbon group having an unsaturated bond of 1 to 5 carbon atoms, a hydrocarbon group having a branched structure of 1 to 5 carbon atoms, or -(CH2) l -C6H4-(CH2) l - (each l is independently an integer of 0 to 5, and -C6H4- is a phenylene group). It may be.

[0129] Y a22 Specific examples include direct bond, -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O)2-, -S (=O)2-NH-, -OC(=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 -OC(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -OC(=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 -OC(=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 of 1 to 5.] is.

[0130] Y a22 is preferably -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O)2-, -S(=O)2-NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-. Y a22 It is more preferred that Y is -NH-C(=O)-, -C(=O)-NH-, -OC(=O)-NH-, -NH-C(=O)-O- or -NH-C(=O)-NH-. a22 may not be a direct bond.

[0131] Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and may have a straight-chain or branched structure. Z preferably has 2 to 4 carbon atoms, and particularly 2. Specific examples of Z include a direct bond, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH= having a branched structure, -CH2(CH-)CH2- having a branched structure, -CH2CH2CH= having a branched structure, -CH2CH2CH2CH2CH= having a branched structure, -CH2CH2(CH-)CH2- having a branched structure, and -CH2CH2CH2CH= having a branched structure. Z does not have to be a direct bond.

[0132] Monomer (A2) is CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-R a2 , CH2=C(-X a2 )-C(=O)-O-(CH2) m -OC(=O)-NH-R a2 , CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-OR a2 , CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-NH-R a2 Preferably, R 3 and X a2 has the same meaning as above.] Monomer (A2) is CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-R a2 It is particularly preferred that:

[0133] Monomer (A2) can be produced by reacting a hydroxyalkyl (meth)acrylate or a hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate, such as lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, or behenyl isocyanate. Alternatively, monomer (A2) can be produced by reacting a (meth)acrylate having an isocyanate group in the side chain, such as 2-methacryloyloxyethyl methacrylate, with a long-chain alkylamine or long-chain alkylalcohol. Examples of long-chain alkylamines include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine. Examples of long-chain alkylalcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

[0134] Preferred examples of the hydrophobic monomer (A) are as follows: Stearyl (meth)acrylate, behenyl (meth)acrylate, stearyl alpha chloroacrylate, behenyl alpha chloroacrylate; Stearyl (meth)acrylamide, Behenyl (meth)acrylamide;

[0135] TIFF2025168981000002.tif2453

[0136] TIFF2025168981000003.tif2253 TIFF2025168981000004.tif2152 TIFF2025168981000005.tif2155

[0137] TIFF2025168981000006.tif2357 TIFF2025168981000007.tif2256 TIFF2025168981000008.tif2156

[0138] TIFF2025168981000009.tif2051 TIFF2025168981000010.tif2054 TIFF2025168981000011.tif2352 TIFF2025168981000012.tif2659

[0139] TIFF2025168981000013.tif2046

[0140] TIFF2025168981000014.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 in which the α-position is a hydrogen atom, but specific examples include a methacrylic compound in which the α-position is a methyl group and an α-chloroacrylic compound in which the α-position is a chlorine atom.

[0141] The monomer (A2) has the formula: R a22 -C(=O)-NH-R a23 -OR a21 [In the formula, R a21 represents an organic residue having an ethylenically unsaturated polymerizable group, R a22 is a hydrocarbon group having 6 to 40 carbon atoms, R a23 is a hydrocarbon group having 1 to 5 carbon atoms. It is preferable that the monomer is an amide group-containing monomer represented by the following formula:

[0142] R a21 is an organic residue having an ethylenically unsaturated polymerizable group, and is not particularly limited as long as it has a carbon-carbon double bond. Specifically, -C(=O)CR a211 =CH2, -CHR a211=CH2, -CH2CHR a211 ═CH2, and the like. a211 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 21 R may have various organic groups in addition to the ethylenically unsaturated polymerizable group, such as chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, and polysiloxane groups, and these organic groups may be substituted with various substituents. a21 is -C(=O)CR a211 It is preferred that =CH2.

[0143] R a22 R is a hydrocarbon group having 6 to 40 carbon atoms, preferably an alkyl group, and examples thereof include chain hydrocarbon groups and cyclic hydrocarbon groups. Among these, a chain hydrocarbon group is preferred, and a linear saturated hydrocarbon group is particularly preferred. a22 The number of carbon atoms is 6 or more and 40 or less, preferably 11 to 27, and particularly preferably 15 to 23.

[0144] R a23 R is a hydrocarbon group having 1 to 5 carbon atoms, preferably an alkyl group. The hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched, and may have an unsaturated bond, but is preferably linear. a23 The number of carbon atoms in R is preferably 2 to 4, and particularly preferably 2. a23 is preferably an alkylene group.

[0145] The amide group-containing monomer is R a22 There is only one type (for example, R a22 is only a compound having 17 carbon atoms), or R a22 is a combination of multiple a22 and a compound having 17 carbon atoms, R a22 and a compound having 15 carbon atoms).

[0146] An example of an amide group-containing monomer is a carboxylic acid amide alkyl (meth)acrylate. Specific examples of the amide group-containing monomer include palmitic acid amidoethyl (meth)acrylate, stearic acid amidoethyl (meth)acrylate, behenic acid amidoethyl (meth)acrylate, myristate amidoethyl (meth)acrylate, laurate amidoethyl (meth)acrylate, isostearate ethyl amido(meth)acrylate, oleic acid ethyl amido(meth)acrylate, tert-butylcyclohexylcaproic acid amidoethyl (meth)acrylate, adamantanecarboxylic acid ethyl amido(meth)acrylate, naphthalenecarboxylic acid amidoethyl (meth)acrylate, anthracenecarboxylic acid amidoethyl (meth)acrylate, palmitic acid amidopropyl (meth)acrylate, stearic acid amidopropyl (meth)acrylate, palmitic acid amidoethyl vinyl ether, stearic acid amidoethyl vinyl ether, palmitic acid amidoethyl allyl ether, stearic acid amidoethyl allyl ether, and mixtures thereof.

[0147] The amide group-containing monomer is preferably stearamidoethyl (meth)acrylate. The amide group-containing monomer may be a mixture containing stearamidoethyl (meth)acrylate. In the mixture containing stearamidoethyl (meth)acrylate, the amount of stearamidoethyl (meth)acrylate may be, for example, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, based on the total weight of the amide group-containing monomers. The amount of stearamidoethyl (meth)acrylate may 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 monomers. The remaining monomer may be, for example, palmitamidoethyl (meth)acrylate.

[0148] The amount of monomer (A2) in monomer (A) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, or 80% by weight or more, and is preferably 30% by weight or more.

[0149] [(B) Hydrophilic monomer] In the present disclosure, the hydrophilic monomer (B) is copolymerized with the hydrophobic monomer (A) to form a copolymer. The hydrophilic monomer (B) is a monomer different from the hydrophobic monomer (A).

[0150] [Characteristics, etc.] The properties that the hydrophilic monomer (B) may have are shown below.

[0151] (solubility characteristics) The hydrophilic monomer (B) is hydrophilic and highly water-soluble. The hydrophilic monomer (B) may have a water solubility at 25°C of more than 3.0 g / L, and may be soluble in water at 25°C to an arbitrary amount (i.e., water-miscible) of 4.0 g / L or more, 5.0 g / L or more, 7.0 g / L or more, 10.0 g / L or more, 15.0 g / L or more, 20.0 g / L or more, 30.0 g / L or more, 50.0 g / L or more, 100.0 g / L or more, or any amount. The water solubility can be calculated by adding the compound in small amounts to a predetermined amount of water (25°C) and calculating the amount dissolved at the point where the compound no longer dissolves (e.g., floating, precipitation, deposition, or cloudiness is observed).

[0152] The solubility parameter (SP value) of the hydrophilic monomer (B) is: The SP value may be 10.0 or more, 11.0 or more, 11.5 or more, 12.0 or more, 12.5 or more, 13.0 or more, 13.5 or more, 14.0 or more, 14.5 or more, 15.0 or more, or 16.0 or more, and may be 24.0 or less, 23.0 or less, 22.0 or less, 21.0 or less, 20.0 or less, 19.0 or less, or 18.0 or less, preferably 10.0 or more, particularly 12.0 or more. The SP value can be calculated using Fedors' formula (Polym. Eng. Sci., 14[2], 147(1974)).

[0153] The octanol / water partition coefficient (logPow) of the hydrophilic monomer (B) may be 2.0 or less, 1.5 or less, 1.0 or less, 0.5 or less, or 0 or less, or may be -5.0 or more, -4.0 or more, -3.0 or more, -2.5 or more, -2.0 or more, -1.5 or more, -1.0 or more, or -0.5 or more.

[0154] (Other characteristics) The hydrophilic monomer (B) is preferably a biobased compound containing carbon of biobased origin. The biobased degree is measured in accordance with ASTM D6866. The biobased degree of each hydrophilic monomer (B) may be independently 20% or more, preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example, 100%. A high biobased degree means that the amount of fossil resource-based materials, such as petroleum, used is reduced. From this perspective, the higher the biobased degree of the hydrophilic monomer (B), the more preferable it is.

[0155] The biodegradability of the hydrophilic monomer (B) after 180 days is preferably 5% or more. Higher biodegradability is preferable because it reduces the environmental impact. The biodegradability of the hydrophilic monomer (B) after 180 days may be, for example, 10% or more, 20% or more, 30% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, and is preferably 30% or more, more preferably 50% or more, even more preferably 70% or more, and most preferably 80% or more. The biodegradability of the hydrophilic monomer (B) after 60 days is preferably 5% or more. Higher biodegradability is preferable because it reduces the environmental impact. The biodegradability of the hydrophilic monomer (B) after 60 days may be, for example, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, or 45% or more, preferably 10% or more, more preferably 30% or more. Such biodegradability may be the biodegradability specified in JIS K 6953-1 or ASTM D6400.

[0156] The melting point of the hydrophilic monomer (B) 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. The melting point of the hydrophilic monomer (B) 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.

[0157] [Structure, etc.] The hydrophilic monomer (B) may be a monomer having a hydrophilic group. The hydrophilic group may be an oxyalkylene group, a hydroxyl group, an ion-donating group, or the like. The ion-donating group may be an anion-donating group and / or a cation-donating group. Examples of the anion-donating group include a carboxyl group, a sulfonic acid group, or a phosphate group. The cation-donating group may be an amino group, preferably a tertiary amino group or a quaternary amino group.

[0158] The hydrophilic monomer (B) may contain an amide group, a urea group, or a urethane group. The hydrophilic monomer (B) may be a combination of a hydrophilic monomer having an amide group, a urea group, or a urethane group with a hydrophilic monomer not having an amide group, a urea group, or a urethane group. By including such a group in the hydrophilic monomer (B), the effects of the present disclosure can be effectively achieved.

[0159] The hydrophilic monomer (B) is Formula B: CH2=C(-X b )-Y b -Z b -(R b ) k [In the formula, X b is a hydrogen atom, a monovalent organic group, or a halogen atom, Y bis 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-, -NR'-, -C(OR')R'-, and -C(OR')(-)2, -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms); Z b represents a direct bond, a divalent to tetravalent hydrocarbon group having 1 to 4 carbon atoms, or a trivalent or tetravalent hydrocarbon group having 1 to 6 carbon atoms, or -(Z b1 O) n -Z b2 - and Z b1 are each independently an alkylene group having 2 to 6 carbon atoms, Z b2 is an alkylene group having 1 to 4 carbon atoms, n is an integer from 0 to 90, R b are each independently a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, or a phosphate group, k is 1 to 3. It is a monomer represented by the formula:

[0160] X b X may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. b Examples of X are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. b is preferably a hydrogen atom, a methyl group, or a chlorine atom. b is particularly preferably a hydrogen atom.

[0161] Y b is a group consisting of one or more members selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2, -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms).

[0162] In one aspect, Y b is —O—, —OC(═O)—, —OC(═O)—O—, —C(═O)—NR′—, —OC(═O)—NR′—, —NR′—C(═O)—, —NR′—C(═O)—O—, —NR′—C(═O)—NR′—, —C(═O)—O—, —C(═O)—NR′—, —C(OR′)R′—, or —C(OR′)(-)2 (wherein R′ in each occurrence is independently a hydrogen atom or a hydrocarbon having 1 to 4 carbon atoms).

[0163] Y b may preferably be -C(=O)-O-, -C(=O)-NH-, -O-, or -OC(=O)-.

[0164] Y b may preferably be -C(=O)-O-.

[0165] Z b represents a direct bond, a divalent to tetravalent hydrocarbon group having 1 to 4 carbon atoms, or a trivalent or tetravalent hydrocarbon group having 1 to 6 carbon atoms, or -(Z b1 O) n -Z b2 -It is.

[0166] The divalent to tetravalent hydrocarbon group having 1 to 4 carbon atoms may have a straight-chain structure or a branched structure. The divalent to tetravalent hydrocarbon group having 1 to 4 carbon atoms is preferably a divalent or trivalent hydrocarbon group having 1 to 4 carbon atoms, more preferably a divalent hydrocarbon group having 1 to 4 carbon atoms. The carbon number of the hydrocarbon group having 1 to 4 carbon atoms is preferably 1 or 2, more preferably 2.

[0167] The trivalent or tetravalent hydrocarbon group having 1 to 6 carbon atoms may have a linear or branched structure. The number of carbon atoms in the trivalent or tetravalent hydrocarbon group having 1 to 6 carbon atoms is preferably 2 to 4, and more preferably 2 or 3.

[0168] -(Z b1 O) n -Z b2- is an oxyalkylene group, and Z b1 is an alkylene group having 2 to 6 carbon atoms, and Z b2 is an alkylene group having 1 to 4 carbon atoms, and n is an integer of 0 to 90.

[0169] Z b1 is an alkylene group having 2 to 6 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and more preferably an alkylene group having 2 carbon atoms (i.e., an ethylene group). The alkylene group may be a linear or branched alkylene group.

[0170] Z b2 is an alkylene group having 1 to 4 carbon atoms, preferably an alkylene group having 2 or 3 carbon atoms, more preferably an alkylene group having 2 carbon atoms (i.e., an ethylene group). The alkylene group may be a linear or branched alkylene group.

[0171] n is an integer from 0 to 90, and may be 0 or more, 1 or more, 2 or more, 3 or more, 5 or more, 7 or more, 10 or more, 15 or more, 20 or more, 25 or more, 30 or more, 35 or more, or 40 or more, or may be 90 or less, 85 or less, 80 or less, 75 or less, 70 or less, 65 or less, 60 or less, 55 or less, or 50 or less. For example, n may be 2.

[0172] R b are each independently a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, or a phosphate group. b is preferably a hydroxyl group.

[0173] k is 1 to 3, and may be 1 or more, 2 or more, or 3 or more, and may be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0174] The hydrophilic monomer (B) may be the hydrophilic monomer (B1) shown below.

[0175] (B1) Monomer The hydrophilic monomer (B) is formula: CH2=C(-X b )-C(=O)-Y b -Z b -(R b ) k [In the formula, X b is a hydrogen atom, a monovalent organic group, or a halogen atom, Y b is a direct bond, —O—, or —NH—; Z b represents a direct bond, a divalent to tetravalent hydrocarbon group having 1 to 4 carbon atoms, or a trivalent or tetravalent hydrocarbon group having 1 to 6 carbon atoms, or -(Z b1 O) n -Z b2 - and Z b1 are each independently an alkylene group having 2 to 6 carbon atoms, Z b2 is an alkylene group having 1 to 4 carbon atoms, n is an integer from 0 to 90, R b are each independently a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, or a phosphate group, k is 1 to 3. It is preferable that the monomer is a monomer represented by the following formula:

[0176] X b X may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. b Examples of X are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. b is preferably a hydrogen atom, a methyl group, or a chlorine atom. b is particularly preferably a hydrogen atom.

[0177] Y b is a direct bond, —O—, or —NH—, preferably —O— or —NH—.

[0178] Z brepresents a direct bond, a divalent to tetravalent hydrocarbon group having 1 to 4 carbon atoms, or a trivalent or tetravalent hydrocarbon group having 1 to 6 carbon atoms, or -(Z b1 O) n -Z b2 -It is.

[0179] The divalent to tetravalent hydrocarbon group having 1 to 4 carbon atoms may have a straight-chain structure or a branched structure. The divalent to tetravalent hydrocarbon group having 1 to 4 carbon atoms is preferably a divalent or trivalent hydrocarbon group having 1 to 4 carbon atoms, more preferably a divalent hydrocarbon group having 1 to 4 carbon atoms. The carbon number of the hydrocarbon group having 1 to 4 carbon atoms is preferably 1 or 2, more preferably 2.

[0180] The trivalent or tetravalent hydrocarbon group having 1 to 6 carbon atoms may have a linear or branched structure. The number of carbon atoms in the trivalent or tetravalent hydrocarbon group having 1 to 6 carbon atoms is preferably 2 to 4, and more preferably 2 or 3.

[0181] -(Z b1 O) n -Z b2 - is an oxyalkylene group, and Z b1 is an alkylene group having 2 to 6 carbon atoms, and Z b2 is an alkylene group having 1 to 4 carbon atoms, and n is an integer of 0 to 90.

[0182] Z b1 is an alkylene group having 2 to 6 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and more preferably an alkylene group having 2 carbon atoms (i.e., an ethylene group). The alkylene group may be a linear or branched alkylene group.

[0183] Z b2 is an alkylene group having 1 to 4 carbon atoms, preferably an alkylene group having 2 or 3 carbon atoms, more preferably an alkylene group having 2 carbon atoms (i.e., an ethylene group). The alkylene group may be a linear or branched alkylene group.

[0184] n is an integer from 0 to 90, and may be 0 or more, 1 or more, 2 or more, 3 or more, 5 or more, 7 or more, 10 or more, 15 or more, 20 or more, 25 or more, 30 or more, 35 or more, or 40 or more, or may be 90 or less, 85 or less, 80 or less, 75 or less, 70 or less, 65 or less, 60 or less, 55 or less, or 50 or less. For example, n may be 2.

[0185] R b are each independently a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, or a phosphate group. b is preferably a hydroxyl group.

[0186] k is 1 to 3, and may be 1 or more, 2 or more, or 3 or more, and may be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0187] The hydrophilic monomer (B) may be the hydrophilic monomer (B2) shown below.

[0188] (B2) Monomer The hydrophilic monomer (B) is formula: CH2=C(-X b )-C(=O)-Y b -(Z b1 O) n -Z b2 -OH [In the formula, X b is a hydrogen atom or a methyl group, Y b is —O— or —NH—, Z b1 is an alkylene group having 1 to 6 carbon atoms, Z b2 is an alkylene group having 1 to 4 carbon atoms, n is an integer from 0 to 90. It is preferable that the oxyalkylene group-containing monomer is represented by the following formula:

[0189] X b is a hydrogen atom or a methyl group, preferably a hydrogen atom.

[0190] Y b is —O— or —NH—, preferably —O—.

[0191] Z b1 is an alkylene group having 1 to 6 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and even more preferably an alkylene group having 2 carbon atoms (i.e., an ethylene group). The alkylene group may be a linear or branched alkylene group.

[0192] Z b2 is an alkylene group having 1 to 4 carbon atoms, preferably an alkylene group having 2 or 3 carbon atoms, and more preferably an alkylene group having 2 carbon atoms (i.e., an ethylene group). The alkylene group may be a linear or branched alkylene group.

[0193] n is an integer from 0 to 90, and may be 0 or more, 1 or more, 2 or more, 3 or more, 5 or more, 7 or more, 10 or more, 15 or more, 20 or more, 25 or more, 30 or more, 35 or more, or 40 or more, or may be 90 or less, 85 or less, 80 or less, 75 or less, 70 or less, 65 or less, 60 or less, 55 or less, or 50 or less. For example, n may be 2.

[0194] Specific examples of the hydrophilic monomer (B) include methacrylic acid, acrylic acid, dimethylaminoethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl acrylamide, and hydroxypropyl acrylamide, and particularly preferred are hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl acrylamide, and hydroxypropyl acrylamide.

[0195] Preferred examples of the hydrophilic monomer (B) are as follows, but are not limited to these. CH2=CHCOO-CH2CH2O-H CH2=CHCOO-CH2CH2CH2O-H CH2=CHCOO-CH2CH(CH3)OH CH2=CHCOO-CH(CH3)CH2O-H CH2=CHCOO-(CH2CH2O)2-H CH2=CHCOO-(CH2CH2O)4-H CH2=CHCOO-(CH2CH2O)6-H CH2=CHCOO-(CH2CH2O) 10 -H CH2=CHCOO-(CH2CH2O)5-CH3 CH2=CHCOO-(CH2CH2O)9-CH3 CH2=CHCOO-(CH2CH2O) 23 -CH3 CH2=CHCOO-(CH2CH2O) 90 -CH3

[0196] The copolymer of the present disclosure may contain the following monomers in addition to the hydrophobic monomer (A) and the hydrophilic monomer (B).

[0197] (C) Ion-donor group-containing monomer The copolymer may contain an ion-donating group-containing monomer (C). Monomer (C) is preferably a monomer containing an olefinic carbon-carbon double bond and an ion-donating group (particularly, an acrylic monomer). The ion-donating group is an anion-donating group and / or a cation-donating group. Monomer (C) is a monomer other than monomer (B), particularly a monomer containing an ion-donating group.

[0198] Examples of the monomer having an anion donating group include a monomer having a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Specific examples of the monomer having an anion donating group include crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, (meth)acrylate phosphate, vinylbenzenesulfonic acid, acrylamido-tertiarybutylsulfonic acid, and salts thereof.

[0199] Salts of anion-donating groups include alkali metal salts, alkaline earth metal salts, and ammonium salts such as methylammonium salts, ethanolammonium salts, and triethanolammonium salts.

[0200] In the monomer having a cation donating group, examples of the cation donating group include an amino group, preferably a tertiary amino group or a quaternary amino group. In the tertiary amino group, the two groups bonded to the nitrogen atom are preferably the same or different and are an aliphatic group (particularly an alkyl group) having 1 to 5 carbon atoms, an aromatic group (an aryl group) having 6 to 20 carbon atoms, or an araliphatic group (particularly an aralkyl group, such as a benzyl group (CH-CH-)) having 7 to 25 carbon atoms. In the quaternary amino group, the three groups bonded to the nitrogen atom are preferably the same or different and are an aliphatic group (particularly an alkyl group) having 1 to 5 carbon atoms, an aromatic group (an aryl group) having 6 to 20 carbon atoms, or an araliphatic group (particularly an aralkyl group, such as a benzyl group (CH-CH-)) having 7 to 25 carbon atoms. In the tertiary amino group and the quaternary amino group, the remaining group bonded to the nitrogen atom may have a carbon-carbon double bond. The cation donating group may be in the form of a salt.

[0201] The cation-donating group in the form of a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, such as carboxylic acids having 1 to 20 carbon atoms (particularly monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid), are preferred. Dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and salts thereof are preferred.

[0202] Specific examples of the monomer having a cation donor group are as follows: CH2=CHCOO-CH2CH2-N(CH3)2 and its salts (e.g. acetate) CH2=CHCOO-CH2CH2-N(CH2CH3)2 and its salts (e.g. acetate) CH2=C(CH3)COO-CH2CH2-N(CH3)2 and its salts (e.g. acetate) CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2 and its salts (e.g. acetate salts) CH2=CHC(O)N(H)-CH2CH2CH2-N(CH3)2 and its salts (e.g. acetate) CH2=CHCOO-CH2CH2-N(-CH3)(-CH2-C6H5) and its salts (e.g. acetate) CH2=C(CH3)COO-CH2CH2-N(-CH2CH3)(-CH2-C6H5) and its salts (e.g. acetate) CH2=CHCOO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH2-N + (-CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (-CH2CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Br - CH2=C(CH3)COO-CH2CH2-N + (CH3)3I - CH2=C(CH3)COO-CH2CH2-N + (CH3)3O - SO3CH3 CH2=C(CH3)COO-CH2CH2-N + (CH3)(-CH2-C6H5)2Br -

[0203] The ion-donor group-containing monomer (C) is preferably methacrylic acid, acrylic acid, or dimethylaminoethyl methacrylate, and more preferably methacrylic acid or dimethylaminoethyl methacrylate.

[0204] (D) Halogenated olefin monomers The copolymer may have a repeating unit derived from a halogenated olefin monomer (D). The halogenated olefin monomer (D) may not have a fluorine atom. The halogenated olefin monomer (D) is preferably an olefin having 2 to 20 carbon atoms and substituted with 1 to 10 chlorine, bromine, or iodine atoms. The halogenated olefin monomer (D) is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms and having 1 to 5 chlorine atoms. Preferred examples of the halogenated olefin monomer (D) include vinyl halides such as vinyl chloride, vinyl bromide, and vinyl iodide, and vinylidene halides such as vinylidene chloride, vinylidene bromide, and vinylidene iodide. Vinyl chloride or vinylidene chloride is preferred because it enhances water repellency (particularly water repellency durability). The presence of repeating units derived from the halogenated olefin monomer (D) enhances the washing durability of the copolymer.

[0205] (E) Crosslinkable monomer The copolymer has a crosslinkable monomer having at least two reactive groups and / or ethylenically unsaturated double bonds (preferably, (meth)acrylate groups), and the crosslinkable monomer (E) may be a monomer not containing fluorine atoms or a compound not containing fluorine atoms. The crosslinkable monomer (E) may be a compound having at least two ethylenically unsaturated double bonds (preferably, (meth)acrylate groups), or a compound having at least one ethylenically unsaturated double bond and at least one reactive group. Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, and a carboxyl group.

[0206] The crosslinking monomer may be a mono(meth)acrylate, di(meth)acrylate or di(meth)acrylamide having a reactive group.

[0207] One example of a crosslinkable monomer is a vinyl monomer having a reactive group.

[0208] Examples of crosslinkable monomers include, but are not limited to, diacetone (meth)acrylamide, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

[0209] (F) Cyclic hydrocarbon group-containing monomer The copolymer may have a repeating unit derived from a cyclic hydrocarbon group-containing monomer (F). The cyclic hydrocarbon group-containing monomer (F) is a monomer having a cyclic hydrocarbon group, and may be a monomer having one ethylenically unsaturated double bond and a cyclic hydrocarbon group.

[0210] The cyclic hydrocarbon group-containing monomer (F) preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, and may, for example, have a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0211] The cyclic hydrocarbon group may be alicyclic or aromatic, preferably alicyclic. The cyclic hydrocarbon group may be saturated or unsaturated, preferably saturated. The cyclic hydrocarbon group may be a monocyclic group, a polycyclic group, or a bridged ring group, preferably a bridged ring group. The cyclic hydrocarbon group may have a chain group (e.g., a linear or branched chain hydrocarbon group).

[0212] The cyclic hydrocarbon group may have 4 or more, 6 or more, or 8 or more carbon atoms, and may have 30 or less, 26 or less, 22 or less, 18 or less, or 14 or less carbon atoms.

[0213] Specific examples of cyclic hydrocarbon groups include cyclohexyl, t-butylcyclohexyl, adamantyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, bornyl, isobornyl, norbornyl, dicyclopentanyl, dicyclopentenyl, benzyl, phenyl, naphthyl, 2-t-butylphenyl, residues obtained by removing one or more hydrogen atoms from these groups (e.g., cyclohexylene, adamantylene, phenylene, naphthylene, etc.), and groups that are substitution products thereof.

[0214] Specific examples of the cyclic hydrocarbon group-containing monomer include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and compounds in which these acrylates are substituted with acrylamide, etc. These may be used alone or in combination of two or more.

[0215] (G) Other monomers The other monomers are not limited to these examples, but include acrylonitrile, organosiloxane-containing (meth)acrylates, short-chain alkyl (meth)acrylates, vinyl acetate, styrene, α-methylstyrene, p-methylstyrene, vinyl alkyl ethers, etc. The other monomers (G) may be used alone or in combination of two or more.

[0216] [Polymer composition] The combination of monomers (A) to (G) constituting the repeating units of the copolymer is not particularly limited as long as it contains monomer (A) and monomer (B), and examples are as follows (parentheses omitted): A+B A+B+C 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 combination. In the case of pulp products, it is preferable to use the monomer (A), the monomer (B), and the monomer (C) in combination.

[0217] The amount of repeating units derived from the hydrophilic monomer (B) may be 51% by weight or more, 53% by weight or more, 55% by weight or more, 57% by weight or more, 60% by weight or more, 62% by weight or more, 65% by weight or more, 67% by weight or more, 70% by weight or more, 72% by weight or more, or 75% by weight or more, and may be 99% by weight or less, 97% by weight or less, 95% by weight or less, 93% by weight or less, 90% by weight or less, 88% by weight or less, 85% by weight or less, 83% by weight or less, 80% by weight or less, 77% by weight or less, 75% by weight or less, 72% by weight or less, or 70% by weight or less, based on the total amount of repeating units derived from the hydrophobic monomer (A) and the hydrophilic monomer (B).

[0218] In one embodiment, the amount of repeating units derived from the hydrophilic monomer (B) may be 51 to 99% by weight, 55 to 95% by weight, or 60 to 90% by weight relative to the total amount of repeating units derived from the hydrophobic monomer (A) and the hydrophilic monomer (B).

[0219] The amount of repeating units derived from monomer (A) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the copolymer. The amount of repeating units derived from monomer (A) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the copolymer.

[0220] The amount of repeating units derived from monomer (B) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the copolymer. The amount of repeating units derived from monomer (B) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the copolymer. The amount of repeating units derived from monomer (B) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of the amount of repeating units derived from monomer (A). The amount of repeating units derived from monomer (B) may 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, relative to 100 parts by weight of the amount of repeating units derived from monomer (A).

[0221] The total amount of the hydrophobic monomer (A) and the hydrophilic monomer (B) relative to the copolymer may be 50% by weight or more, 55% by weight or more, 60% by weight or more, 65% by weight or more, 70% by weight or more, or 75% by weight or more, and may be 100% by weight or less, 95% by weight or less, 90% by weight or less, 85% by weight or less, 80% by weight or less, 75% by weight or less, or 70% by weight or less.

[0222] In one embodiment, the total amount of the hydrophobic monomer (A) and the hydrophilic monomer (B) relative to the copolymer is: It may be 50% to 100% by weight, 60% to 100% by weight, or 70% to 100% by weight.

[0223] The amount of repeating units derived from monomer (C) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the copolymer. The amount of repeating units derived from monomer (C) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the copolymer. The amount of the repeating units derived from monomer (C) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of the amount of the repeating units derived from monomer (A). The amount of repeating units derived from monomer (C) may 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, relative to 100 parts by weight of the amount of repeating units derived from monomer (A).

[0224] The amount of repeating units derived from monomer (D) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the copolymer. The amount of repeating units derived from monomer (D) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the copolymer. The amount of repeating units derived from monomer (D) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of the amount of repeating units derived from monomer (A). The amount of repeating units derived from monomer (D) may 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, per 100 parts by weight of the amount of repeating units derived from monomer (A).

[0225] The amount of repeating units derived from monomer (E) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the copolymer. The amount of repeating units derived from monomer (E) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the copolymer. The amount of repeating units derived from monomer (E) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of the amount of repeating units derived from monomer (A). The amount of repeating units derived from monomer (E) may 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, relative to 100 parts by weight of the amount of repeating units derived from monomer (A).

[0226] The amount of repeating units derived from monomer (F) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the copolymer. The amount of repeating units derived from monomer (F) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the copolymer. The amount of repeating units derived from monomer (F) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of the amount of repeating units derived from monomer (A). The amount of repeating units derived from monomer (F) may 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, relative to 100 parts by weight of the amount of repeating units derived from monomer (A).

[0227] The amount of repeating units derived from monomer (G) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the copolymer. The amount of repeating units derived from monomer (G) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the copolymer. The amount of repeating units derived from monomer (G) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of the amount of repeating units derived from monomer (A). The amount of repeating units derived from monomer (G) may 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, per 100 parts by weight of the amount of repeating units derived from monomer (A).

[0228] [Polymerization method] The copolymer of the present disclosure can be produced by a known polymerization method, and the polymerization reaction conditions can be selected arbitrarily. Examples of such polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization.

[0229] In solution polymerization, a method is employed in which monomers are dissolved in an organic solvent in the presence of a polymerization initiator, and after purging with nitrogen, the mixture is heated and stirred at a temperature in the range of 30 to 120°C for 1 to 10 hours. Examples of polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, per 100 parts by weight of the monomers.

[0230] The organic solvent is inert to the monomers and dissolves them, and may be, for example, an ester (e.g., an ester having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), a ketone (e.g., a ketone having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone), or an alcohol (e.g., an alcohol having 1 to 40 carbon atoms, specifically, ethanol, butanol, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane. The organic solvent is used in an amount of 10 to 3000 parts by weight, for example, 50 to 2000 parts by weight, relative to 100 parts by weight of the total of the monomers.

[0231] Emulsion polymerization involves emulsifying monomers in water in the presence of a polymerization initiator and an emulsifier, purging with nitrogen, and then polymerizing the mixture at 50-80°C for 1-20 hours with stirring. Polymerization initiators include water-soluble initiators such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, sodium peroxide, potassium persulfate, and ammonium persulfate, as well as oil-soluble initiators such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01-10 parts by weight per 100 parts by weight of monomer.

[0232] To obtain a polymer aqueous dispersion with excellent shelf stability, it is desirable to polymerize the monomer by microparticulating it in water using an emulsifying device capable of applying powerful crushing energy, such as a high-pressure homogenizer or ultrasonic homogenizer. Furthermore, various anionic, cationic, or nonionic emulsifiers can be used as emulsifiers, and are used in an amount ranging from 0.5 to 20 parts by weight per 100 parts by weight of the monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. If the monomers are not completely compatible, it is preferable to add a compatibilizer, such as a water-soluble organic solvent or a low-molecular-weight monomer, that will fully compatibilize these monomers. Addition of a compatibilizer can improve emulsifiability and copolymerizability.

[0233] The water-soluble organic solvent may be any of the organic solvents described above. Examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol. These may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of water. Examples of low-molecular-weight monomers include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate. These may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of the total amount of monomers.

[0234] A chain transfer agent may be used in the polymerization. The molecular weight of the polymer can be changed depending on the amount of chain transfer agent used. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (e.g., having 1 to 40 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite. The amount of chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, per 100 parts by weight of the total amount of monomers.

[0235] <Repellent> The repellent agent of the present disclosure comprises the copolymer of the present disclosure. The repellent agent of the present disclosure adheres to a substrate (particularly a pulp substrate) and can impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the substrate, and can also function as a water resistance agent, oil resistance agent, water repellent agent, oil repellent agent, and / or stain resistance agent. The copolymer itself may be used as a repellent agent, or it may be used in combination with other components as described below.

[0236] The repellent agent of the present disclosure may not contain any compound selected from the group consisting of a compound having a fluoroalkyl group having 8 or more carbon atoms, a compound having a perfluoroalkyl group having 8 or more carbon atoms, a compound having a fluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The repellent agent of the present disclosure can impart liquid repellency to a substrate even if it does not contain these fluorine compounds.

[0237] The volumetric abundance ratio of particles of 100 μm or larger in the repellent agent of the present disclosure, as measured by laser diffraction scattering, may be 0.1% or 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. The volumetric abundance ratio of particles of 100 μm or larger in the repellent agent of the present disclosure, as measured by laser diffraction scattering, may be 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 achieving the volumetric abundance ratio of particles of 1 μm or larger in the above range, as measured by laser diffraction scattering, is not limited, and may be, for example, by micronizing the particles in the raw material and / or dispersion using a grinder, homogenizer, or the like.

[0238] The volume median diameter of the repellent of the present disclosure measured by laser diffraction scattering method may be 0.1 μm or more, 1 μm or more, 3 μm or more, 5 μm or more, 10 μm or more, 15 μm or more, 30 μm or more, or 50 μm or more. The volume median diameter of the repellent of the present disclosure measured by laser diffraction scattering method may be 300 μm or less, 200 μm or less, 100 μm or less, 50 μm or less, 30 μm or less, 20 μm or less, 10 μm or less, 5 μm or less, or 1 μm or less. In the present disclosure, the volume median diameter refers to the median diameter (D50) in a volume-based particle size distribution measured by laser diffraction scattering method.

[0239] [Amount of copolymer] The repellent of the present disclosure may contain the copolymer in an amount of 0.1 wt % or more, 0.5 wt % or more, 1.0 wt % or more, 2.0 wt % or more, 3.0 wt % or more, 5.0 wt % or more, 7.0 wt % or more, or 10 wt % or more, and may contain the copolymer in an amount of 20 wt % or less, 15 wt % or less, 13 wt % or less, 10 wt % or less, 8 wt % or less, or 5 wt % or less.

[0240] [Dispersant] The repellent of the present disclosure may contain a dispersant. The dispersant may be at least one selected from an organic dispersant and an inorganic dispersant. The dispersant may be at least one selected from an anionic dispersant, a nonionic dispersant, a cationic dispersant, an amphoteric dispersant, and an inorganic dispersant.

[0241] As the dispersant, an organic dispersant and an inorganic dispersant may be used individually, or a combination of an organic dispersant and an inorganic dispersant may be used.

[0242] An organic dispersant may be used as the dispersant. The organic dispersant can be classified into a nonionic dispersant, an anionic dispersant, a cationic dispersant, and an amphoteric dispersant, and the organic dispersant may refer to a surfactant.

[0243] The dispersant may be fluorine-free.

[0244] [Nonionic dispersant] The dispersant may include a nonionic dispersant, which may be a nonionic surfactant.

[0245] The nonionic dispersant may be a low molecular weight or a high molecular weight dispersant. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more. The molecular weight may be 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0246] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols and amine oxides.

[0247] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0248] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a mono- to trideca-hydric (particularly di- to deca-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0249] An example of an ester ether is a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. An example of an alcohol is a mono- to trideca-hydric (particularly di- to deca-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0250] An example of an alkanolamide is formed from a fatty acid and an alkanolamine. The alkanolamide may be a monoalkanolamide or a dialkanolamine. An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, and having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0251] The polyol may be a di- to penta-hydric alcohol having 10 to 30 carbon atoms. The amine oxide may be an oxide (having, for example, 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0252] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic dispersant is generally preferably 2 to 100.

[0253] 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.

[0254] The nonionic dispersant may be an alkylene oxide adduct of a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sorbitan ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a glycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyglycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sucrose ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, or the like. Among these, those in which the structure of the alkylene oxide adduct moiety and the polyalkylene glycol moiety is polyoxyethylene (POE) or polyoxypropylene (POP) or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Additionally, the nonionic dispersant may be free of aromatic groups.

[0255] The nonionic dispersant has the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [In the formula, R 1is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or acyl group having 2 to 22 carbon atoms, R 2 are independently the same or different and are alkylene groups having 3 or more carbon atoms (e.g., 3 to 10), R 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number greater than or equal to 2, q is a number of 0 or 1 or more. The compound may be a compound represented by the formula:

[0256] R 1 R preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. 1 Preferred specific examples include an octyl group, a nonyl group, a trimethylnonyl group, a lauryl group, a tridecyl group, an oleyl group, and a stearyl group. R 2 Examples of the alkyl group include a propylene group and a butylene group. In the nonionic dispersant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R 2 O) q - may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) at the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, with the oxypropylene chain being preferred.

[0257] Specific examples of nonionic dispersants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkanes (C 12 -C 16 ) Thiol, Sorbitan Mono Fatty Acid (C7-C 19 ) or alkyl (C 12 -C 18) amines, etc., sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lecithin derivatives, etc. Examples of nonionic dispersants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycol, polyethyleneimine ethoxylate, etc.

[0258] 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 type or a mixture of two or more types. The nonionic dispersant may be a mixture of a compound having an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. Specifically, it is preferable to select from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, and polyoxypropylenes having an HLB value of 1 to 18, and sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, and polyoxyethylene sorbitan fatty acid esters having an HLB value of less than 7.

[0259] [Cationic dispersant] The dispersant may include a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a compound having no amide group.

[0260] The cationic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the cationic dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more. The molecular weight of the cationic dispersant may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0261] The cationic dispersant may be aliphatic or aromatic, and examples thereof include ammonium salts (e.g., quaternary ammonium salts). The cationic dispersant may be an oxyethylene adduct ammonium salt. Specific examples include amine salt-type dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines; quaternary ammonium salt-type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, and benzethonium chloride; and polymeric cationic dispersants such as polyquaternium-1 to -47. Examples of cationic dispersants include alkylamine salts and quaternary ammonium salts.

[0262] Low molecular weight cationic dispersants are R 21 -N + (-R 22 )(-R 23 )(-R 24 )X - [In the formula, R 21 , R 22 , R 23 and R 24 is hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, X is an anionic group. R 21 , R 22, R 23 and -R 24 Specific examples of X are alkyl groups (e.g., methyl, butyl, stearyl, and palmityl). Specific examples of X are halogens (e.g., chlorine) and acids (e.g., hydrochloric acid and acetic acid). The cationic dispersant may be a monoalkyltrimethylammonium salt (alkyl having 4 to 40 carbon atoms).

[0263] Specifically, the low molecular weight cationic dispersant is represented by the formula: R 1 p -N + R 2 q X - [In the formula, R 1 is C12 or higher (e.g., C 12 ~C 50 ) is a linear and / or branched aliphatic (saturated and / or unsaturated) group of R 2 is H or a C1-4 alkyl group, a benzyl group, or a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, especially 3) to 50) (CH3 and C2H5 are particularly preferred), X is a halogen atom (e.g., chlorine), or a C1-C4 fatty acid salt, or a C1-C4 sulfonate; p is 1 or 2, q is 2 or 3, and p+q=4. R 1 may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0264] Low molecular weight cationic dispersants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride, and the like.

[0265] The polymeric cationic dispersant may be any of various polymers (e.g., polyquaternium-1 to 47) having cationic groups (e.g., ammonium groups, quaternary ammonium groups). Examples of polymeric cationic dispersants include cationic natural products (particularly cationic sugars) such as cationic starch, cationic cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propylhydroxyethylcellulose chloride), cationic guar gum, cationic xanthan gum, and chitosan; and polymers of cationic group-containing monomers such as aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternized dimethylammonium ethyl methacrylate, diallyldimethylammonium chloride, dimethylaminopropylamine, and quaternized vinylimidazole.

[0266] [Anionic dispersant] The dispersant may include an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may be free of an anionic dispersant.

[0267] The anionic dispersant may be a low molecular weight or a high molecular weight dispersant. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more. The molecular weight may be 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0268] Examples of anionic dispersants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonic acid salts, N-acylamino acid dispersants, phosphate mono- or diester dispersants, and sulfosuccinates. An example of an anionic dispersant is a carboxylate (e.g., a fatty acid salt).

[0269] [Amphoteric dispersant] The dispersant may comprise an amphoteric dispersant, which may be an amphoteric surfactant.

[0270] The amphoteric dispersant may be a low molecular weight or a high molecular weight dispersant. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more. The molecular weight may be 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0271] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amido betaines, and acetic acid betaine, and specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetic acid betaine, and fatty acid amidopropyl dimethylamino acetic acid betaine.

[0272] [Inorganic dispersant] The dispersant may include an inorganic dispersant.

[0273] The average primary particle size of the inorganic dispersant may be 5 nm or more, 30 nm or more, 100 nm or more, 1 μm or more, 10 μm or more, or 25 μm or more. The average primary particle size of the inorganic dispersant may be 100 μm or less, 50 μm or less, 10 μm or less, 1 μm or less, 500 nm or less, or 300 nm or less. The average primary particle size can be measured, for example, by observation using a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant may be hydrophilic particles.

[0274] Examples of inorganic dispersants include polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and hydroxyapatite; carbonates such as calcium carbonate and magnesium carbonate; silicates such as calcium metasilicate; sulfates such as calcium sulfate and barium sulfate; and hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

[0275] [Amount of dispersant] The amount of the dispersant may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the copolymer. The amount of the dispersant may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the copolymer.

[0276] [Liquid medium] The repellent agent of the present disclosure may include a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The repellent agent may be a dispersion or a solution. The repellent agent of the present disclosure may include at least water.

[0277] Examples of organic solvents include esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate and butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically, naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxy group (e.g., alcohol, polyol such as glycol-based solvent, ether form of polyol (e.g., monoether form), etc.). These may be used alone or in combination of two or more.

[0278] [Amount of liquid medium] The amount of the liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 1 part by weight of the copolymer. The amount of the liquid medium may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the copolymer.

[0279] 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, relative to 1 part by weight of the copolymer. The amount of water may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the copolymer.

[0280] 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, relative to 1 part by weight of the copolymer. The amount of the organic solvent may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the copolymer.

[0281] 〔silicone〕 The repellent agent of the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, it is possible to achieve good texture and durability in addition to good liquid repellency.

[0282] As the silicone, known silicones can be used, and examples of silicones include polydimethylsiloxane and modified silicones (amino-modified, epoxy-modified silicone, carboxy-modified silicone, methylhydrogen silicone, etc.). The silicone may be a silicone wax having wax-like properties. These may be used alone or in combination of two or more.

[0283] The weight average molecular weight of the silicone may be 1,000 or more, 10,000 or more, or 50,000 or more. The weight average molecular weight of the silicone may be 500,000 or less, 2,500,000 or less, 100,000 or less, or 50,000 or less.

[0284] [Silicone amount] The amount of silicone may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the copolymer. The amount of silicone may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the copolymer.

[0285] 〔wax〕 The repellent agent of the present disclosure may contain wax. By including wax, it is possible to impart good liquid repellency to the substrate.

[0286] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, silicone wax, animal and vegetable wax, mineral wax, etc. Paraffin wax is preferred. Specific examples of compounds constituting the wax include normal alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane), and normal alkenes (e.g., 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane). The number of carbon atoms in the compounds constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be from 200 to 2000, for example, from 250 to 1500, or from 300 to 1000. These may be used alone or in combination of two or more.

[0287] 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.

[0288] [Amount of wax] The amount of wax may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the copolymer. The amount of wax may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the copolymer.

[0289] [Organic acid] The repellent of the present disclosure may contain an organic acid. Known organic acids can be used. Preferred organic acids include carboxylic acids, sulfonic acids, sulfinic acids, etc., with carboxylic acids being particularly preferred. Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., with formic acid or acetic acid being particularly preferred. In the present disclosure, one type of organic acid may be used, or two or more types may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0290] [Amount of organic acid] The amount of organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, based on 100 parts by weight of the copolymer. The amount of organic acid 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, based on 100 parts by weight of the copolymer. The amount of organic acid may be adjusted so that the pH of the repellent is 3 to 10, for example, 5 to 9, particularly 6 to 8. The repellent may be acidic (pH 7 or less, for example, 6 or less).

[0291] [Curing agent] The repellent of the present disclosure may include a curing agent (an active hydrogen reactive compound or an active hydrogen containing compound).

[0292] The curing agent (crosslinking agent) in the repellent agent can effectively cure the copolymer. The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen-reactive groups of the copolymer. Examples of active hydrogen-reactive compounds include isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of active hydrogen-containing compounds include hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0293] The curing agent may contain an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. A polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound functions as a crosslinking agent. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (for example, a blocked polyisocyanate compound). A blocked isocyanate compound is a compound in which the isocyanate group of an isocyanate compound is masked with a blocking agent to inhibit reaction.

[0294] Examples of aliphatic polyisocyanates are trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate, Aliphatic diisocyanates such as cyanatomethyl caproate, and aliphatic triisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane. These may be used alone or in combination of two or more.

[0295] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used alone or in combination of two or more.

[0296] Examples of araliphatic polyisocyanates include araliphatic diisocyanates and araliphatic triisocyanates. Specific examples of araliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used alone or in combination of two or more.

[0297] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used alone or in combination of two or more.

[0298] Examples of the polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, uretimines, isocyanurates, and iminooxadiazinediones. These may be used alone or in combination of two or more.

[0299] These polyisocyanates can be used alone or in combination of two or more. As the polyisocyanate compound, it is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of a polyisocyanate compound is blocked with a blocking agent.The use of a blocked polyisocyanate compound is preferable for reasons such as its relative stability in solution and its usability in the same solution as the repellent.

[0300] The blocking agent blocks free isocyanate groups. When the blocked polyisocyanate compound is heated to, for example, 100°C or higher, e.g., 130°C or higher, the isocyanate groups are regenerated and can easily react with hydroxyl groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. The polyisocyanate compounds can be used alone or in combination.

[0301] The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. The chloromethyl group-containing compound is a compound having a chloromethyl group. Examples of the chloromethyl group-containing compound include chloromethyl polystyrene. The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound include (poly)acrylic acid and (poly)methacrylic acid.

[0302] Specific examples of the ketone group-containing compound include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of the hydrazide compound include hydrazine, carbohydrazide, and adipic acid hydrazide. Specific examples of the melamine compound include melamine resins and methyl etherified melamine resins.

[0303] [Amount of hardener] The amount of the curing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the copolymer. The amount of the curing agent may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the copolymer.

[0304] [Other ingredients] The repellent may contain other components in addition to the above components. Examples of the other components include polysaccharides, paper strength agents, flocculants, retention aids, coagulants, binder resins, anti-slip agents, sizing agents, paper strength agents, fillers, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorizers, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above ingredients, other ingredients may include other water and / or oil repellents, dispersants, texture adjusters, softeners, flame retardants, paint fixatives, wrinkle inhibitors, drying speed adjusters, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity adjusters, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage inhibitors, anti-wrinkle agents after washing, shape retention agents, drape retention agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, dye transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain release agents, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Ciba Specialty Chemicals' Tinopal CBS-X), dye fixatives, and anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine. The following may be blended: stain removers, enzymes such as cellulase, amylase, protease, lipase, and keratinase as fiber surface modifiers; foam inhibitors; and agents capable of imparting silk texture and functionality such as moisture absorption and release. These include silk protein powder, surface-modified products, or emulsified dispersions thereof (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemicals), hydrolyzed silk liquid (Jomo), Silkgen G Soluble S (Ichimaru Falcos)). Stain inhibitors (e.g., nonionic polymeric compounds consisting of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by GOO Chemical Industry Co., Ltd., SRC-1 manufactured by Clariant Japan, etc.) can also be blended. These may be used alone or in combination of two or more.

[0305] [Polysaccharides] Examples of polysaccharides include starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, chitin nanofiber, cellulose nanofiber, pullulan, etc. The polysaccharide may be a substituted modified polysaccharide, in particular a modified polysaccharide into which a hydroxyl group or a cationic group has been introduced.

[0306] [Paper strength agents, flocculants, retention aids or coagulants] Examples of paper strength agents, flocculants, retention aids or coagulants include styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichlorides and polyalkylenepolyamines, dicyandiamide-formaldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0307] [Sizing agent] Examples of sizing agents include cellulose-reactive sizing agents, e.g., rosin-based sizing agents such as rosin-based soaps, rosin-based emulsions / dispersions, cellulose-reactive sizing agents, e.g., emulsions / dispersions of acid anhydrides such as alkyl and alkenyl succinic anhydrides (ASA), alkenyl and alkyl ketene dimers (AKD) and polymers, and anionic, cationic and amphoteric polymers of ethylenically unsaturated monomers, e.g., copolymers of styrene and acrylates.

[0308] [Antistatic agent] Examples of antistatic agents include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate ester salts, phosphonates, and phosphate ester salts; amphoteric antistatic agents such as alkylbetaine and its derivatives, imidazoline and its derivatives, alanine and its derivatives, and nonionic antistatic agents such as aminoalcohols and their derivatives, glycerin and its derivatives, and polyethylene glycol and its derivatives. Ion-conductive polymers obtained by polymerizing or copolymerizing monomers having these cationic, anionic, or amphoteric ion-conductive groups may also be used. These may be used alone or in combination.

[0309] [Preservatives] The preservatives are mainly used to enhance the antiseptic and bactericidal properties and maintain the antiseptic properties during long-term storage. Examples of the preservatives include isothiazolone organic sulfur compounds, benzisothiazolone organic sulfur compounds, benzoic acids, 2-bromo-2-nitro-1,3-propanediol, etc.

[0310] [UV absorber] An ultraviolet absorber is a chemical agent that has the effect of protecting against ultraviolet rays, and is a component that absorbs ultraviolet rays and converts them into infrared rays, visible light, etc. Examples of ultraviolet absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, and 4-t-butyl-4'-methoxybenzoylmethane.

[0311] [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 caused by microbial decomposition products. Examples of antibacterial agents include cationic disinfectants such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide) zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, and polylysine.

[0312] [Deodorant] Examples of deodorizing agents include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, and aminocarboxylic acid metal complexes (e.g., zinc complex of trisodium methylglycinediacetate described in WO 2012 / 090580).

[0313] [Amount of other ingredients] The amount of each of the other components or the total amount thereof may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the copolymer. The amount of each of the other components or the total amount thereof may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the copolymer.

[0314] <Processed products and their manufacturing methods> The method of manufacturing a repellent treated product of the present disclosure includes treating a substrate with the repellent agent described above.

[0315] "Treatment" means applying the repellent to a substrate by immersion, spraying, coating, or the like. The treatment causes the polyol-modified compound, which is the active ingredient of the repellent, to adhere to the interior and / or surface of the substrate. Here, adhesion may be physical or chemical; for example, the polyol-modified compound may be physically or chemically modified (by reaction) with hydroxyl groups of the substrate (fiber, paper, glass, etc.).

[0316] [Base material] The substrate to be treated with the repellent agent of the present disclosure is not limited, but is preferably a textile product or a paper product, particularly a paper product.

[0317] The repellent agent of the present disclosure imparts liquid repellency to a substrate (e.g., a fiber substrate or a paper substrate) and can function as at least one selected from the group consisting of a water repellent agent, an oil repellent agent, an oil-resistant agent, and a water-resistant agent. The substrate treated with the repellent agent of the present disclosure is, for example, oil-resistant paper or water-resistant paper.

[0318] Examples of substrates for textile products include natural fibers of animal or plant origin such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber, or mixtures of these fibers. Textile products include woven fabrics, knitted fabrics, and nonwoven fabrics, as well as cloth in the form of clothing (for example, water-repellent clothing such as raincoats) and carpets, but the treatment may also be applied to fibers, yarns, and intermediate textile products (for example, slivers or rovings) in a state prior to being made into cloth.

[0319] Examples of substrates for paper products include paper made from bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp or thermomechanical pulp, recycled paper pulp such as recycled newspaper, recycled magazine paper, recycled corrugated cardboard or deinked recycled paper, paper containers, paper molded articles, etc. Specific examples of paper products include food packaging materials, food containers, gypsum board base paper, coated base paper, medium-quality paper, general liners and corrugating media, neutral white roll paper, neutral liner, rust-proof liner and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc., and suitable examples include food packaging materials and food containers.

[0320] Substrates that can be treated with the repellent of the present disclosure are not limited to textiles or paper products, but also include stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, resins (which may be natural or synthetic resins, for example, common plastic materials), wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster.

[0321] When the substrate is glass, examples of the glass include sapphire glass, soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass.

[0322] When the substrate is glass, the glass product may be an optical component. A layer (or film), such as a hard coat layer or an anti-reflection layer, may be formed on the surface (outermost layer) of the glass substrate. The anti-reflection layer may be either a single-layer or a multi-layer. Examples of inorganic substances that can be used for the anti-reflection layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, and WO3. These inorganic substances may be used alone or in combination (e.g., as a mixture) of two or more of these. When a multi-layer anti-reflection layer is used, it is preferable to use SiO2 and / or SiO for the outermost layer. When the article to be manufactured is an optical glass component for a touch panel, a transparent electrode, such as a thin film using indium tin oxide (ITO) or indium zinc oxide, may be formed on a portion of the surface of the substrate (glass). In addition, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomizing film layer, a hard coating film layer, a polarizing film, a phase difference film, and a liquid crystal display module, etc., depending on its specific specifications.

[0323] [Processing method] The repellent agent of the present disclosure can be applied to a substrate as a treatment agent (particularly a surface treatment agent) by conventionally known methods. The treatment method may involve dispersing and diluting the repellent agent in an organic solvent or water, as needed, and applying it to the interior and / or surface of the substrate by known methods such as dip coating, spray coating, foam coating, etc., followed by drying. After drying, a textile product is obtained with the solid components of the repellent attached. If necessary, the repellent agent may be applied together with an appropriate crosslinking agent and cured. The repellent agent of the present disclosure may also be used in combination with various additives, such as water and / or oil repellents, antislip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, wrinkle inhibitors, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, and antifoaming agents. Examples of various additives may be the same as those described above under "Other Components." The concentration of the repellent in the treatment agent to be brought into contact with the substrate may be changed as appropriate depending on the application, but may be 0.01 to 10% by weight, for example 0.05 to 5% by weight.

[0324] The repellent can be applied to the substrate by any known method for treating a substrate with a liquid. The substrate may be immersed in the repellent, or the solution may be applied or sprayed onto the substrate. The treated substrate is preferably dried and cured by heating to develop liquid repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In the present disclosure, good performance can be obtained even at low temperatures (e.g., 100°C to 140°C). In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes. When the textile product is paper, the repellent may be coated on the paper, or the solution may be applied or sprayed onto the paper, or the repellent may be mixed with pulp slurry before papermaking. The treatment may be an external or internal addition treatment. Alternatively, the repellent may be applied to the textile product by a cleaning method, such as washing or dry cleaning. [Processing of paper products] The paper substrate includes paper, paper containers, paper molded articles (e.g., pulp molds), etc. The hydrocarbon polymer (1) of the present disclosure adheres well to paper substrates.

[0325] The paper can be produced by a conventional papermaking method, such as an internal treatment method in which the repellent is added to the pulp slurry before papermaking, or an external treatment method in which the repellent is applied to the paper after papermaking.

[0326] The size press for external addition treatment can be divided into the following types depending on the application method: One application method is the so-called pond-type two-roll size press, in which a coating liquid (size liquid) is supplied to the nip formed by passing paper between two rubber rolls, creating a pool of coating liquid called a pond. The paper is then passed through this pool to apply the size liquid to both sides of the paper. Other application methods include the gate roll type, in which the size liquid is applied using a surface transfer method, and the rod metering size press. In the pond-type two-roll size press, the size liquid easily penetrates into the paper, while in the surface transfer type, the size liquid components tend to remain on the paper surface. In the surface transfer type, the coating layer tends to remain on the paper surface compared to the pond-type two-roll size press, and a larger coating layer is formed on the surface than in the pond-type two-roll size press. In the present disclosure, performance can be imparted to paper even when the former pond-type two-roll size press is used. Paper treated in this manner can exhibit excellent oil resistance, water resistance, etc. by simply drying at room temperature or a high temperature, optionally followed by heat treatment, which can be performed at temperatures up to 300°C, for example up to 200°C, particularly in the range of 80°C to 180°C, depending on the paper properties.

[0327] The internal treatment method may refer to a treatment method in which a repellent is added to a pulp slurry before papermaking. The internal treatment method may include, but is not limited to, one or more of the following steps: adding a repellent to a pulp slurry and stirring and mixing it; suction-dehydrating the pulp composition prepared in the above step through a mesh of a predetermined shape to deposit the pulp composition and form a pulp molded intermediate; and molding and drying the pulp molded intermediate in a heated mold to obtain paper, a paper container, or a molded paper product. The treated paper may be briefly dried at room temperature or at an elevated temperature, and then optionally subjected to a heat treatment depending on the paper's properties. The heat treatment temperature may be 150°C or higher, 180°C or higher, or 210°C or higher, or 300°C or lower, 250°C or lower, or 200°C or lower, and particularly may be in the range of 80°C to 180°C. Heat treatment within this temperature range can exhibit excellent oil resistance, water resistance, etc.

[0328] The present disclosure can be used in gypsum board base paper, coated base paper, medium paper, general liners and corrugating media, neutral pure white roll paper, neutral liners, anti-rust liners and metal interleaving paper, kraft paper, etc. It can also be used in 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.

[0329] Pulp raw materials include bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, groundwood pulp, mechanical pulp, or thermomechanical pulp. Any of bleached or unbleached high-yield pulp, recycled paper pulp from newspapers, magazines, corrugated cardboard, deinked paper, etc. can be used. Also, mixtures of the above pulp raw materials with synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, polyvinyl alcohol, etc. can be used.

[0330] A sizing agent can be added to improve the water resistance of paper. Examples of sizing agents include cationic sizing agents, anionic sizing agents, and rosin-based sizing agents (e.g., acidic rosin-based sizing agents and neutral rosin-based sizing agents). The amount of sizing agent may be 0.01 to 5% by weight of the pulp.

[0331] If necessary, the paper may contain additives used in paper production, such as paper strength agents (e.g., starch, modified starch, carboxymethyl cellulose, polyamide polyamine-epichlorohydrin resin), flocculants, fixing agents, retention aids, dyes, fluorescent dyes, slime control agents, and antifoaming agents, in amounts commonly used in papermaking. Starch and modified starch are preferred. If necessary, repellents can be applied to the paper using starch, polyvinyl alcohol, dyes, coating colors, anti-slip agents, etc., using a size press, gate roll coater, bill blade coater, calendar, etc.

[0332] In the case of external addition, the amount of the polyol modified substance contained in the coating layer is 0.01 to 2.0 g / m 2 , especially 0.1 to 1.0 g / m 2 The coating layer is preferably formed from a repellent and starch and / or modified starch. The solid content of the paper repellent in the coating layer is preferably 2 g / m 2 It is preferable that: For internal addition, it is preferable to mix the repellent with the pulp so that the amount of repellent is 0.01 to 50 parts by weight or 0.01 to 30 parts by weight, for example 0.01 to 10 parts by weight, particularly 0.2 to 5.0 parts by weight, per 100 parts by weight of the pulp that forms the paper.

[0333] In external addition, oil resistance can also be imparted to paper using a so-called pond-type two-roll size press process, in which a treatment solution is stored between rolls and the base paper is passed through the treatment solution between the rolls at any roll speed and nip pressure.

[0334] In the external additive treatment, the paper substrate may contain additives such as sizing agents, paper strength agents, flocculants, retention agents, or coagulants. The additives may be nonionic, cationic, anionic, or amphoteric. The ionic charge density of the additives may be -10,000 to 10,000 μeq / g, preferably -4,000 to 8,000 μeq / g, and more preferably -1,000 to 7,000 μeq / g. Additives (solids or active ingredients) such as sizing agents, paper strength agents, flocculants, retention agents, or coagulants are generally used in an amount of 0.1 to 10% by weight (e.g., 0.2 to 5.0% by weight) based on the pulp. In the case of a paper substrate containing cationic additives (e.g., sizing agents, paper strength agents, flocculants, retention agents, or coagulants), the repellent is preferably anionic.

[0335] In the internal addition treatment, it is preferable to make paper from a pulp slurry having a pulp concentration of 0.5 to 5.0% by weight (e.g., 2.5 to 4.0% by weight).Additives (e.g., sizing agents, paper strength agents, flocculants, retention agents, coagulants, etc.) and polyol modifiers can be added to the pulp slurry. Examples of additives (e.g., sizing agents, paper strength agents, flocculants, retention agents, or coagulants) include alkylketene dimers, alkenyl succinic anhydrides, styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichlorides and polyalkylenepolyamines, dicyandiamide-formaldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0336] [Pretreatment of textile products] The textile may be pretreated before being treated with the repellent of the present disclosure. Pretreatment of the textile may impart excellent durability to the textile after treatment with the repellent.

[0337] Examples of pretreatments for textile products include cationization treatment by reaction with a reactive quaternary ammonium salt, anionization treatment such as sulfonation, carboxylation, and phosphate, acetylation treatment after anionization treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, and polymer coating treatment.

[0338] The method for pretreating textile products is not limited, and textile products can be pretreated by conventionally known methods. The pretreatment liquid may be dispersed and diluted in an organic solvent or water as necessary, and applied to the interior and / or surface of the textile product by known methods such as dip coating, spray coating, foam coating, etc., followed by drying. The pH and temperature of the pretreatment liquid may be adjusted depending on the desired degree of treatment. As an example of a method for pretreating textile products, a method for pretreating textile products with the above-mentioned treatment agent will be described in detail below.

[0339] The pretreatment method for textile products is to add -SO3M to the fibers. 1 (In the formula, M 1 represents a monovalent cation), -COOM 2 (In the formula, M 2 represents a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(wherein, X 1 and X 2 and each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) (hereinafter, also referred to as "specific functional groups").

[0340] M 1 Examples of M include H, K, Na, and ammonium ions which may have a substituent. 2 Examples of X include H, K, Na, and an ammonium ion which may have a substituent. 1 or X 2 When is an alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms, and more preferably an alkyl group having 4 to 12 carbon atoms.

[0341] The fibers containing the specific functional groups (hereinafter, sometimes referred to as "functional group-containing fibers") can be prepared, for example, by the following method. (i) A compound having the specific functional group is attached to a fiber material. The attachment of the compound may be in a state where a part of the compound is chemically bonded to a part of the fiber, to the extent that a sufficient amount of the specific functional group remains. (ii) A fiber is prepared in which the specific functional group is directly introduced into the material that constitutes the fiber.

[0342] In the case of (i), for example, functional group-containing fibers can be obtained by a functional group introduction step in which a fiber material is treated with a pretreatment liquid containing one or more compounds having the above-mentioned specific functional groups.

[0343] The material of the fiber material is not particularly limited, and examples thereof include natural fibers such as cotton, linen, silk, and wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene, and composite fibers and blended fibers thereof. The form of the fiber material may be any of fibers (tow, sliver, etc.), yarn, knitted fabric (including interwoven fabric), woven fabric (including interwoven fabric), nonwoven fabric, etc.

[0344] In this embodiment, from the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use textile materials containing polyamide and polyester as raw materials, and it is particularly preferable to use nylons such as nylon 6 and nylon 6,6, polyesters such as polyethylene terephthalate (PET), polytrimethyl terephthalate and polylactic acid, and mixed fibers containing these.

[0345] Above -SO3M 1 A phenolic polymer can be used as the compound having the formula:

[0033] Such a phenolic polymer can be, for example, one containing at least one compound represented by the following general formula:

[0346] [ka] [where, X 2 Ha-SO3M 3 (In the formula, M 3 represents a monovalent cation) or a group represented by the following general formula, and n is an integer of 20 to 3000.

[0347] [ka] [In the formula, M 4 represents a monovalent cation.]

[0348] The above M 3 Examples of the cation include H, K, Na, and an ammonium ion which may have a substituent.

[0349] The above M 4 Examples of the cation include H, K, Na, and an ammonium ion which may have a substituent.

[0350] The compound represented by the above general formula may be, for example, a formalin condensate of phenolsulfonic acid or a formalin condensate of sulfonated bisphenol S.

[0351] Above - COOM 2 Examples of compounds having the formula include polycarboxylic acid polymers.

[0352] As the polycarboxylic acid polymer, for example, a polymer synthesized by a conventionally known radical polymerization method using acrylic acid, methacrylic acid, maleic acid, or the like as a monomer, or a commercially available product can be used.

[0353] Examples of methods for producing polycarboxylic acid polymers include adding a radical polymerization initiator to an aqueous solution of the above-mentioned monomer and / or its salt and reacting the mixture at 30 to 150°C for 2 to 5 hours. At this time, an alcohol such as methanol, ethanol, or isopropyl alcohol, or an aqueous solvent such as acetone may be added to the aqueous solution of the above-mentioned monomer and / or its salt. Examples of radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; redox-based polymerization initiators such as combinations of persulfates and sodium bisulfite; hydrogen peroxide; and water-soluble azo-based polymerization initiators. These radical polymerization initiators may be used alone or in combination. Furthermore, during radical polymerization, a chain transfer agent (e.g., octyl thioglycolate) may be added to adjust the degree of polymerization.

[0354] In addition to the above-mentioned monomers, copolymerizable monomers can be used in radical polymerization. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, acrylamide, acrylates, and methacrylates. Preferred acrylates and methacrylates have a hydrocarbon group having 1 to 3 carbon atoms, which may have a substituent such as a hydroxyl group. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, and propyl methacrylate. These copolymerizable monomers may be used alone or in combination.

[0355] The carboxyl group in the polycarboxylic acid polymer may be free or may be neutralized with an alkali metal, an amine compound, etc. Examples of the alkali metal include sodium, potassium, and lithium, and examples of the amine compound include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0356] The weight average molecular weight of the polycarboxylic acid polymer is preferably from 1,000 to 20,000, more preferably from 3,000 to 15,000, from the viewpoint of improving the water repellency of the resulting textile product.

[0357] As the polycarboxylic acid polymer, commercially available products such as "Neocrystal 770" (trade name, manufactured by Nicca Chemical Co., Ltd.) and "Ceropol PC-300" (trade name, manufactured by Sanyo Chemical Industries, Ltd.) can be used.

[0358] Above -OP(O)(OX 1 )(OX 2 ) includes, for example, phosphate ester compounds represented by the following general formula: [ka] [where, X 1 or X 2 is the same as above, and X 3 represents an alkyl group having 1 to 22 carbon atoms.]

[0359] As the phosphate ester compound, phosphate monoesters, diesters and triesters, in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, and mixtures thereof can be used.

[0360] From the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use lauryl phosphate and decyl phosphate.

[0361] As the phosphate ester compound, for example, commercially available products such as "Phosphanol ML-200" (trade name, manufactured by Toho Chemical Industry Co., Ltd.) can be used.

[0362] The pretreatment liquid containing one or more compounds having the specific functional group may be, for example, an aqueous solution of the compounds described above. The pretreatment liquid may also contain an acid, an alkali, a surfactant, a chelating agent, etc.

[0363] Methods for treating textile materials with the pretreatment solution include, for example, padding, immersion, spraying, and coating. Examples of padding include methods using padding devices, such as those described on pages 396-397 of "Textile Dyeing and Processing Dictionary" (published by Nikkan Kogyo Shimbun, 1963) and pages 256-260 of "Color Dyeing Chemistry III" (published by Jikkyo Publishing Co., Ltd., 1975). Examples of coating include methods using coating machines, such as those described on pages 473-477 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). Examples of immersion include methods using batch dyeing machines, such as those described on pages 196-247 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). These machines include jet dyeing machines, air jet dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, and cheese dyeing machines. Examples of spray treatments include air spraying, which sprays the treatment liquid in a mist form using compressed air, and methods using hydraulic atomization air spraying. The treatment conditions, such as the concentration of the treatment liquid and the heat treatment after application, can be appropriately adjusted taking into account various conditions, such as the purpose and performance. Furthermore, if the pretreatment liquid contains water, it is preferable to dry the pretreatment liquid after application to the fiber material to remove the water. The drying method is not particularly limited, and can be either a dry heat method or a wet heat method. The drying temperature is also not particularly limited, and can be, for example, drying at room temperature to 200°C for 10 seconds to several days. If necessary, heat treatment at a temperature of 100 to 180°C for 10 seconds to 5 minutes may be performed after drying.

[0364] When the textile material is to be dyed, the treatment with the pretreatment liquid may be carried out before dyeing or in the same bath as the dyeing. However, when reduction soaping is carried out, there is a risk that the compound having the above-mentioned specific functional group (e.g., a phenolic polymer compound) adsorbed during the process may fall off, so it is preferable to carry out the treatment after reduction soaping after dyeing.

[0365] The treatment temperature in the immersion treatment can be set to 60 to 130° C. The treatment time can be set to 5 to 60 minutes.

[0366] In the functional group introduction step using a pretreatment liquid, the amount of the compound having the specific functional group attached is preferably 1.0 to 7.0 parts by weight per 100 parts by weight of the textile material. Within this range, durable water repellency and texture can both be achieved at high levels.

[0367] The pH of the pretreatment liquid is preferably adjusted to 3 to 5. The pH can be adjusted using a pH adjuster such as acetic acid or malic acid.

[0368] The pretreatment solution may contain a salt in order to effectively adsorb the compound having the specific functional group onto the fiber material by a salting-out effect. Examples of salts that can be used include sodium chloride. Examples of suitable ammonium carbonate include sodium carbonate, sodium carbonate, ammonium sulfate, and sodium sulfate.

[0369] In the functional group introduction step using a pretreatment liquid, it is preferable to remove the compound having the specific functional group that has been treated in excess. An example of a removal method is washing with water. By performing sufficient removal, it is possible to prevent the development of water repellency in the subsequent water-repellent treatment from being hindered, and in addition, the feel of the resulting textile product is improved. Furthermore, it is preferable to thoroughly dry the resulting functional group-containing fiber before contacting it with the above-mentioned treatment agent.

[0370] (ii) An example of a fiber in which the specific functional group is directly introduced into the material that constitutes the fiber is cationic dyeable polyester (CD-PET).

[0371] From the viewpoint of improving the water repellency of the resulting textile product, the functional group-containing fiber preferably has a surface zeta potential of −100 to −0.1 mV, more preferably −50 to −1 mV. The zeta potential of the fiber surface can be measured, for example, using a zeta potential / particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0372] 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. [Example]

[0373] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0374] <Test Method> The test procedure is as follows:

[0375] <X-ray diffraction measurement of polymer> X-ray diffraction measurements of the polymer were performed using X-ray diffraction (XRD) with a RIGAKU SmartLab. Cu Kα radiation was used as the light source. In the obtained spectrum, the peak intensity of the maximum peak detected in the 2θ = 1.5 to 5° region was designated "Peak Intensity A [1.5 to 5°]," and the peak intensity of the maximum peak detected in the 2θ = 15 to 25° region was designated "Peak Intensity B [15 to 25°]." If no clear reflection was observed, the peak intensity was designated as 0.

[0376] <Water contact angle in air [θwater * air]> A polymer solution (or dispersion) with a solids concentration of 1.0% was spin-coated onto a silicon wafer at 2500 rpm for 25 seconds to obtain a spin-coated film. This was then heated at 120°C for 10 minutes to produce a polymer-treated silicon wafer. Chloroform was used as the solvent or dispersion medium. 2 μL of water was dropped onto the polymer-treated silicon wafer, and the contact angle 1 second after the drop was applied was taken as the "water contact angle in air [θwater * air]" of the polymer.

[0377] <Contact angle of air bubbles in water [θAir*Water]> A polymer solution (or dispersion) with a solids concentration of 1.0% was spin-coated onto a silicon wafer at 2500 rpm for 25 seconds to obtain a spin-coated film. This was then heated at 120°C for 10 minutes to produce a polymer-treated silicon wafer. Chloroform was used as the solvent or dispersion medium. The polymer-treated silicon wafer was fixed to a jig with a convex portion so that the surface opposite the polymer-treated surface was in contact with the jig. The polymer-treated silicon wafer was immersed in a glass container filled with pure water with the polymer-treated surface facing downwards and left for 5 minutes. After that, a 2 μl air bubble was created with a syringe and the bubble was attached to the polymer-treated silicon wafer surface, and the contact angle of the air bubble in water was measured. The contact angle of the air bubble obtained in this way was taken as the "contact angle of the air bubble in water [θ Air * Water]."

[0378] <Contact angle of water in water [θ water * water]> The "contact angle of water in water [θwater * underwater]" was calculated by subtracting the "contact angle of air bubbles in water [θAir * underwater]" from 180°, as shown in the following formula. [θWater*Underwater]=180°―[θAir*Underwater]

[0379] <Environmental responsiveness> "Environmental responsiveness" was calculated by subtracting "water contact angle in water [θwater * underwater]" from "water contact angle in air [θwater * under air]" according to the following formula. [Environmental responsiveness] = [θ water * in air] - [θ water * in water]

[0380] [Example 1] 3.86 g (80 mol%) of hydroxyethyl acrylate (HEA), 2 g (20 mol%) of octadecyl acrylate (ODA), 41.5 mL of 1,4-dioxane, and 68 mg (1 mol%) of azoisobutyronitrile were placed in a reaction vessel and heated to 60°C for 24 hours. The reaction solution was concentrated and purified to obtain a HEA-ODA copolymer. The resulting copolymer was subjected to X-ray diffraction analysis, and its contact angle with water in air and the contact angle with an air bubble in water were measured. The results are shown in Table 1.

[0381] [Examples 2 to 6] Polymerization was carried out in the same manner as in Example 1 at the blending ratios shown in Table 1 to obtain various copolymers. The resulting copolymers were subjected to X-ray diffraction measurement, and the contact angles with water in air and the contact angles of air bubbles in water were measured. The results are shown in Table 1.

[0382] [Comparative Examples 1 to 4] Polymerization was carried out in the same manner as in Example 1 using the blending ratios shown in Table 2 to obtain various copolymers. The resulting copolymers were subjected to X-ray diffraction measurement, and the contact angles with water in air and the contact angles of air bubbles in water were measured. The results are shown in Table 2.

[0383] [Table 1]

[0384] [Table 2] [Explanation of symbols]

[0385] 1 Base material 2 copolymer 21 Hydrophobic component-rich layer 22 Layer rich in hydrophilic ingredients 3 water 4 underwater 5. Bubbles α Static contact angle of water β Static contact angle of bubbles

Claims

1. A copolymer comprising a repeating unit derived from a hydrophobic monomer (A) and a repeating unit derived from a hydrophilic monomer (B), the amount of the repeating units derived from the hydrophilic monomer (B) is 51 to 99% by weight based on the total amount of the repeating units derived from the hydrophobic monomer (A) and the repeating units derived from the hydrophilic monomer (B); In X-ray diffraction (XRD) measurement, a reflection peak is exhibited in the region where 2θ is 5° or less, The copolymer, wherein the intensity of the reflection peak at 2θ of 5° or less is 0.7 times or more the intensity of the peak at 2θ of 15 to 25°.

2. 2. The copolymer according to claim 1, wherein, in X-ray diffraction (XRD) measurement, the intensity of a peak at 2θ of 5° or less is greater than the intensity of a peak at 2θ of 15 to 25°.

3. When the static contact angle of water in air is CA(Air), and the contact angle of water obtained by measuring the static contact angle of an air bubble in water is CA(Water), 2. The copolymer according to claim 1, wherein the difference in contact angle, defined as CA(Air)-CA(Water), is 20° or more.

4. 2. The copolymer according to claim 1, wherein the hydrophobic monomer (A) is a monomer having a hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent.

5. The hydrophobic monomer (A) is Formula A: CH 2 =C(-X Ｖ )-Y Ｖ -(R ａ ) ｋ [In the formula, X Ｖ is a hydrogen atom, a monovalent organic group, or a halogen atom, Y Ｖ Is Y Ｖ１ and Y Ｖ２ is a 1+k valent group consisting of one or more groups selected from the group consisting of Y Ｖ１ represents a direct bond, —O—, —C(═O)—, —C(═NR′)—, —S—, —S(═O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ , -N(-) ２ (wherein R' is independently in each occurrence a hydrogen atom or an organic group having 1 to 30 carbon atoms), Y Ｖ２ is a group consisting of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles, R ａ are each independently a hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, k is 1 to 3. The copolymer according to claim 1, comprising at least one monomer represented by the formula:

6. Y Ｖ teeth, -Y Ｖ１１ -Y Ｖ２１ — [In the formula, Y Ｖ１１ 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'-, -SO ２ -, -SO ２ NR'-, -C(OR')R'-, or -C(OR')(-) ２ and Y Ｖ２１ is a direct bond, a divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a divalent to tetravalent hydrocarbon aromatic ring. The copolymer according to claim 5 ,

7. Y Ｖ teeth, -Y Ｖ３ -Y Ｖ４ — [In the formula, Y Ｖ３ is —C(═O)—, —O—, or —O—C(═O)—, Y Ｖ４ represents a direct bond, a divalent to tetravalent hydrocarbon group having 1 to 4 carbon atoms, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ - or -NR'- (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms). The copolymer according to claim 5 ,

8. The hydrophilic monomer (B) is Formula B: CH ２ =C(-X ｂ )-Y ｂ -Z ｂ -(R ｂ ) ｋ [In the formula, X b is a hydrogen atom, a monovalent organic group, or a halogen atom, Y b represents a direct bond, —O—, —C(═O)—, —C(═NR′)—, —S—, —S(═O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ , -N(-) ２ (wherein R' is independently in each occurrence a hydrogen atom or an organic group having 1 to 30 carbon atoms), Z ｂ represents a direct bond, a divalent to tetravalent hydrocarbon group having 1 to 4 carbon atoms, or a trivalent or tetravalent hydrocarbon group having 1 to 6 carbon atoms, or -(Z ｂ１ O) ｎ -Z ｂ２ - and Z ｂ１ are each independently an alkylene group having 2 to 6 carbon atoms, Z ｂ２ is an alkylene group having 1 to 4 carbon atoms, n is an integer from 0 to 90, R ｂ are each independently a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, or a phosphate group, k is 1 to 3. The copolymer according to claim 1, wherein the monomer is represented by the formula:

9. Y b is a direct bond, -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'-, -C(OR')R'-, or -C(OR')(-) ２ 9. The copolymer according to claim 8, wherein R' is, independently in each occurrence, a hydrogen atom or a hydrocarbon having 1 to 4 carbon atoms.

10. Y b The copolymer according to claim 8, wherein is a direct bond, —C(═O)—O—, —C(═O)—NH—, —O—, or —O—C(═O)—.

11. The hydrophilic monomer (B) is formula: CH ２ =C(-X ｂ )-C(=O)-Y ｂ -(Z ｂ１ O) ｎ -Z ｂ２ -OH [In the formula, X ｂ is a hydrogen atom or a methyl group, Y ｂ is —O— or —NH—, Z ｂ１ are each independently an alkylene group having 1 to 6 carbon atoms, Z ｂ２ is an alkylene group having 1 to 4 carbon atoms, n is an integer from 0 to 90. The copolymer according to claim 1, wherein the oxyalkylene group-containing monomer is represented by the formula:

12. The copolymer according to claim 1, which has a static contact angle of water in air [CA(Air)] of 80° or more.

13. The copolymer according to claim 1, wherein the number average molecular weight Mn of the copolymer is 5,000 or more.

14. 2. The copolymer according to claim 1, wherein the total amount of the hydrophobic monomer (A) and the hydrophilic monomer (B) relative to the copolymer is 50% by weight to 100% by weight.

15. The hydrophobic monomer (A) is formula: CH 2 =C(-X Ｖ )-C(=O)-Y Ｖ (R ａ ) ｋ [In the formula, X Ｖ is a hydrogen atom, a monovalent organic group, or a halogen atom, Y Ｖ represents a divalent to tetravalent hydrocarbon group having 1 to 4 carbon atoms, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ - or -NR'- (R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), R ａ are each independently a hydrocarbon group having 6 to 40 carbon atoms, and k is 1 to 3. The hydrophilic monomer (B) is formula: CH ２ =C(-X ｂ )-C(=O)-Y ｂ -(Z ｂ１ O) ｎ -Z ｂ２ -OH [In the formula, X ｂ is a hydrogen atom or a methyl group, Y ｂ is —O— or —NH—, Z ｂ１ is an alkylene group having 2 to 6 carbon atoms, Z ｂ２ is an alkylene group having 1 to 4 carbon atoms, n is an integer from 0 to 90. is an oxyalkylene group-containing monomer represented by 2. The copolymer according to claim 1, wherein the total amount of the hydrophobic monomer (A) and the hydrophilic monomer (B) relative to the copolymer is 50% by weight to 100% by weight.

16. A repellent comprising the copolymer according to any one of claims 1 to 15 and a liquid medium.

17. The repellent according to claim 16, which is for textile products, paper products, glass, or resin.

18. 17. A product treated with the repellent of claim 16.

19. The product according to claim 18, which is a textile product, a paper product, a glass product, or a resin product.

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