Oil-resistant agent

Abstract

To provide an oil-resistant agent capable of imparting sufficient oil resistance while achieving environmental harmonization.SOLUTION: Disclosed is an oil-resistant agent involving a modified natural product comprising a bio-base compound bearing at least one carboxyl group and having hydroxy group of the carboxyl group substituted with R group, or, a modified natural product having carboxyl group substituted with Ra group; wherein R group is -X-R1 or -X-D-X'-R1, and Ra group is represented by the formula [in the formula, X is a direct bond, -O-, -NR11-, or -S-, R1 is a hydrocarbon group with a carbon number of 1-40, or polysiloxane, D is an alkylene group with a carbon number of 1-10, X' is -C(=O)-O-, -O-C(=O)-, -C(=O)-NR12-, or -NR12-C(=O)- (here, R11 and R12 are hydrogen, or an alkyl group with a carbon number of 1-40).]SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to an oil repellent using a modified natural product obtained by modifying a bio-based compound. [Background technology]

[0002] Paper containers are gaining attention as an alternative to disposable plastic containers. Paper food packaging materials and containers are required to prevent moisture and oil from seeping out of food, and oil-resistant agents are applied to the paper either internally or externally. Furthermore, from an environmental perspective, there is a growing need for bio-based materials.

[0003] Patent Document 1 (Japanese Patent Publication No. 9-286768) discloses a hydroxycarboxylic acid amide derivative having a polybasic hydroxycarboxylic acid as the acid component group.

[0004] Patent Document 2 (Japanese Unexamined Patent Publication No. 7-120876) discloses a support for photographic paper containing a reaction product of an aliphatic oxy acid and a monohydric alcohol of an alkyl or alkenyl group having 8 to 24 carbon atoms and / or an amine substituted with an alkyl or alkenyl group having 4 to 24 carbon atoms and an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 3 to 24 carbon atoms or hydrogen, in a base paper. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 9-286768 [Patent Document 2] Japanese Patent Application Publication No. 7-120876 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] The purpose of this disclosure is to provide an oil-resistant agent that can impart sufficient oil resistance using modified natural products while being in harmony with the environment. [Means for solving the problem]

[0007] This disclosure relates to modified natural products in which bio-based compounds are modified to have organic modification groups. Examples of organic modification groups are C1-C40 hydrocarbon groups that may have substituents, or polysiloxanes. Modified natural products can be used as oil-resistant agents.

[0008] Preferred embodiments of this disclosure are as follows: Appearance 1: An oil-resistant agent comprising a modified natural product in which the hydroxyl group of a bio-based compound having at least one carboxyl group is substituted with an R group, or a modified natural product in which the carboxyl group is substituted with an Ra group. R base:-XR 1 Or -XD-X'-R 1 Ra base: JPEG2023101503000001.jpg1733[In the formula, X is a direct join, -O-, -NR 11 -or -S- R 1 This is a hydrocarbon group having 1 to 40 carbon atoms, which may have substituents, or a polysiloxane. D is an alkylene group with 1 to 10 carbon atoms. X' is -C(=O)-O-, -OC(=O)-, -C(=O)-NR 12 -, or -NR 12 -C(=O)- (However, R 11 and R 12 (This is a hydrogen atom or an alkyl group having 1 to 40 carbon atoms, which may have substituents.) Appearance 2: The oil-resistant agent according to embodiment 1, wherein the carboxyl group of the modified natural product has a salt structure. Appearance 3: An oil-resistant agent according to any one of embodiments 1 to 2, wherein the bio-based compound has a hydroxyl group. Appearance 4: The oil-resistant agent according to any one of Aspects 1 to 3, wherein the hydrogen of the hydroxyl group of the bio-based compound is substituted with an Rb group. Rb group: -Y-R 21 [In the formula, Y is a direct bond, -C(=O)-, -C(=O)-NR 22 - or C=S- (R 22 is hydrogen or a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent), and R 21 is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a polysiloxane. ] Aspect 5: The oil-resistant agent according to any one of Aspects 1 to 4, wherein the carboxyl group or the hydroxyl group is cross-linked with a polyfunctional cross-linking agent. Aspect 6: The oil-resistant agent according to any one of Aspects 1 to 5, wherein the bio-based compound is a compound as it is a natural product or a compound derived from a natural product. Aspect 7: The oil-resistant agent according to any one of Aspects 1 to 6, wherein the bio-based compound is at least one selected from the group consisting of citric acid, malic acid, gluconic acid, alginic acid, butyric acid, lactic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, chlorogenic acid, aldonic acid, uronic acid, aldaluronic acid, and derivatives thereof. Aspect 8: The bio-based compound is of the formula: JPEG2023101503000002.jpg2347 [In the formula, each E 1 is the same or different and is hydrogen or -COOH, each E 2 is the same or different and is hydrogen or -OH, E 3 is -COOE 4 (however, E 4 is hydrogen or an alkyl group having 1 to 22 carbon atoms), -CH3, -NH2 or -OH, m is a number from 0 to 10. ] The oil-resistant agent according to any one of Aspects 1 to 7, which is a compound represented by Appearance 9: An oil-resistant agent according to any one of embodiments 1 to 8, wherein the bio-based compound has two or more carboxyl groups. Appearance 10: R 1 The oil-resistant agent according to any one of embodiments 1 to 9, wherein the aliphatic hydrocarbon group having 1 to 40 carbon atoms may have substituents. Appearance 11: The carboxyl groups of the modified natural product are crosslinked with a polyfunctional crosslinking agent, and the hydroxyl groups of the carboxyl groups are bonded to the Z group (where Z is -O-, -NR). 31 -(R 31 A hydrogen atom is a C1-C8 alkyl group which may have substituents. The oil-resistant agent according to any one of embodiments 1 to 10, having a structure bonded by )). Appearance 12: The hydroxyl groups of modified natural products are crosslinked with a polyfunctional crosslinking agent, and the hydrogen atoms of the hydroxyl groups are bonded to the group Z'(Z' is -C(=O)-, -C(=O)-NR) 41 -(R 41 An oil-resistant agent according to any one of embodiments 1 to 11, having a structure in which is bonded by hydrogen or an alkyl group having 1 to 4 carbon atoms which may have substituents. Appearance 13: An oil-resistant agent according to any one of embodiments 1 to 12, wherein the bio-based content is 30% or more. Appearance 14: An oil-resistant agent according to any one of embodiments 1 to 13, wherein the biodegradability is 5% or more. Appearance 15: An oil-resistant agent according to any one of embodiments 1 to 14, which is a water-dispersible composition. Appearance 16: An oil-resistant agent according to any one of embodiments 1 to 15, comprising an emulsifier or dispersant. Appearance 17: An oil-resistant agent according to any one of embodiments 1 to 16, comprising an emulsifier or dispersant, wherein the emulsifier or dispersant is a cationic, nonionic, and / or anionic emulsifier or dispersant. Appearance 18: An oil-resistant agent according to any one of claims 1 to 17, comprising at least one selected from the group consisting of yield agents, sizing agents, pH adjusters, fillers, and paper strength enhancers. Appearance 19: An oil-resistant agent according to any one of claims 1 to 18, comprising a yield agent, wherein the yield agent comprises at least one selected from the group consisting of aluminum sulfate, acrylic polymer, starch, modified starch, cellulose, modified cellulose, and silica. Appearance 20: An oil-resistant agent according to any one of claims 1 to 19, comprising a sizing agent, wherein the sizing agent comprises at least one selected from the group consisting of rosin-based sizing agents, alkyl ketene dimers (AKD), alkenyl succinic anhydride (ASA), polyvinyl alcohol (PVA), modified starch, styrene-acrylic copolymers, and styrene-methacrylic copolymers. Appearance 21: An oil-resistant agent according to any one of claims 1 to 20, comprising a paper strength enhancer, wherein the paper strength enhancer comprises at least one selected from the group consisting of urea-formaldehyde resin, melamine-formaldehyde resin, polyamide-polyamine epichlorohydrin (PAE), polyvinylamine (PVAm), dry-modified starch, polyacrylamide, and polyvinyl alcohol. Appearance 22: An oil-resistant agent according to any one of embodiments 1 to 21, wherein the melting point is 25°C or higher. Appearance 23: An oil-resistant agent according to any one of embodiments 1 to 22, wherein the HD contact angle is 10° or more. Appearance 24: An oil-resistant agent according to any of embodiments 1 to 23, which is for use with paper. Appearance 25: A textile product containing an oil-resistant agent as described in any of embodiments 1 to 24. Appearance 26: Oil-resistant paper containing an oil-resistant agent as described in any of embodiments 1 to 24. Appearance 27: A food packaging material or food container containing an oil-resistant agent as described in any of embodiments 1 to 24. Appearance 28: A processing method for externally or internally applying an oil-resistant agent described in any of embodiments 1 to 24 to paper. Appearance 29: A method for treating fibers, comprising molding or desolventing a fibrous substrate containing an oil-resistant agent as described in any of embodiments 1 to 24, at a pressure higher than 0.1 MPa. Appearance 30: A method for treating fibers, comprising heating, molding, or drying a fibrous substrate containing an oil-resistant agent as described in any of embodiments 1 to 24 at a temperature of 25°C or higher. Appearance 31: formula: JPEG2023101503000003.jpg1525 or JPEG2023101503000004.jpg927[In the formula, each R'' is either the same or different, -OH or -NH-R 1 (R 1 (This is a hydrocarbon group having 1 to 40 carbon atoms, which may have substituents.) R' represents a hydrogen atom or an acetyl group. The compound shown by [this symbol]. [Effects of the Invention]

[0009] The oil-resistant agent disclosed herein exhibits excellent oil resistance. Since the oil-resistant agent disclosed herein is bio-based, it has a low impact on the ecological environment. [Modes for carrying out the invention]

[0010] Oil-resistant agents impart oil resistance to the object to be treated (substrate) by applying a treatment. Oil resistance includes, but is not limited to, functions such as preventing oil stains on the treated object, or providing oil repellency or stain resistance. Here, "oil" refers to fats and oils and organic solvents. Examples of fats and oils include edible oils (vegetable oils, animal oils, vegetable fats, animal fats) and industrial oils. Examples of edible oils include salad oil, corn oil, sesame oil, rapeseed oil, and olive oil, while examples of industrial oils include castor oil. Organic solvents may be polar or nonpolar solvents. Examples of nonpolar solvents include hexane and hexadecane, but are not limited to these. Furthermore, the treated object may have water resistance and water repellency. In addition to the modified natural product, the oil repellent may contain a liquid medium (water, organic solvent, or a mixture thereof). The oil repellent may further contain at least one selected from surfactants, dispersants, blocked isocyanate compounds, and additives.

[0011] Biobased compounds are preferably compounds that contain carbon of bio-derived origin. The degree of bio-basedness is measured in accordance with ASTM D6866. Compounds containing carbon of bio-derived origin do not have a bio-basedness of 0%. The degree of bio-basedness is preferably 10% or more, more preferably 30% or more, even more preferably 50% or more, and most preferably 80% or more or 90% or more, for example 100%. A high degree of bio-basedness means that the amount of fossil resource-based materials, such as petroleum, used is small, and from this viewpoint, a higher degree of bio-basedness of the biobased compound is preferable.

[0012] Bio-based compounds may be compounds that are natural products in their original form or compounds derived from natural products. In other words, bio-based compounds also include derivatives of natural products.

[0013] The modified natural product is preferably a compound containing carbon of biobase origin. The degree of biobase is measured in accordance with ASTM D6866. The degree of biobase is not 0%. The degree of biobase is preferably 10% or more, more preferably 30% or more, even more preferably 50% or more, and most preferably 80% or more or 90% or more, for example 100%. A high degree of biobase means that the amount of fossil resource-based materials, such as petroleum, used is small, and from this viewpoint, a higher degree of biobase in the modified natural product is preferable.

[0014] This disclosure provides an oil-resistant agent comprising a modified natural product in which at least one of the hydroxyl groups of a bio-based compound having at least one carboxyl group is substituted with an R group, or a modified natural product in which the carboxyl group is substituted with an Ra group, preferably a modified natural product in which at least one of the hydroxyl groups of the carboxyl group is substituted with an R group. The R group is represented by formula: -XR 1 [In the formula, X is a direct bond, -O-, -NR] 11 - (R 11 is hydrogen, or an alkyl group having 1 to 40 carbon atoms (e.g., 1 to 10 or 1 to 4 carbon atoms), which may have substituents. ) or -S- R 1 is a hydrocarbon group having 1 to 40 carbon atoms, which may have substituents, or a polysiloxane. Formula: -XD-X'-R 1 [In the formula, X' is -C(=O)-O-, -OC(=O)-, -C(=O)-NR 12 -, or -NR 12 -C(=O)-(R 12 is hydrogen, or an alkyl group having 1 to 40 carbon atoms (e.g., 1 to 10 or 1 to 4 carbon atoms), which may have substituents. D is an alkylene group with 1 to 10 carbon atoms. X and R 1 This is synonymous with the above. It is the group shown by . The Ra group is represented by the formula: JPEG2023101503000005.jpg1733[wherein, R 1 This is a hydrocarbon group having 1 to 40 carbon atoms, which may have substituents, or a polysiloxane. It is the group shown by .

[0015] Examples of substituents include hydroxyl groups, carboxyl groups, alkoxyester groups, alkoxy groups, (Rc)3Si groups, (RcO)3Si groups, amino groups, and amine salts (wherein Rc is the same or different, a hydrogen atom or an alkyl group with 1 to 4 carbon atoms).

[0016] The carboxyl group of the modified natural product may have a salt structure. Corresponding cations include ammonium ions, quaternary ammonium ions, alkali metals, and alkaline earth metals.

[0017] Bio-based compounds may have functional groups other than carboxyl groups, and examples of other functional groups include hydroxyl groups.

[0018] If the bio-based compound has a hydroxyl group, the hydrogen atoms of the hydroxyl group may be substituted with Rb groups. Rb base: -YR 21 [In the formula, Y is a direct bond, -C(=O)-, -C(=O)-NR] 22 -or C=S-(R 22 (is hydrogen, or an alkyl group having 1 to 40 carbon atoms which may have substituents, preferably hydrogen or a methyl group, and more preferably hydrogen), R 21 This is a hydrocarbon group having 1 to 40 carbon atoms, which may have substituents, or a polysiloxane.

[0019] The hydroxyl groups in modified natural products may have a salt structure. Corresponding cations include ammonium ions, quaternary ammonium ions, alkali metals, and alkaline earth metals.

[0020] Modified natural products may have carboxyl groups or hydroxyl groups crosslinked with a polyfunctional crosslinking agent.

[0021] The carboxyl groups of modified natural products may be crosslinked with polyfunctional crosslinking agents, and may have a structure in which the hydroxyl groups of the carboxyl groups are bonded by a bonding group Z. Z is -O-, -NR 31 -(R 31It is preferably a bonding group represented by ) which is hydrogen or an alkyl group having 1 to 9 or 1 to 4 carbon atoms, which may have substituents, preferably hydrogen or a methyl group, and more preferably hydrogen.

[0022] The hydroxyl groups of modified natural products may be crosslinked with a polyfunctional crosslinking agent, and the hydrogen atoms of the hydroxyl groups may have a structure in which they are bonded by a group having a bonding group Z'. Z' is -C(=O)-, -C(=O)-NR 41 -(R 41 The bonding group is preferably represented by (a hydrogen atom or an alkyl group having 1 to 9 or 1 to 4 carbon atoms, which may have substituents, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom).

[0023] Examples of polyfunctional crosslinking agents include diamines, putrescine, cadaverine, hexanemethylenediamine, phenylenediamine, ethylene glycol, propylene glycol, diethylene glycol, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, citric acid, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and hexamethylene diisocyanate (HDI).

[0024] -XR 1 The base example is -R 1 , -OR 1 , -NR 11 -R 1 , -SR 1 (In the formula, R 1 and R 11 This is equivalent to the above. ) Preferably, -OR 1 , -NR 11 -R 1 And more preferably, -NR 11 -R 1 And more preferably, since it gives a higher contact angle -NH-R 1 That is the case.

[0025] -XD-X'-R 1 An example of the base is -ODOC(=O)-R1 、 -O-D-C(=O)-NR 11 R 1 、 -O-D-NR 12 -C(=O)-R 1 、 -NR 13 -D-O-C(=O)-R 1 、 -NR 13 -D-C(=O)-NR 11 R 1 、 -NR 13 -D-NR 12 -C(=O)-R 1 (In the formula, R 1 and R 11 and R 12 have the same meanings as described above, and R 13 is hydrogen or an alkyl group having 1 to 40 carbon atoms which may have a substituent. D is an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 4 carbon atoms.). Preferably, -NR 13 -D-O-C(=O)-R 1 、 -NR 13 -D-C(=O)-O-R 1 、 -NR 13 -D-C(=O)-NR 11 R 1 、 -NR 13 -D-NR 12 -C(=O)-R 1 ; more preferably, -NH-D-O-C(=O)-R 1 、 -NH-D-C(=O)-O-R 1 、 -NR 13 -D-C(=O)-NHR 1 、 -NR 13 -D-NH-C(=O)-R 1 .

[0026] When the biobased compound or modified natural product has two or more carboxyl groups, the hydroxyl groups of the two carboxyl groups may be substituted with an Rd group and bonded. The Rd group has the formula: -NR 1 - [In the formula, R 1 has the same meaning as described above.] It is preferably a group represented by.

[0027] R 1 has 1 to 40 carbon atoms, and may be 2 or more, 4 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, or 20 or more, preferably 8 or more or 12 or more. The number of carbon atoms of the hydrocarbon group may be 40 or less, 35 or less, 30 or less, 25 or less, 22 or less, 20 or less, or 18 or less. Preferably it is 30 or less. For example, R 1 may have 4 to 35, 6 to 30, 8 to 25 or 10 to 22 carbon atoms.

[0028] R 1 is a saturated or unsaturated hydrocarbon group which may have a substituent, preferably an aliphatic hydrocarbon group which may have a substituent, and more preferably an aliphatic hydrocarbon group. The hydrocarbon group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. For example, R 1 may be a linear or branched alkyl group.

[0029] R 1 may be a substituent having carbon of biobased origin. Preferably, the biobased content according to ASTM D6866 is not 0% or is 10% or more, more preferably 30% or more, still more preferably 50% or more, and most preferably 80% or more. The upper limit of the biobased content may be 100%, 95%, 90% or 85%.

[0030] R 1 Specific examples of R include alkyl groups such as n-propyl, iso-propyl group, n-butyl group, t-butyl group, neopentyl group, octyl group, isooctyl group, nonyl group, decyl group, undecyl group, lauryl group, tridecyl group, tetradecyl group, pentadecyl group, palmityl group, heptadecyl group, stearyl group, behenyl group, 2-ethylhexyl group, isostearyl group; alkenyl groups such as oleyl group, palmitoyl group, eicosenyl group; cycloalkyl groups such as cyclohexyl.

[0031] R1 This may be a hydrocarbon group having an A group, such as an amino group or an ammonium group. A is the formula: -NA 1 A 2 Alternatively, -N + A 1 A 2 A 3 B - (A 1 , A 2 and A 3 This is hydrogen or an alkyl group having 1 to 10 carbon atoms, preferably hydrogen or an alkyl group having 1 to 3 carbon atoms, most preferably hydrogen or a methyl group. - It is preferably an ion such as a halide ion or acetate ion, or a group represented by ).

[0032] R 11 and R 12 is hydrogen, or an alkyl group having 1 to 40 carbon atoms which may have substituents, preferably hydrogen or an aliphatic hydrocarbon having 1 to 40 carbon atoms, more preferably hydrogen or an aliphatic hydrocarbon having 1 to 25 carbon atoms, even more preferably hydrogen or an aliphatic hydrocarbon having 1 to 10 carbon atoms, and most preferably hydrogen.

[0033] R 13 is hydrogen, or an alkyl group having 1 to 40 carbon atoms which may have substituents, preferably hydrogen or an aliphatic hydrocarbon having 1 to 40 carbon atoms, more preferably hydrogen or an aliphatic hydrocarbon having 1 to 25 carbon atoms, even more preferably hydrogen or an aliphatic hydrocarbon having 1 to 10 carbon atoms, and most preferably hydrogen.

[0034] Modified natural products are given by the following formula JPEG2023101503000006.jpg2349[In the formula, each E 1 It is the same or different hydrogen or -COOH, Each E 2 They are the same or different hydrogen or -OH, E 3 -COOE 4(However, E 4 (where is hydrogen or an alkyl group having 1 to 22 carbon atoms), -CH3, -NH2, or -OH, m is a number between 0 and 10. It is preferable that the compound represented by has at least one hydroxyl group of a carboxyl group substituted with an R group, or that the carboxyl group is substituted with an Ra group. E 4 When the alkyl group is an alkyl group, the number of carbon atoms in the alkyl group may be 1 to 4 or 1 to 10. m can be 1-8, 2-6, or 3-5.

[0035] Examples of modified natural products are as follows: E5-CH2-COE 11 [In the formula, E5 is NHE6, and E6 is Boc, H, and COE 12 There is one of the following, E 11 and E 12 Each of these is either R or OH, and at least one of them is R. E7-CHE8-CHE9-COE 11 [In the formula, E7 is NHE6, COE 12 OCOR 1 It is one of the following, preferably COE 12 Therefore, E8 and E9 are H, OH, or OCOR, respectively. 1 E8 is preferably H, E9 is preferably H or OAc, and E 6、 E 11 , and E 12 This is as stated above. E 12 -CO-CH2-C(OH)E 10 -CH2-COE 11 [In the formula, E 10 COE 13 or H and E 11 , E 12 , E 13 Each of these is either R or OH, and at least one of them is R. In the above example, the R group is -XR1 Or -XD-X'-R 1 X, R 1 D and X' are as described above. In the above example, Ac is an acetyl group and Boc is a t-butoxycarbonyl group. Although the above examples show cases where an R group is present, one or more -CO-R groups in each modified natural product in the above examples may be replaced with Ra groups.

[0036] In some embodiments, specific examples of modified natural products are as follows: JPEG2023101503000007.jpg2255 JPEG2023101503000008.jpg2357 JPEG2023101503000009.jpg1555 JPEG2023101503000010.jpg1530 JPEG2023101503000011.jpg2033 JPEG2023101503000012.jpg1347[In the formula, Ac is an acetyl group, Boc is a t-butoxycarbonyl group.

[0037] R 1 may be a polysiloxane group. A polysiloxane group is, for example, a group of the formula: -R 51 -[Si(R 52 )(R 53 )] a -[Si(R 54 )(R 55 )] b -Si(R 56 )(R 57 )(R 58 ) [In the formula, R 51 O (oxygen atom) or a hydrocarbon group having 1 to 10 carbon atoms, R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58These are hydrogen, a hydroxyl group, an alkoxy group with 1 to 40 carbon atoms, and a hydrocarbon group with 1 to 40 carbon atoms, respectively, and may be the same or different, a represents an integer greater than or equal to 0, b represents an integer greater than or equal to 1, and (a+b) is between 3 and 200. These are the groups represented by ].

[0038] R 51 is O or a hydrocarbon group having 1 to 10 carbon atoms, preferably O or an alkylene group having 1 to 5 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms.

[0039] R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 These are hydrogen, a hydroxyl group, an alkoxy group having 1 to 40 carbon atoms, and a hydrocarbon group having 1 to 40 carbon atoms, and may be the same or different. Preferably, they are hydrogen, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a saturated hydrocarbon group having 1 to 40 carbon atoms, and an aryl group having 6 to 20 carbon atoms. More preferably, they are hydrogen, a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, and a saturated hydrocarbon group having 1 to 30 carbon atoms. Even more preferably, they are hydrogen, a hydroxyl group, a methyl group, a methoxy group, an ethylene group, a propyl group, and a saturated hydrocarbon group having 10 to 24 carbon atoms.

[0040] R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 In this, the alkyl group having 1 to 40 carbon atoms and the aryl group having 6 to 20 carbon atoms may be unsubstituted or substituted. R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58Specific examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, phenyl group, tolyl group, naphthyl group, and the like.

[0041] R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 In this context, the alkoxy group having 1 to 10 carbon atoms may be linear or branched. Examples include the methoxy group, ethoxy group, propoxy group, and butoxy group.

[0042] In terms of being easy to manufacture industrially and readily available, R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 It is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

[0043] The sum of a and b is 3 to 200 or 5 to 200. Preferably, the sum of a and b is 10 to 100, and more preferably 40 to 60, in terms of ease of industrial manufacture, availability, and handling. a may be 0 to 150, for example, 1 to 100. The lower limit of b may be 1, 2, or 3, and the upper limit of b may be 150, 10, or 5.

[0044] Bio-based compounds are compounds that have at least one carboxyl group (carboxyl group-containing natural compounds). Bio-based compounds may be low molecular weight (e.g., weight-average molecular weight less than 1000 or 500 or less) and / or high molecular weight. The weight-average molecular weight of high molecular weight compounds may be 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more. The weight-average molecular weight of high molecular weight compounds may be 7,500,000 or less, 5000,000 or less, 3000000 or less, 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, or 50000 or less. The weight-average molecular weight can be measured in pullulan equivalent by gel permeation chromatography (GPC). The bio-based compound may be a high molecular weight natural product, a low molecular weight natural product, or a derivative thereof.

[0045] Bio-based compounds (natural products or compounds derived from natural products) may include, for example, glycine, citric acid, malic acid, glutaric acid, gluconic acid, alginic acid, butyric acid, lactic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, chlorogenic acid, aldonic acid, uronic acid, aldalic acid, or derivatives thereof.

[0046] Bio-based compounds (natural products or compounds derived from natural products) are defined by the formula: JPEG2023101503000013.jpg2553[In the formula, each E 1 It is the same or different hydrogen or -COOH, Each E 2 They are the same or different hydrogen or -OH, E 3 -COOE 4 (However, E 4 (where is hydrogen or an alkyl group having 1 to 22 carbon atoms), -CH3, -NH2, or -OH, m is a number between 0 and 10. It is preferable that the compound is one shown in [the formula]. E 4 When the alkyl group is an alkyl group, the number of carbon atoms in the alkyl group may be 1 to 4 or 1 to 10. m can be 1-8, 2-6, or 3-5.

[0047] Modified natural products may be biodegradable according to ASTM D5338. Preferably, the biodegradability is 5% or more, more preferably 10% or more, preferably 20% or more, 30% or more, more preferably 50% or more, even more preferably 80% or more, and most preferably 90% or more. Since higher biodegradability results in less environmental impact, it can be said that higher biodegradability of modified natural products is preferable.

[0048] Modified natural products can be produced by reacting a modifying agent with the carboxyl group of a bio-based compound. Examples of synthetic methods for reacting a modifying agent with a carboxyl group include methods for forming ester bonds, amide bonds, and oxazole rings.

[0049] The modifier is preferably a compound having a hydrocarbon group, particularly a compound having an aliphatic hydrocarbon group. Examples of modifiers are as follows: Alcohol (R 1 -OH), Amine (R 1 -NR 2 H), Isocyanate (R 1 -N=C=O), Isothiocyanate (R 1 -N=C=S) [In the formula, R 1 This is equivalent to the above (a hydrocarbon group having 1 to 40 carbon atoms, which may have substituents, or a polysiloxane), R 2 This is a hydrogen atom, or an alkyl group having 1 to 40 carbon atoms (e.g., 1 to 10 or 1 to 4 carbon atoms), which may have substituents.

[0050] It is more preferable that the substitution rate of carboxyl groups, or hydroxyl groups of carboxyl groups, by the modifying agent is greater than 0 and is 1% or more, 3% or more, 5% or more, or 10% or more, for example, 15% or more, 20% or more, or 30% or more, 80% or more, 90% or more, or 95% or more. "Substitution rate" means the average percentage of carboxyl groups, or hydroxyl groups of carboxyl groups, present in the structure of the modified natural product that are substituted by the modifying agent.

[0051] The percentage of unmodified carboxyl groups (i.e., the remaining carboxyl group percentage) may be less than 100%, and may be 95% or less, 90% or less, 60% or less, 40% or less, or 20% or less. "Remaining percentage" refers to the proportion (%) of carboxyl groups present in the structure of the modified natural product that have not been substituted by the modifying agent.

[0052] <Method for forming ester bonds> Alcohol (R 1 -OH) is used to form an ester bond with the carboxyl group of the bio-based compound. Synthetic methods for converting carboxyl groups in natural products to ester groups include, for example, (a) Bio-based compounds, alcohols (R 1 -OH), a method for forming ester bonds using an acid catalyst, (b) Bio-based compounds, alcohols (R 1 -OH), a method for forming ester bonds using a condensing agent, (c) After converting the bio-based compound to an acyl compound, alcohol (R 1 A method for forming ester bonds using -OH) (Add a solvent as needed for each.) Alcohol (R 1 -OH) 1 This is synonymous with the above.

[0053] Specific examples of aliphatic alcohols include CH3OH, CH3CH2OH, CH3(CH2)2OH, CH3(CH2)3OH, CH3(CH2)4OH, CH3(CH2)5OH, CH3(CH2)6OH, CH3(CH2)7OH, CH3(CH2)8OH, CH3(CH2)9OH, and CH3(CH2). 10 OH, CH3(CH2) 11 OH, CH3(CH2) 12 OH, CH3(CH2) 13 OH, CH3(CH2) 14 OH, CH3(CH2) 15 OH, CH3(CH2) 16 OH, CH3(CH2) 17 OH, CH3(CH2) 18 OH, CH3(CH2) 19 OH, CH3(CH2) 20 OH, CH3(CH2) 21 OH, CH3(CH2) 22 OH, CH3(CH2) 23 OH,(CH3)2CHOH,(CH3)3COH,(CH3)2CHCH2OH,(CH3)3CCH2OH,(CH3)2CH(CH2)2OH, (CH3)3C(CH2) 14 OH,(CH3)2CH(CH2) 15 OH, (CH3)3C(CH2) 18 OH,(CH3)2CH(CH2) 18 OH is one example.

[0054] <Method for forming amide bonds> The carboxyl group of the bio-based compound is reacted to form an amide bond. The amide bond is formed by the reaction of the bio-based compound with an amine (R 1 -NR 2 H), isocyanate (R 1 -N=C=O), or isothiocyanate (R 1 It is formed by reacting it with (-N=C=S).

[0055] For example, synthetic methods for converting carboxyl groups to amide groups in bio-based compounds include: (a) Bio-based compounds and amines (R 1 -NR 2 H), isocyanate (R 1 -N=C=O), or isothiocyanate (R 1 A method of forming an amide bond by mixing any of the following: (N=C=S) (b) Bio-based compounds and amines (R 1 -NR 2 H), isocyanate (R 1 -N=C=O), or isothiocyanate (R 1 A method of forming an amide bond using a condensing agent, either N=C=S. (c) Bio-based compounds and amines (R 1 -NR 2 H), isocyanate (R 1 -N=C=O), or isothiocyanate (R 1 A method for forming an amide bond using any of the following metal catalysts (e.g., tin catalyst): (d) After converting the bio-based compound to an acyl compound, the amine (R 1 -NR 2 H), isocyanate (R 1 -N=C=O), or isothiocyanate (R 1 A method of forming an amide bond by adding one of the following (-N=C=S): Examples include: Amine (R 1 -NR 2 H), isocyanate isocyanate (R 1 -N=C=O), and isothiocyanates (R 1 In -N=C=S), R 1 This is synonymous with the above.

[0056] Specific examples of amines include CH3NH2, CH3CH2NH2, CH3(CH2)2NH2, CH3(CH2)3NH2, CH3(CH2)4NH2, CH3(CH2)5NH2, CH3(CH2)6NH2, CH3(CH2)7NH2, CH3(CH2)8NH2, CH3(CH2)9NH2, and CH3(CH2). 10 NH2, CH3(CH2)11 NH2, CH3(CH2) 12 NH2, CH3(CH2) 13 NH2, CH3(CH2) 14 NH2, CH3(CH2) 15 NH2, CH3(CH2) 16 NH2, CH3(CH2) 17 NH2, CH3(CH2) 18 NH2, CH3(CH2) 19 NH2, CH3(CH2) 20 NH2, CH3(CH2) 21 NH2, CH3(CH2) 22 NH2, CH3(CH2) 23 NH2, (CH3)2CHNH2, (CH3)3CNH2, (CH3)2CHCH2NH2, (CH3)3CCH2NH2, (CH3)2CH(CH2)2NH2, (CH3)3C(CH2) 14 NH2, (CH3)2CH(CH2) 15 NH2, (CH3)3C(CH2) 18 NH2, (CH3)2CH(CH2) 18 Examples include NH2.

[0057] Specific examples of the isocyanate include CH3NCO, CH3CH2NCO, CH3(CH2)2NCO, CH3(CH2)3NCO, CH3(CH2)4NCO, CH3(CH2)5NCO, CH3(CH2)6NCO, CH3(CH2)7NCO, CH3(CH2)8NCO, CH3(CH2)9NCO, CH3(CH2) 10 NCO, CH3(CH2) 11 NCO, CH3(CH2) 12 NCO, CH3(CH2) 13 NCO, CH3(CH2) 14 NCO, CH3(CH2) 15 NCO, CH3(CH2) 16 NCO, CH3(CH2) 17 NCO, CH3(CH2) 18 NCO, CH3(CH2) 19 NCO, CH3(CH2)20NCO, CH3(CH2)21 NCO, CH3(CH2) 22 NCO, CH3(CH2) 23 NCO, (CH3)2CHNCO, (CH3)3CNCO,(CH3)2CHCH2NCO, (CH3)3CCH2NCO, (CH3)2CH(CH2)2NCO, (CH3)3C(CH2) 14 NCO, (CH3)2CH(CH2) 15 NCO, (CH3)3C(CH2) 18 NCO, (CH3)2CH(CH2) 18 Examples include NCO.

[0058] Specific examples of isothiocyanate include CH3NCS, CH3CH2NCS, CH3(CH2)2NCS, CH3(CH2)3NCS, CH3(CH2)4NCS, CH3(CH2)5NCS, CH3(CH2)6NCS, CH3(CH2)7NCS, CH3(CH2)8NCS, CH3(CH2)9NCS, CH3(CH2) 10 NCS, CH3(CH2) 11 NCS, CH3(CH2) 12 NCO, CH3(CH2) 13 NCO, CH3(CH2) 14 NCO, CH3(CH2) 15 NCO, CH3(CH2) 16 NCS, CH3(CH2) 17 NCS, CH3(CH2) 18 NCS, CH3(CH2) 19 NCS, CH3(CH2) 20 NCS, CH3(CH2) 21 NCS, CH3(CH2) 22 NCS, CH3(CH2) 23 NCS, (CH3)2CHNCS, (CH3)3CNCS, (CH3)2CHCH2NCS, (CH3)3CCH2NCS, (CH3)2CH(CH2)2NCS, (CH3)3C(CH2) 14 NCS,(CH3)2CH(CH2) 15 NCS, (CH3)3C(CH2) 18 NCS,(CH3)2CH(CH2)18 NCS is one example.

[0059] R 21 It is preferably an aliphatic hydrocarbon group having 1 to 40 carbon atoms, which may have substituents. The number of carbon atoms is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, preferably 35 or less, more preferably 30 or less, and even more preferably 25 or less.

[0060] In this disclosure, modified natural products modified with primary amines are preferred.

[0061] This disclosure provides novel compounds, namely malic acid compounds or glutaric acid compounds. Malate compounds or glutarate compounds are given by formula: JPEG2023101503000014.jpg1525 or JPEG2023101503000015.jpg927[In the formula, each R'' is either the same or different, -OH or -NH-R 1 (R 1 (This is a hydrocarbon group having 1 to 40 carbon atoms, which may have substituents.) R' represents a hydrogen atom or an acetyl group. It is a compound represented by [the formula shown]. Only one R'' is -NH-R 1 This is acceptable, but if two R'' are simultaneously -NH-R 1 It is preferable that this be the case.

[0062] R 1 It is preferably a hydrocarbon group having 12 to 22 carbon atoms, particularly an alkyl group. R' is preferably an acetyl group.

[0063] Specific examples of malic acid compounds or glutaric acid compounds are as follows: JPEG2023101503000016.jpg2033 JPEG2023101503000017.jpg1555

[0064] <Oil-resistant agent> Modified natural products can be used as "oil repellents" because they possess oil resistance. An oil repellent may be a composition containing a modified natural product, or it may consist solely of a modified natural product. An oil repellent may further possess water resistance, water repellency, and oil repellency. In addition to the modified natural product, an oil repellent may contain a liquid medium (water, organic solvent, or a mixture thereof). An oil repellent may further contain at least one selected from surfactants, dispersants, crosslinking agents such as blocked isocyanate compounds, and additives.

[0065] The amount of the modified natural product may be 0.01% or more by weight, 0.1% or more by weight, 1% or more by weight, 10% or more by weight, 20% or more by weight, or 30% or more by weight relative to the oil resistant agent. The amount of the modified natural product may be 100% or less by weight, 95% or less by weight, 90% or less by weight, or 80% or less by weight relative to the oil resistant agent.

[0066] The oil-resistant agent may contain a liquid medium. The liquid medium is water alone, an organic solvent alone, or a mixture of water and an organic solvent, preferably water alone.

[0067] The amount of liquid medium relative to the oil-resistant agent may be 60% by weight or more, 80% by weight or more, or 90% by weight or more, and the amount of liquid medium may be less than 100% by weight, 99% by weight or less, 95% by weight or less, 90% by weight or less, or 80% by weight or less.

[0068] <Surfactants or dispersants> Oil-resistant agents may or may not contain surfactants (emulsifiers) or dispersants. A small amount of surfactant or dispersant (for example, 0.01 to 100 parts by weight or 0.01 to 50 parts by weight, e.g., 0.1 to 30 parts by weight, per 100 parts by weight of the modified natural product) may be added during or after the reaction. Generally, the addition of a surfactant or dispersant improves the stability of the aqueous dispersion.

[0069] The surfactant preferably includes one or more surfactants selected from cationic surfactants, nonionic surfactants, anionic surfactants, and amphoteric surfactants, and more preferably a nonionic surfactant, a cationic surfactant, or a combination of a nonionic surfactant and a cationic surfactant.

[0070] Nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants may each be one or a combination of two or more types. The amount of surfactant or dispersant may be 0.01% or more, 0.1% or more, 1% or more, 5% or more, 10% or more, 30% or more, 50% or more, or 100% or less, 95% or less, 90% or less, or 70% or less, per 100 parts by weight of the modified natural product. Generally, the stability of the aqueous dispersion is improved when surfactants or dispersants are added.

[0071] Examples of nonionic surfactants (emulsifiers) or dispersants include glycerin fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycol, fatty acid polyethylene glycol, fatty acid polyoxyethylene sorbitan, fatty acid alkanolamides, and polyethyleneimine ethoxylates.

[0072] Cationic surfactants (emulsifiers) or dispersants include alkylamine salts and quaternary ammonium salts. Alkylamine salts include monoalkylamine salts, dialkylamine salts, and trialkylamine salts, while quaternary ammonium salts include trimethylammonium chloride, dialkyldimethylammonium chloride, and alkylbenzalkonium chloride.

[0073] Anionic surfactants (emulsifiers) or dispersants include carboxylates, sulfonates, sulfate esters, and phosphate esters. Examples of carboxylates include aliphatic monocarboxylic acids and alkyl ether carboxylates; examples of sulfonates include dialkyl sulfosuccinates, alkanesulfonates, alkylbenzenesulfonates, and alkylnaphthalenesulfonates; examples of sulfate esters include alkyl sulfates and oil sulfates; and examples of phosphate esters include alkyl phosphates and polyoxyethylene alkyl ether phosphates.

[0074] Examples of amphoteric surfactants (emulsifiers) or dispersants include alkyl betaines, fatty acid amidopropyl betaines, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium salts, alkyldiethylenetriaminoacetic acid, dialkyldiethylenetriaminoacetic acid, and alkylamine oxides.

[0075] When adding a surfactant (emulsifier) ​​or dispersant during or after the reaction of the modified natural product, heating may be used. After adding the modified natural product and dispersant, the mixture may be heated and melted before dispersion, or a solution (preferably water) may be added and dispersed or dissolved while further heating. The heating temperature may be 40°C or higher, 60°C or higher, or 80°C or higher.

[0076] The oil-resistant agent may or may not contain a blocked isocyanate compound. The blocked isocyanate compound may be added before the carboxyl group substitution reaction or after the reaction (for example, before the curing step).

[0077] Preferred blocked isocyanates include oxime-blocked toluene diisocyanate, blocked hexamethylene diisocyanate, and blocked diphenylmethane diisocyanate.

[0078] The amount of the blocked isocyanate compound may be 15 parts by weight or less, 10 parts by weight or less, 7.5 parts by weight or less, 5 parts by weight or less, or 2.5 parts by weight or less per 100 parts by weight of the modified natural product.

[0079] Oil-resistant agents may contain additives. Examples of additives include binder resins, dispersants, water-resistant agents, oil-resistant agents, water-repellent agents, oil-repellent agents, drying rate modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, defoaming agents, texture modifiers, slipperiness modifiers, antistatic agents, hydrophilic agents, antibacterial agents, preservatives, insecticides, fragrances, flame retardants, yield agents, sizing agents, paper strength enhancers, and fillers.

[0080] Examples of yield-enhancing agents include aluminum sulfate, acrylic polymers, starch, modified starch, cellulose, modified cellulose, and silica.

[0081] Examples of sizing agents include rosin-based sizing agents, alkyl ketene dimers (AKD), alkenyl succinic anhydride (ASA), polyvinyl alcohol (PVA), modified starch, styrene-acrylic copolymers, and styrene-methacrylic copolymers.

[0082] Examples of pH adjusters include lactic acid, carbon dioxide, succinic acid, gluconic acid, citric acid, trisodium citrate, phosphoric acid, potassium carbonate, and sodium bicarbonate.

[0083] Examples of fillers include talc, kaolin, calcium carbonate, titanium dioxide, and barium sulfate.

[0084] Examples of paper strength enhancers include urea-formaldehyde resin, melamine-formaldehyde resin, polyamide-polyamine epichlorohydrin (PAE), polyvinylamine (PVAm), modified starch, polyacrylamide, and polyvinyl alcohol.

[0085] The amount of additive is more than 0, preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, 100 parts by weight or less, more preferably 80 parts by weight or less, and even more preferably 50 parts by weight or less, per 100 parts by weight of the modified natural product.

[0086] <Properties of oil-resistant and modified natural products> The melting point of the functional groups (side chains) in the modified natural product is preferably 0°C or higher, or absent, and preferably 20°C or higher, 40°C or higher, or 60°C or higher. Furthermore, the melting point of the functional groups (side chains) is preferably 180°C or lower, 140°C or lower, or 120°C or lower. Having the melting point of the functional groups (side chains) within the above range improves resistance to temperature, which is particularly preferable from the viewpoint of high-temperature oil resistance. Here, the functional groups (side chains) in the modified natural product refer to the R groups of the modified natural product, particularly hydrocarbon groups having 1 to 40 carbon atoms. The melting point of the functional groups (side chains) in the modified natural product is the temperature at which the arrangement of the R groups of the modified natural product collapses when the solid of the modified natural product is heated from a low temperature, and may be the glass transition temperature of the modified natural product.

[0087] Regarding the oil resistant agent, the contact angle of n-hexadecane (on the glass substrate) may be 5° or more, 10° or more, or 15° or more, preferably 20° or more, 25° or more, more preferably 30° or more, and most preferably 35° or more, 40° or more. Having the contact angle of n-hexadecane within the above range makes the oil resistant agent exhibit excellent liquid repellency, which is particularly preferable from the viewpoint of oil resistance.

[0088] The melting point of the modified natural product is preferably 20°C or higher, more preferably 40°C or higher, even more preferably 60°C or higher, and most preferably 80°C or higher. The melting point of the oil-resistant agent is preferably 200°C or lower, 180°C or lower, or 160°C or lower. Having the melting point of the oil resistant agent within the above range improves the coating properties and temperature resistance when applied to textile products, which is particularly desirable from the viewpoint of high-temperature oil resistance.

[0089] The glass transition temperature of the modified natural product is preferably 0°C or higher or none, more preferably 20°C or higher or none, even more preferably 40°C or higher or none, and most preferably 60°C or higher or none. Furthermore, the glass transition temperature of the oil resistant agent is preferably 180°C or lower, 140°C or lower, or 120°C or lower. Having the glass transition temperature of the oil resistant agent within the above range improves the coating properties and temperature resistance when applied to textile products, and is particularly preferable from the viewpoint of oil resistance.

[0090] The viscosity of the oil-resistant agent (solution or dispersion) with a modified natural product concentration of 14.8 mg / mL is preferably 3 cP or higher, 5 cP or higher, 7 cP or higher, or 10 cP or higher. Furthermore, the viscosity of the oil-resistant agent (solution or dispersion) with a modified natural product concentration of 14.8 mg / mL is preferably 1000 cP or lower, 500 cP or lower, or 100 cP or lower. Having the viscosity of the solution (or dispersion) within the above range improves the coating properties when applied to textile products, and is particularly preferable from the viewpoint of oil resistance.

[0091] The air permeability of the treated paper, which is prepared by applying an oil-resistant agent (solution or dispersion) with a modified natural product concentration of 14.8 mg / mL to a base paper of 45 g / m2 with a paper density of 0.58 g / cm3 using a Baker-type applicator set to 0 mil, drying the treated paper three times, and then annealing it at a temperature of 70°C to 100°C for 10 minutes, is preferably 10,000 s / 100 cc or less, more preferably 5,000 s / 100 cc or less, even more preferably 3,000 s / 100 cc or less, and most preferably 1,000 s / 100 cc or less.

[0092] The preferred ranges for the contact angle and melting point combination of the oil-resistant hexadecane (hexadecane contact angle × melting point) may be 5° or more × 0°C or higher, 10° or more × 20°C or higher, 20° or more × 40°C or higher, or 30° or more × 60°C or higher.

[0093] <Uses of oil-resistant agents> Oil-resistant agents can also be used as various agents or components of water-resistant agents, water-repellent agents, oil-repellent agents, antifouling agents, dirt-removing agents, release agents, or mold-releasing agents.

[0094] Oil-resistant agents can be used as treatment agents, such as external treatment agents (surface treatment agents) or internal treatment agents, or as components thereof.

[0095] By treating the substrate with an oil-resistant agent, the modified natural product can form a surface coating structure on the substrate surface.

[0096] The surface coating structure can be formed by applying an oil-resistant agent to the substrate (workpiece) using conventionally known methods, allowing it to adhere to the substrate surface. Typically, the modified natural product is dispersed and diluted in an organic solvent or water, then applied to the surface of the workpiece using known methods such as immersion coating, spray coating, or foam coating, followed by drying. If necessary, it may also be applied together with a suitable crosslinking agent (e.g., a blocked isocyanate compound) and curing may be performed. Furthermore, it is possible to add and use insecticides, softeners, antibacterial agents, flame retardants, antistatic agents, paint fixatives, wrinkle inhibitors, sizing agents, paper strength enhancers, etc., to the modified natural product.

[0097] Examples of materials treated with oil-resistant agents include textiles, stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster.

[0098] As for textile products, various examples can be given, but some examples include cloth products and paper products.

[0099] Examples of textile products include natural animal and plant fibers such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers; or blends thereof. Textile products include woven fabrics, knitted fabrics, and nonwoven fabrics, as well as fabrics and carpets, but treatment may also be applied to fibers, yarns, and intermediate textile products (e.g., slivers or rovings) before they are made into fabric.

[0100] Examples of paper products include paper made from bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulps such as crushed wood pulp, mechanical pulp or thermomechanical pulp, recycled paper pulp such as recycled newspaper, recycled magazine, recycled corrugated cardboard or deinked paper, paper containers, and molded articles made from paper. Specific examples of paper products include food packaging paper, gypsum board base paper, coated base paper, medium-grade paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-preventive liners and metal laminates, 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. The modified natural materials of this disclosure have excellent oil resistance (e.g., high-temperature oil resistance), and are therefore suitably used in applications requiring oil resistance, particularly in food packaging materials and food containers.

[0101] Oil repellents can be applied to fibrous substrates (e.g., textile products, fibrous raw materials such as pulp, etc.) by any known method for treating textile products with liquids. Fibrous substrates refer to both textile products and fibrous raw materials. When the textile product is cloth, the cloth may be immersed in the solution (or dispersion), or the solution (or dispersion) may be applied to or sprayed onto the cloth. The treatment may be external or internal. When the textile product is paper, the paper may be coated, or the solution (or dispersion) may be applied to or sprayed onto the paper, or it may be mixed with the pulp slurry before papermaking. The treatment may be external or internal.

[0102] The oil-resistant agent may be applied to pre-formed textile products (especially paper, cloth, etc.), or it may be applied at various stages of papermaking, for example, during the drying period of the paper.

[0103] Alternatively, the fibrous substrate may be leather. Oil repellents may be applied to the leather in the form of aqueous solutions or aqueous emulsions at various stages of leather processing, for example, during the wetting process or during the finishing process, in order to make the leather hydrophobic and oleophobic.

[0104] Oil-resistant agents can also be used as external release agents. For example, they can easily peel the surface of a substrate from other surfaces (other surfaces on the same substrate, or surfaces on other substrates). <Processing> "Treatment" refers to applying an oil-resistant agent (treatment agent) to the object to be treated by immersion, spraying, coating, etc. Through treatment, the modified natural products, which are the active ingredients of the oil-resistant agent, penetrate into the interior of the object to be treated and / or adhere to the surface of the object to be treated.

[0105] The treated material (substrate) is dried to develop oil resistance, and preferably heated to a temperature above the glass transition temperature (Tg) of the modified natural product, for example, 40°C or higher, 60°C or higher, 80°C or higher, or 250°C or lower, or 200°C or lower. Treating at a temperature above the Tg of the modified natural product may induce the arrangement of side chains. More preferably, a temperature above the melting point (Tm) is preferred. By treating at a temperature above the Tm of the modified natural product, the substrate surface is coated with the modified natural product. This can form a surface coating structure with excellent hydrophobicity.

[0106] When the oil-resistant agent is applied in liquid form, the treated fibrous substrate may be pressurized to improve its solvent-removing (dehydrating) properties or the adhesion between the modified natural product and the substrate. The pressure is greater than 0.1 MPa, preferably 0.15 MPa or higher, and more preferably 0.2 MPa or higher.

[0107] <Additives for paper> Oil repellents are particularly suitable for use in paper additives. Paper additives containing oil repellents can be used as water repellents, water repellents, and / or oil repellents in addition to being oil repellents. Paper additives are preferably in the form of solutions, emulsions, or aerosols. Paper additives may contain modified natural products and a medium (e.g., an organic solvent and a liquid medium such as water), and are preferably aqueous dispersions of modified natural products. In paper additives, the concentration of the modified natural product may be, for example, 0.01 to 50% by weight. Paper additives do not need to contain surfactants.

[0108] The removal of solutions (organic solvents, water) contained in paper additives can be achieved by heating the modified natural product solution (dispersion) at temperatures of 40°C or higher, 60°C or higher, 80°C or higher, or 250°C or lower, or 200°C or lower.

[0109] Paper additives can be used to treat (e.g., surface treat) paper substrates. Paper additives can be applied to the substrate by conventionally known methods. Typically, the paper additive is dispersed and diluted in an organic solvent or water, and then applied to the surface of the substrate by known methods such as dipping, spraying, or foaming, followed by drying (surface treatment). Examples of paper substrates to be treated include paper, paper containers, and paper molded products (e.g., pulp molds). The modified natural products of this disclosure adhere well to paper substrates. Here, adhesion refers to physical or chemical bonding. Oil-resistant paper is obtained by the adhesion of the modified natural products to the paper substrate.

[0110] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims. [Examples]

[0111] Next, the present disclosure will be specifically described with reference to examples. However, these descriptions will not limit the present disclosure. In the following, parts, percent, or ratios refer to parts by weight, weight percent, or weight ratio, unless otherwise specified.

[0112] The test methods used below are as follows:

[0113] Creating processed paper As wood pulp, the weight ratio of LBKP (hardwood bleached kraft pulp) and NBKP (softwood bleached kraft pulp) is 60% by weight and 40% by weight, and the pulp's filtration degree is 400 ml (Canadian Standard Freeness). A pulp slurry is prepared, and a wet paper strength agent and a sizing agent are added to this pulp slurry. Paper is then processed on a wire screen paper machine to achieve a paper density of 0.58 g / cm³. 3 Basis weight 45g / m² 2 This paper was used as the base paper for external processing (size press processing). The oil resistance (KIT value) of this base paper is 0, and the water resistance (Cobb value) is 52 g / m². 2 That was the case.

[0114] Polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycols, alkylamine salts, quaternary ammonium salts, carboxylates, polyethyleneimine ethoxylates, and similar compounds were used as emulsifiers and dispersants.

[0115] When preparing a modified natural product solution (or dispersion) using an organic solvent, add 14.9 mg / cm³ of the base paper. 3 A modified natural product solution (or dispersion) (using chloroform, toluene, or acetone as the solvent) was applied using a Baker-type applicator with a gap set to 0 mil, and the drying process was repeated three times. The paper was then annealed at 70°C for 10 minutes to prepare the treated paper.

[0116] When preparing a modified natural product aqueous solution (or dispersion) using water, a 1 wt% modified natural product aqueous solution (or dispersion) was applied to the base paper with a Baker applicator set at a gap of 0 mil, and the operations of coating and drying were repeated three times, followed by annealing at 100 °C for 10 minutes to produce the treated paper.

[0117] KIT test (oil resistance) Measured by the 3M Kit Test (TAPPI T-559cm-02). The 3M Kit Test method involves placing a test oil containing castor oil, toluene, and heptane on the surface of the treated paper, wiping the test oil after 15 seconds, and evaluating based on the presence or absence of oil stains on the treated paper. Tests were conducted with the test oils of Kit Numbers 1 to 6, and the largest kit number with no visible stain was taken as the evaluation result of oil resistance.

[0118] Corn oil resistance evaluation (oil resistance) Castor oil was placed on the surface of the treated paper, and after wiping the test oil 15 seconds later, it was evaluated based on the presence or absence of oil stains on the treated paper. When there was no stain, it was marked as "〇", and when a stain was visible, it was marked as "×".

[0119] Liquid repellency (static contact angle) The liquid repellency was measured by spin-coating a solution (or dispersion) with a solid content concentration of 1.0% of the modified natural product on a glass substrate with a cellophane film attached and measuring the static contact angle. The static contact angle was obtained by dropping 2 μL of hexadecane (HD) onto the coating film and measuring the contact angle 1 second after droplet deposition.

[0120] Air permeability The air permeability (air resistance) of the treated paper was measured in accordance with JIS P8117 (2009) using an automatic Gurley densometer (Product No. 323-AUTO, ventilation pore diameter 28.6 ± 0.1 mm) manufactured by Yasuda Seiki Co., Ltd.

[0121] melting point The melting points were obtained by measuring using a differential scanning calorimeter. The temperature of the peak with the greatest endothermic activity was taken as the melting point of the modified natural product, and the temperature of the peak with the next greatest endothermic activity was taken as the melting point of the functional group (side chain) in the modified natural product.

[0122] Mold creation An automatic mold forming machine was used to form the mold. At the bottom, a mesh structure was placed on top of a metal pulp mold with numerous suction holes, and at the top, a metal tank was placed, into which the pulp slurry was placed. From the side of the pulp mold opposite the mesh structure, the pulp-containing aqueous composition was sucked and dewatered at 0.1 to 1 MPa using a vacuum pump, and the solid components (pulp, etc.) contained in the pulp-containing aqueous composition were deposited on the mesh structure to obtain a pulp mold intermediate. Next, the obtained pulp mold intermediate was dried from above and below at a pressure of 0.1 to 1 MPa using a metal male-female mold heated to 60 to 200°C. This produced a pulp mold product molded into the shape of a container.

[0123] Practical oil resistance test 100 ml of corn oil at 65°C was poured into the mold and left at room temperature for 45 minutes. The degree of oil staining on the mold was then evaluated. The following evaluation values ​​were set based on the degree of staining. 5: No stains on the inside. 4: Stain on the inside. No stain on the reverse side. 3: There is a stain on the inside. There is a slight seepage on the reverse side. 2: There is a stain on the inside. The stain has seeped through to the back over less than 50% of the area. 1: There is a stain on the inside. The stain has seeped through to the back, covering more than 50% but less than 100% of the area. 0: Staining across the entire back side.

[0124] Practical water resistance test 100 ml of 100°C water was poured into the mold and left at room temperature for 30 minutes. The degree of staining in the mold was then evaluated. The following evaluation values ​​were set based on the degree of staining. 5: No stains on the inside. 4: Stain on the inside. No stain on the reverse side. 3: There is a stain on the inside. There is a slight seepage on the reverse side. 2: There is a stain on the inside. The stain has seeped through to the back over less than 50% of the area. 1: There is a stain on the inside. The stain has seeped through to the back, covering more than 50% but less than 100% of the area. 0: Staining across the entire back side.

[0125] Example 1 In a reaction vessel equipped with a reflux condenser and a Dean-Stark condenser, a stirring bar, 2.8 g of citric acid, and 13 g of octadecylamine were added and heated to 70°C. 20 ml of toluene was then added. The mixture was heated and stirred at 135°C for 64 hours. The reaction vessel was cooled to room temperature, another 20 ml of toluene was added, and the mixture was washed with acetone and then ethanol to obtain the modified natural product. The biobase of the obtained modified natural product was 100%. The melting point of this modified natural product and its content of 14.9 mg / cm³ were also determined. 3 Table 1 shows the results of the KIT test, evaluation of corn oil resistance, liquid repellency, and air permeability of the chloroform solution prepared.

[0126] Example 2 In a reaction vessel equipped with a reflux condenser and a Dean-Stark condenser, a stirring bar, 1.9 g of citric acid, 11 g of stearyl alcohol, and 15 ml of toluene were added, and 0.2 g of sulfuric acid was added dropwise while stirring. The temperature was gradually raised to 140°C and heated and stirred at 140°C for 3 hours. After cooling to room temperature, 30 ml of chloroform was added, heated to dissolve, and then washed with ethanol to obtain the modified natural product. The biobase of the obtained modified natural product was 100%. The melting point of this modified natural product and the biobase content of 14.9 mg / cm³ of this modified natural product were also determined. 3 Table 1 shows the results of the KIT test, corn oil resistance, liquid repellency, and air permeability evaluation of the chloroform solution prepared.

[0127] Comparative Example 1 As an oil-resistant agent, cellulose (20 μm powder) was used in the KIT test to evaluate corn oil resistance, liquid repellency, and air permeability. The results are shown in Table 1.

[0128]

Table 1

[0129] Example 3 30 mg of the modified natural product obtained in Example 1, 30 mg of sodium oleate, and 0.3 g of water were added and heated at 100°C. After that, hot water was added so that the modified natural product became 1 wt%. While heating to 90°C, it was dispersed with an ultrasonic homogenizer to prepare a dispersion. Using this dispersion, the KIT test, corn oil resistance, and air permeability were evaluated. The results are shown in Table 2.

[0130]

Table 2

[0131] Example 4 500 mg of the modified natural product obtained in Example 1 and 500 mg of an emulsifier (polyoxyethylene oleyl ether) were added and heated at 110°C. After that, hot water was added so that the modified natural product became 1 wt%. While heating to 90°C, it was dispersed with a mechanical shear homogenizer to obtain a dispersion.

[0132] Example 5 A dispersion was obtained by operating in the same manner as the method described in Example 4 except that the emulsifier was changed to sodium oleate.

[0133] Examples 6 - 9 1300 ml of water was added to 700 g of a 1.4 wt% aqueous dispersion of a mixture of 70 parts of bleached hardwood kraft pulp and 30 parts of bleached softwood kraft pulp beaten to a Canadian freeness of 550 cc. While stirring, the aqueous dispersion of the modified natural product obtained in Examples 4 and 5 was added per pulp weight such that the modified natural product was as described in Table 3 in terms of solid content concentration to prepare a pulp slurry.

[0134] Mold forming The pulp slurries from Examples 6-9 were placed in an automatic mold testing machine and pressed for 10 seconds at a pressure of 0.3 MPa and a temperature of 80°C, followed by pressing for 60 seconds at a pressure of 0.3 MPa and a temperature of 180°C to create pulp molds weighing approximately 10 g. The obtained pulp molds were subjected to practical oil resistance tests and practical water resistance tests. The results are shown in Table 3.

[0135] Comparative Example 2 A pulp slurry was prepared by adding 1300 ml of water to 700 g of a 1.4 wt% aqueous dispersion of a mixture of 70 parts hardwood bleached kraft pulp and 30 parts softwood bleached kraft pulp, which had been beaten to a filtration degree of 550 cc (Canadian freeness). This slurry was then placed in an automatic mold testing machine and pressed for 10 seconds at a pressure of 0.3 MPa and a temperature of 80°C, followed by pressing for 60 seconds at a pressure of 0.3 MPa and a temperature of 180°C to create a pulp mold weighing approximately 10 g. The obtained pulp mold was subjected to practical oil resistance tests and practical water resistance tests. The results are shown in Table 3.

[0136] [Table 3]

[0137] Example 10 100 mg of the modified natural product obtained in Example 1, 10 mg of polyoxyethylene trimethyl nonyl ether, and 300 mg of isopropyl alcohol were added and heated at 85°C, causing the modified natural product to dissolve. Hot water was then added until the modified natural product content reached 1 wt%, and the mixture was ground three times at 245 MPa using a Starbust Mini (model number HJP-25001) manufactured by Sugino Machine Co., Ltd. to obtain a dispersion.

[0138] Examples 11-15 A dispersion was obtained by following the same procedure as in Example 10, except that polyoxyethylene trimethylnonyl ether was replaced with the emulsifiers and dispersants shown in Table 4. [Table 4]

[0139] Examples 16-18 Dispersions were obtained by following the same procedures as described in Examples 10-15, except that the concentration of the modified natural product was changed to 10 wt%, the number of grinding cycles was changed to one, and the emulsifier or dispersant was changed as shown in Table 5. Compared to the case where the concentration of the modified natural product was 1 wt%, the dispersibility was improved.

[0140] Molding 700 g of a 1.4 wt% aqueous dispersion of a mixture of 70 parts hardwood bleached kraft pulp and 30 parts softwood bleached kraft pulp, beaten to a filtration density of 550 cc (Canadian freeness), was mixed with 1300 ml of water. While stirring, the aqueous dispersions of modified natural products obtained in Examples 16-18 were added to the mixture so that the modified natural products constituted 2.5% of the pulp weight in terms of solid content, thereby preparing a pulp slurry. This pulp slurry was placed in an automatic mold testing machine and pressed for 10 seconds at a pressure of 0.3 MPa and a temperature of 80°C, followed by pressing for 60 seconds at a pressure of 0.3 MPa and a temperature of 180°C to create a pulp mold weighing approximately 10 g. A practical oil resistance test was performed on the obtained pulp mold. The results are shown in Table 5. [Table 5]

[0141] Example 19 200 mg of emulsifier A (polyoxyethylene polyoxypropylene alkyl ether) was mixed with 17.8 g of water to prepare an aqueous emulsifier solution (dispersion). Then, 2 g of the modified natural product obtained in Example 1 was added and stirred. The mixture was then ground three times at 245 MPa using a Starbust Mini to obtain a dispersion.

[0142] Example 20 10 mg of emulsifier A (polyoxyethylene polyoxypropylene alkyl ether) and 53 mg of emulsifier B (bishydroxyethylalkylmethylammonium chloride) were added to 17.8 g of water to prepare an aqueous emulsifier solution (dispersion). Then, 2 g of the modified natural product obtained in Example 1 was added and stirred. The mixture was then ground three times at 245 MPa using a Starbust Mini to obtain a dispersion.

[0143] Examples 21-28 A dispersion was obtained by performing the same procedure as in Example 20, except that emulsifier B and additives were changed as shown in Table 6.

[0144] Molding 700 g of a 1.4 wt% aqueous dispersion of a mixture of 70 parts hardwood bleached kraft pulp and 30 parts softwood bleached kraft pulp, beaten to a filtration density of 550 cc (Canadian freeness), was mixed with 1300 ml of water. While stirring, the aqueous dispersions of modified natural products obtained in Examples 21-28 were added to the mixture so that the modified natural products constituted 2.5% of the pulp weight in terms of solid content, thereby preparing a pulp slurry. This pulp slurry was placed in an automatic mold testing machine and pressed for 10 seconds at a pressure of 0.3 MPa and a temperature of 80°C, followed by pressing for 60 seconds at a pressure of 0.3 MPa and a temperature of 180°C to create a pulp mold weighing approximately 10 g. The obtained pulp mold was subjected to a practical oil resistance test. The results are shown in Table 6. [Table 6]

[0145] Example 29 3.24 g of dimethyl 3-hydroxyglutarate was dissolved in 20.0 mL of anhydrous toluene, then 2.91 g of stearylamine was added, and the mixture was stirred overnight at an oil bath temperature of 132 °C. The next day, after cooling to room temperature, 30 mL of methanol was added, and the reaction solution was filtered. Compound A was obtained by drying the solid.

[0146] (Compound A) TIFF2023101503000024.tif2281 1 H NMR (CDCl3, 400 MHz) δ: 0.87 (t, 3 H), 1.10-1.50 (m, 32 H), 2.30-2,42 (m, 2 H), 2.45-2.54 (m, 2 H), 3.20-3.24 (m, 2 H), 3.73 (s, 3 H), 4.34-4.45 (m, 1 H), 5.99 (br s, 1 H).

[0147] Compound A at 14.9 mg / cm³ 3 A chloroform solution containing the specified ingredients was prepared, and the KIT test and corn oil resistance were evaluated. The results are shown in Table 7.

[0148] Example 30 0.15 g of D,L-malic acid was dissolved in 10.0 mL of acetyl chloride, and the mixture was stirred in an oil bath at 60°C for 5 hours. After 5 hours, the mixture was concentrated to dryness to obtain 0.18 g of the intermediate compound.

[0149] (intermediate compound) TIFF2023101503000025.tif2242 1 H NMR (CDCl3, 400 MHz) δ: 2.21 (s, 3 H), 3.39 (dd, 1 H), 3.03 (dd, 1 H), 5.52 (dd, 1 H). 0.18 g of the above intermediate compound was dissolved in 20.0 mL of anhydrous dichloromethane, then 0.46 g of stearylamine was added, and the mixture was stirred overnight at an oil bath temperature of 40°C. The next day, after concentration to dryness, the mixture was suspended in 6 mL of dichloromethane, filtered, and dried to obtain 0.41 g of compound B.

[0150] (Compound B) TIFF2023101503000026.tif2244[In the formula, Ac represents an acetyl group.] 1 H NMR (CDCl3, 400 MHz) δ: 0.87 (t, 3 H), 1.10-1.50 (m, 32 H), 2.16 (s, 3 H), 2.89-3.03 (m, 2 H), 3.20-3.30 (m, 2 H), 5.45 (t, 1 H), 6.25 (br s, 1 H).

[0151] 0.41 g of compound B was dissolved in 15.0 mL of anhydrous chloroform, and the mixture was stirred in an ice bath for 5 minutes. Then, 0.334 g of stearylamine, 11.7 mg of 4,4-dimethylaminopyridine, and 0.22 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride were added in that order. The reaction solution was stirred overnight and then concentrated to dryness. Subsequently, the residue was washed with 20 mL of water and then 20 mL of methanol, filtered, and dried to obtain 0.43 g of compound C.

[0152] (Compound C) TIFF2023101503000027.tif2238 [In the formula, Ac represents an acetyl group.] 1 H NMR (CDCl3, 400 MHz) δ: 0.87 (t, 3 H), 1.10-1.50 (m, 64 H), 2.13 (s, 3 H), 2.70-2.83 (m, 2 H), 3.10-3.27 (m, 4 H), 5.42 (br s, 1 H).

[0153] Compound C at 14.9 mg / cm³ 3 A chloroform solution containing the specified ingredients was prepared, and the KIT test and corn oil resistance were evaluated. The results are shown in Table 7.

[0154] Example 31 (Compound D) TIFF2023101503000028.tif1764 [In the formula, Boc is a t-butoxycarbonyl group.]

[0155] Compound D at 14.9 mg / cm³ 3 A chloroform solution containing the specified ingredients was prepared, and the KIT test and corn oil resistance were evaluated. The results are shown in Table 7.

[0156] [Table 7] [Industrial applicability]

[0157] The modified natural products of the bio-based compounds disclosed herein can be used as oil repellents, and further as water repellents, water repellents, oil repellents, antifouling agents, dirt removers, release agents, or mold release agents. The modified natural products are suitably used in applications where oil resistance is required, particularly in food applications such as food packaging materials and food containers.

Claims

1. formula: or [In the formula, Each R″ may be the same or different and is —OH or —NH—R １ (R １ is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, R' is hydrogen or an acetyl group. A compound represented by the formula:

2. R″ is —NH—R １ 2. The compound of claim 1,

3. One of R″ is —NH—R １ and the other is -OH.

4. R １ The compound according to any one of claims 1 to 3, wherein is an alkyl group having 12 to 22 carbon atoms.

5. The compound shown below. or

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