Modified natural products and uses thereof

Abstract

The present invention relates to an environmentally harmonious oil-resistant agent capable of imparting sufficient oil resistance using a natural material as a biomass material. In the oil-resistant agent, hydrogen atoms of hydroxyl groups in a natural product containing at least one hydroxyl group are substituted by R groups. In the formula, the R group is a group represented by-Y-Z (in the formula, Y is a direct bond,-C (= O)-,-C (= O)-NR '-or-C (= S)-NR'-(where R 'is a hydrogen atom or an alkyl group having C1-C4 carbon atoms, and Z is an optionally substituted hydrocarbon group having 1-40 carbon atoms, or a polysiloxane). The natural product is preferably cellulose, dextrin, glycerol or polyglycerol.

Description

[0001] This case is a divisional application with an application date of September 22, 2021 and an application number of 202180057302.0 ,

[0002] and an invention title of " Modified natural product and its uses ". Technical Field

[0003] The present invention relates to a modified natural product obtained by modifying a natural product and its uses, and particularly relates to an oil-resistant agent. Background Art

[0004] Paper containers are highly anticipated as alternatives to disposable plastic containers. Paper food packaging materials and food containers need to prevent the leakage of moisture and oil from food, and this requirement is met by internally mixing an oil-resistant agent in the paper or externally coating the paper surface. In addition, from the perspective of environmental considerations, the demand for biodegradable materials and bio-based materials is also increasing.

[0005] Patent Document 1 (Japanese Patent Application Laid-Open No. 2019-99953) discloses a technique for achieving oil resistance by combining oxidized starch or hydrophobic starch with an epichlorohydrin-modified fatty acid sizing agent. However, in order to prevent acetic acid odor, it is necessary to adjust the pH value of the mixture. Moreover, the compatibility of the modified starch and the fatty acid sizing agent is important, and it is difficult to adjust the composition.

[0006] Patent Document 2 (Japanese Patent Application Laid-Open No. 2020-066805) discloses an oil-resistant agent using modified starch, clay, styrene-butadiene copolymer, and an antifoaming agent.

[0007] Patent Document 3 (Japanese Patent Application Laid-Open No. 2019-70202) discloses an oil-resistant paper composed of a fluoropolymer containing no perfluoroalkyl group having 7 or more carbon atoms and a water-soluble or water-dispersible cellulose derivative.

[0008] Patent Document 4 (International Publication No. 2015 / 162787) discloses the use of cellulose having a long-chain alkyl group (12 to 18 carbon atoms) in the form of acetylated cellulose acetate in optical film applications. Although water resistance is described, oil resistance is not disclosed.

[0009] Patent Document 5 (Japanese Patent Application Laid-Open No. 2002-012258) discloses the content of imparting properties such as oil resistance, water resistance, and heat resistance to food containers by coating with cellulose acetate. However, in its examples, only water resistance and heat resistance were evaluated, and oil resistance was not evaluated.

[0010] Prior Art Documents

[0011] Patent Documents

[0012] Patent Document 1: Japanese Patent Application Laid-Open No. 2019-99953

[0013] Patent Document 2: Japanese Patent Application Laid-Open No. 2020-066805

[0014] Patent Document 3: Japanese Patent Application Laid-Open No. 2019-70202

[0015] Patent Document 4: International Publication No. 2015 / 162787

[0016] Patent Document 5: Japanese Patent Application Laid-Open No. 2002-012258 Summary of the Invention

[0017] Problems to be Solved by the Invention

[0018] An object of the present invention is to provide an oil-resistant agent that is harmonious with the environment and uses natural substances as biomass materials and can impart sufficient oil resistance.

[0019] Technical Solution for Solving the Problems

[0020] The present invention relates to a modified natural substance (modified natural compound) in which a natural substance (natural compound) is modified to have an organic modification group. Examples of the organic modification group are an aliphatic hydrocarbon group having 1 to 40 carbon atoms, a substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, or a polysiloxane.

[0021] The modified natural substance can be used as an oil-resistant agent.

[0022] Preferred embodiments of the present invention are as follows.

[0023] First Embodiment:

[0024] An oil-resistant agent, which contains a modified natural substance in which a hydrogen atom of a hydroxyl group in a natural substance having at least one hydroxyl group is replaced by an R group,

[0025] The R group is a group represented by -Y-Z,

[0026] In the formula, Y is a direct bond, -C(=O)-, -C(=O)-NR'- or -C(=S)-NR', where R' is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

[0027] Z is a hydrocarbon group having 1 to 40 carbon atoms that may have a substituent, or a polysiloxane.

[0028] Second Embodiment:

[0029] The oil-resistant agent according to the first embodiment, wherein the natural substance is a natural substance other than starch.

[0030] Third Embodiment:

[0031] The oil-resistant agent according to the first or second aspect, wherein the natural product is a compound of the natural product itself or a compound derived from the natural product.

[0032] Fourth aspect:

[0033] The oil-resistant agent according to any one of the first to third aspects, wherein the natural product is a monosaccharide or a polysaccharide, glycerol, or polyglycerol.

[0034] Fifth aspect:

[0035] The oil-resistant agent according to any one of the first to fourth aspects, wherein

[0036] the natural product is at least one selected from high-molecular natural products and low-molecular natural products,

[0037] the high-molecular natural product is at least one selected from cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa-carrageenan, iota-carrageenan, polyglycerol, isomaltooligosaccharide, xanthan gum, gellan gum, tamarind seed gum, and cyclodextrin;

[0038] the low-molecular natural product is at least one selected from glucose, sucrose, mannitol, sorbitol, sorbose, maltitol, stevioside, cyclodextrin, glycerol, menthol, xylitol, glucosamine, catechin, anthocyanin, and quercetin, gluconic acid, malic acid, xylose, inositol, phytic acid, menthol, sucralose, fructose, maltose, trehalose, lactosucrose, erythritol, erythritol, ascorbic acid, kojic acid, cholesterol, vanillin, lactic acid, tartaric acid, citric acid, and chlorogenic acid.

[0039] Sixth aspect:

[0040] The oil-resistant agent according to any one of the first to fifth aspects, wherein the substitution rate of the hydrogen atom of the hydroxyl group replaced by R is 3 to 100%.

[0041] Seventh aspect:

[0042] The oil-resistant agent according to any one of the first to sixth aspects, wherein Z is an aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a polysiloxane, and the substituent is a hydroxyl group, an ester group, an R'3Si group, an (R'O)3Si group, a carboxyl group, or a salt of a carboxyl group, wherein R' is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0043] Eighth aspect:

[0044] The oil-resistant agent according to any one of the first to seventh aspects, wherein the contact angle of the oil-resistant agent with n-hexadecane shows 11 degrees or more.

[0045] Ninth aspect:

[0046] The oil-resistant agent according to any one of the first to eighth aspects, wherein the modified natural product has a melting point of 40 degrees or higher or has no melting point.

[0047] Tenth aspect:

[0048] The oil-resistant agent according to any one of the first to ninth aspects, wherein the viscosity of the solution concentration of the oil-resistant agent at 14.8 mg / mL is 5 cP or more and 100 cP or less.

[0049] Eleventh aspect:

[0050] The oil-resistant agent according to any one of the first to tenth aspects, wherein the oil-resistant agent is a water-dispersed composition.

[0051] Twelfth aspect:

[0052] The oil-resistant agent according to any one of the first to eleventh aspects, wherein the oil-resistant agent is an oil-resistant agent for paper.

[0053] Thirteenth aspect:

[0054] A fiber product, wherein the oil-resistant agent according to any one of the first to twelfth aspects is attached.

[0055] Fourteenth aspect:

[0056] An oil-resistant paper, which contains the oil-resistant agent according to any one of the first to twelfth aspects.

[0057] Fifteenth aspect:

[0058] The oil-resistant paper according to the fourteenth aspect, wherein the oil-resistant paper is a food packaging material or a food container.

[0059] Sixteenth aspect:

[0060] A treatment method for externally applying or internally mixing paper with the oil-resistant agent according to any one of the first to twelfth aspects.

[0061] Advantages of the invention

[0062] The modified natural product of the present invention exhibits excellent oil resistance. The oil-resistant agent containing the modified natural product of the present invention is bio-based and thus does not impose a burden on the ecological environment and has excellent biodegradability. Detailed implementation mode

[0063] The present invention provides a modified natural product (modified natural compound), wherein a hydrogen atom of a hydroxyl group in a natural product having at least one hydroxyl group is replaced by an R group.

[0064] The R group is a group represented by the formula -Y-Z,

[0065] wherein Y is a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-, and R' is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

[0066] and Z is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a polysiloxane.

[0067] Examples of the substituent are a hydroxyl group, an ester group, an R'3Si group, an (R'O)3Si group, a carboxyl group or a salt of a carboxyl group, where R' is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0068] Any two of the Rs may combine with each other to form a ring.

[0069] The modified natural product (modified natural compound) has an -O-R group that does not exist in the natural product.

[0070] When the modified natural product (modified natural product compound) contains two or more -O-R groups, the -O-R groups may be the same or a combination of -O-R groups having different structures.

[0071] Examples of the R group are -Z, -C(=O)-Z, -C(=O)-NH-Z, -C(=O)-NR'-Z, and -C(=S)-NR'-Z, where the meanings of Z and R' are as described above.

[0072] Z is a monovalent group.

[0073] Z is a hydrocarbon group having 1 to 40 carbon atoms, or a hydrocarbon group having 1 to 40 carbon atoms with a substituent.

[0074] Z may be a hydrocarbon group having 1 to 3 carbon atoms, but is preferably a branched hydrocarbon group or a long-chain hydrocarbon group (or a (long-chain) straight-chain hydrocarbon group) having 4 or more carbon atoms, or a cyclic hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and particularly preferably an alkyl group. The -CH3 group has a lower surface free energy than -CH2- and is more likely to exhibit liquid-repellent properties. Therefore, a structure with many branches and many -CH3 groups is preferred. On the other hand, a long-chain alkyl group having a certain length exhibits high liquid-repellent properties due to its crystallinity.

[0075] In the branched hydrocarbon group, the number of ―CH3 groups is preferably 2 to 15, for example, 3 to 10 or 4 to 9. On the other hand, long-chain alkyl groups having a certain length (for example, 16 to 40 carbon atoms) exhibit high water repellency due to their crystallinity. Therefore, a branched hydrocarbon group (for example, a branched (for example, having 3 to 10 or 4 to 8 carbon atoms) alkyl group), such as a tert-butyl group and a neopentyl group, or a hydrocarbon group having a multi-branched structure with 5 to 30 carbon atoms, or a long-chain hydrocarbon group (or a long-chain straight-chain hydrocarbon group), such as an alkyl group having 16 to 40 or 16 to 26 carbon atoms, particularly 18 to 22 carbon atoms, is preferred. The long-chain hydrocarbon group is preferably a stearyl group, an icosyl group, or a behenyl group.

[0076] The number of carbon atoms of the hydrocarbon group can be 2 or more, 4 or more, 7 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, or 20 or more, preferably 10 or more or 12 or more. The number of carbon atoms of the hydrocarbon group can 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.

[0077] The hydrocarbon group can be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group. The hydrocarbon group can be straight-chain, branched-chain, or cyclic, preferably straight-chain or branched-chain, more preferably straight-chain. The hydrocarbon group can be an unsaturated (for example, monounsaturated, diunsaturated, triunsaturated, tetraunsaturated, or polyunsaturated) hydrocarbon group or a saturated hydrocarbon group, such as an alkyl group.

[0078] Specific examples of the hydrocarbon group include alkyl groups such as n-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl 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, nonadecyl group, behenyl group, 2-ethylhexyl group, isostearyl group, etc.; alkenyl groups such as oleyl group, palmoleyl group, icosene group, etc.; cycloalkyl groups such as cyclohexyl group.

[0079] Z can be a hydrocarbon group substituted with a carboxyl group.

[0080] The hydrocarbon group that can be substituted with a carboxyl group is preferably a group represented by the formula: ―A―C(=O)―OH, wherein A is a direct bond or a hydrocarbon group having 1 to 40 or 1 to 10 carbon atoms, such as an alkylene group.

[0081] Z can be a hydrocarbon group substituted with a salt of a carboxyl group. That is, it can be a hydrocarbon group substituted with a salt of a carboxyl group and a base.

[0082] The hydrocarbon group substituted with a salt of a carboxyl group is preferably a salt of a group represented by the formula: ―A―C(=O)―OH, wherein A is a direct bond or a hydrocarbon group having 1 to 40 or 1 to 10 carbon atoms, such as an alkylene group.

[0083] As the base, ammonia, an organic amine or an alkali metal hydroxide is preferably used.

[0084] Examples of the organic amine include methylamine, ethylamine, diethylamine, dimethylethanolamine, diethanolamine, triethanolamine and the like. Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. These bases may be used alone or in combination of two or more.

[0085] By neutralizing with a base, the modified natural product has good dispersibility in an aqueous dispersion medium, and an aqueous dispersion of a high-quality oil-resistant agent can be obtained.

[0086] Z may be a polysiloxanyl group. The polysiloxanyl group may be a group represented by, for example, the formula:

[0087] ―B―[―Si(R 21 )2―O―] a ―[―Si(R 22 )(R 21 )―O―] b ―A,

[0088] In the formula, A is ―Si(R 21 )3 or ―X 1 ,

[0089] B is ―[―(R 24 )―O―] q ―R 23 ―[―Si(R 21 )2―O―] p ―, where p and q are 0 or 1,

[0090] X 1 is a linear or branched hydrocarbon group having 1 to 20 carbon atoms (or 1 to 40 carbon atoms) which may be interrupted by an oxygen atom and may have an epoxy ring, a hydroxyl group, a (meth)acryloyl group (or acryloyloxy group) and / or a carboxyl group,

[0091] R 21 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (or 1 to 40 carbon atoms), an aryl group having 6 to 20 carbon atoms (or 6 to 40 carbon atoms) or an alkoxy group having 1 to 4 carbon atoms,

[0092] R 22 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (or 1 to 40 carbon atoms), an aryl group having 6 to 20 carbon atoms (or 6 to 40 carbon atoms) or an alkoxy group having 1 to 4 carbon atoms,

[0093] R 23 represents a hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by an oxygen atom,

[0094] R 24 represents a hydrocarbon group having 1 to 20 carbon atoms that can be interrupted by an oxygen atom,

[0095] a represents an integer of 0 or more, b represents an integer of 1 or more, and (a + b) is 3 to 200.

[0096] R 21 may have an epoxy ring, a hydroxyl group, a (meth)acryloyl group (or acryloyloxy group) and / or a carboxyl group.

[0097] p and q are 0 or 1. Preferably, both p and q are 0 or both are 1.

[0098] Examples of the polysiloxanyl group may be represented by the formula

[0099] -(R 24 )-O-(R 23 )-Si(R 21 )2-O-[Si(R 21 )2-O-] a -[-Si(R 22 )(R 21 )-O-] b -Si(R 21 )3

[0100] or

[0101] -(R 24 )-O-(R 23 )-Si(R 21 )2-O-[-Si(R 21 )2-O-] a -[-Si(R 22 )(R 21 )-O-] b -X 1

[0102] or

[0103] -R 23 -[-Si(R 21 )2-O-] a -[-Si(R 22 )(R 21 )-O-] b -Si(R 21 )3

[0104] or

[0105] -R 23 -[-Si(R 21 )2-O-] a -[-Si(R 22 )(R21 )-O-] b -X 1 The group shown

[0106] In the formula, X 1 is a straight-chain or branched hydrocarbon group having 1 to 20 carbon atoms (or 1 to 40 carbon atoms) that can be interrupted by an oxygen atom and can have an epoxy ring, a hydroxyl group, a (meth)acryloyl group (or acryloyloxy group) and / or a carboxyl group,

[0107] R 21 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms,

[0108] R 22 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms,

[0109] R 23 represents a hydrocarbon group having 1 to 20 carbon atoms,

[0110] R 24 represents a hydrocarbon group having 1 to 20 carbon atoms,

[0111] a represents an integer of 0 or more, b represents an integer of 1 or more, and (a + b) is 3 to 200.

[0112] R 21 and R 22 can be a hydrocarbon group having 1 to 40 carbon atoms.

[0113] X 1 Examples of X are a hydrocarbon group having 1 to 40 carbon atoms (e.g., tert-butyl), a hydrocarbon group having 1 to 40 carbon atoms interrupted by an oxygen atom (i.e., having an ether group), a hydrocarbon group having 1 to 40 carbon atoms having an ether group and a hydroxyl group, a hydrocarbon group having 1 to 40 carbon atoms having an epoxy ring, a hydrocarbon group having 1 to 40 carbon atoms having a hydroxyl group (e.g., 1 or 2 hydroxyl groups), a hydrocarbon group having 1 to 40 carbon atoms having a (meth)acryloyl group (or (meth)acryloyloxy group), and a hydrocarbon group having 1 to 40 carbon atoms having a carboxyl group.

[0114] In this specification, the (meth)acryloyl group means an acryloyl group and a methacryloyl group.

[0115] As another example of Z as a polysiloxanyl group, it can be the formula:

[0116] ―(R 3 )2Si―O―[―Si(R 1 )2―O―] a ―[―Si(R 1 )(R2 )—O— b —Si(R 3 )3 represents a group,

[0117] In the formula, R 1 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms,

[0118] R 2 independently represents a saturated hydrocarbon group having 1 to 40 carbon atoms,

[0119] R 3 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a saturated hydrocarbon group having 1 to 40 carbon atoms,

[0120] a represents an integer of 0 or more, b represents an integer of 1 or more, and (a + b) is 3 to 200.

[0121] In the polysiloxanyl group (such as R 21 , R 22 , R 1 and R 3 ), the alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms may be unsubstituted groups, or may also have substituents.

[0122] Specific examples of the alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms (such as R 21 , R 22 , R 1 and R 3 ) may include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl; cyclopentyl, cyclohexyl, cycloheptyl; phenyl, tolyl, naphthyl, or groups in which part or all of the hydrogen atoms bonded to these groups are substituted with halogen atoms, amino groups, cyano groups, etc. R 21 , R 22 , R 1 and R 3 are preferably methyl or ethyl.

[0123] R 21 , R 22 , R 1 and R 3 may have an alkyl group having 3 to 22 carbon atoms or an unsaturated hydrocarbon group having 8 to 40 carbon atoms (such as a hydrocarbon group having an aromatic ring), but preferably do not have these groups.

[0124] In R 21 , R 22 , R1 and R 3 In formula, the alkoxy group having 1 to 4 carbon atoms may be linear or branched. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy group, ethoxy group, propoxy group, and butoxy group.

[0125] From the viewpoints of easy industrial production and easy availability, R 21 、R 22 、R 1 and R 3 are preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

[0126] The polysiloxanyl group has at least one hydrocarbon group having 1 to 40 carbon atoms, particularly a saturated hydrocarbon group.

[0127] Regarding the hydrocarbon group having 1 to 40 carbon atoms in the polysiloxanyl group, the same description as that when Z is a hydrocarbon group having 1 to 40 carbon atoms can be adopted.

[0128] The number of carbon atoms of the hydrocarbon group may also be 7 to 40, such as 18 to 38 or 23 to 36. The saturated hydrocarbon group having 1 to 40 carbon atoms may be linear or branched, and is preferably an alkyl group. Specific examples of the saturated hydrocarbon group having 1 to 40 carbon atoms include methyl group (carbon atom number 1), ethyl group (carbon atom number 2), lauryl group (carbon atom number 12), stearyl group (carbon atom number 18), tricosyl group (carbon atom number 23), carnaubyl group (tetracosyl group, carbon atom number 24), ceryl group (hexacosyl group, carbon atom number 26), montanyl group (octacosyl group, carbon atom number 28), melissyl group (triacontyl group, carbon atom number 30), dotriacontyl group (carbon atom number 32).

[0129] a is an integer of 0 or more. From the viewpoints of easy industrial production and easy availability, a is preferably 40 or less, and more preferably 30 or less.

[0130] The sum of a and b is 3 to 200 or 5 to 200. From the viewpoints of easy industrial production, easy availability, and easy handling, the sum of a and b is preferably 10 to 100, and more preferably 40 to 60. a may be 0 to 150, such as 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.

[0131] When a or b is 2 or more, there are multiple R 1 and R 2 Each R 1 and R 2 may be the same or different.

[0132] Preferably, R 1 、R 2 group, R 3More than 50 mol% of the total of the groups is methyl.

[0133] The order of presence of the repeating units enclosed by a or b in parentheses is not limited to the order of presence represented by the chemical formula and can be in any order. That is, the polysiloxanyl group can be a random copolymer or can also be a block copolymer.

[0134] Examples of the polysiloxanyl group are shown below.

[0135]

[0136] In the formula, a represents an integer from 0 to 150, b represents an integer from 1 to 150, (a + b) is from 5 to 200, and n is an integer from 0 to 36.

[0137] A natural product (natural compound) is a compound that occurs naturally and has at least one hydroxyl group (a natural compound containing a hydroxyl group).

[0138] The natural product can be low molecular weight (for example, the weight average molecular weight is less than 1000, or 500 or less) and / or high molecular weight. The weight average molecular weight of the high molecular weight can be 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, 500000 or more. The weight average molecular weight of the high molecular weight can be 1000000 or less, 7500000 or less, 500000 or less, 3000000 or less, 100000 or less, 75000 or less, 50000 or less. The weight average molecular weight can be measured by gel permeation chromatography (GPC) and converted using pullulan.

[0139] The natural product can be a high molecular weight natural product, a low molecular weight natural product, or a derivative thereof. The natural product also includes compounds transformed by microorganisms.

[0140] Examples of the high molecular weight natural product are starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan. As other examples, locust bean gum, kappa-carrageenan, iota-carrageenan, polyglycerol, isomaltooligosaccharide, xanthan gum, gellan gum, tamarind seed gum, cyclodextrin can be cited. The natural product is preferably a product other than starch.

[0141] Examples of the low molecular weight natural product include glucose, sucrose, mannitol, sorbitol, sorbose, maltitol, stevioside, cyclodextrin, glycerol, menthol, xylitol, glucosamine, catechin, anthocyanin, quercetin, gluconic acid and malic acid, xylose, inositol, phytic acid, menthol, sucralose, fructose, maltose, trehalose, oligofructose, erythritol, erythritol, ascorbic acid, kojic acid, cholesterol, vanillin, lactic acid, tartaric acid, citric acid, chlorogenic acid.

[0142] A natural product can be a compound of the natural product itself or a compound derived from a natural product. That is, natural products also include derivatives of natural products. For example, as derivatives of starch, there are oxidized starch, hydrophobic starch, starch acetate, phosphorylated starch, acetylated starch, etherified starch, cationized starch, starch formate, hydroxymethylated starch, hydroxyethylated starch, and hydroxypropylated starch. As derivatives of cellulose, there are hydroxypropyl cellulose, methyl cellulose, carboxymethyl cellulose (CMC), monoacetate cellulose, triacetate cellulose, hydroxyethyl cellulose (HEC), hydroxypropyl methyl cellulose (HPMC), hydroxyethyl methyl cellulose (HEMC), cellulose TEAE (triethylaminoethyl cellulose), and o-[2-hydroxy-3-(trimethylamino)propyl] hydroxyethyl cellulose chloride.

[0143] When the derivative of a natural product has high oil resistance, it can be used as an oil-resistant agent without modification. That is, the derivative of a natural product can also be a modified natural product (modified natural compound).

[0144] A natural product can also be a monosaccharide or a polysaccharide (such as disaccharides and trisaccharides, etc.). As monosaccharides, there can be mentioned glucose, galactose, fructose, aldose, alditol, ketose, pyranose, furanose, aldonic acid, uronic acid, and aldehyde acid, etc. A polysaccharide is a compound formed by the combination of multiple (more than 3, for example, 3 to ) monosaccharides such as glucose, galactose, and fructose. A polysaccharide can also be an oligosaccharide formed by the combination of 3 to 10 monosaccharides.

[0145] As specific examples of polysaccharides, there can be mentioned starch, cellulose, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, alginic acid, agar, dextran, pullulan, isomaltooligosaccharide, xanthan gum, gellan gum, tamarind seed gum, curdlan, pullulan, and cyclodextrin.

[0146] A natural product can be starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, and particularly preferably cellulose.

[0147] When the natural product is cellulose, the modified cellulose has a repeating unit structure shown by the following formula,

[0148] Formula:

[0149]

[0150] In the formula, at least one R group is a -Y-Z group, and the remaining R groups are hydrogen atoms. It is also possible that all three R groups are -Y-Z groups. The meanings of the Y group and the Z group are as described above. n is a number of 2 or more, for example, a number of 100 or more or 500 or more.

[0151] The natural product can be, for example, an aldose, an alditol, a ketose, a pyranose, a furanose, an aldonic acid, a uronic acid, and an aldehyde acid.

[0152] An aldose is a monosaccharide with a chemical formula of C m H 2m O m (where m is 3 or more, and the upper limit of m is usually 100, 20, or 10). Specific examples of aldoses include erythrose, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, and talose.

[0153] An alditol is a monosaccharide formed by reducing the aldehyde group of an aldose to a hydroxymethyl group, and is a monosaccharide with 3 or more carbon atoms (the upper limit of the number of carbon atoms is usually 100, 20, or 10). Specific examples of alditols include erythritol, threitol, ribitol, arabinitol, xylitol, arabitol, allitol, adonitol, sorbitol (glucitol), mannitol, sorbitol (glucitol), iditol, galactitol, and adonitol.

[0154] A ketose is a monosaccharide containing a keto group (ketonic carbonyl) inside a chain structure (the upper limit of the number of carbon atoms is usually 100, 20, or 10). Specific examples of ketoses (specific examples with 3 to 6 carbon atoms) include dihydroxyacetone, erythrulose, ribulose, xylulose, psicose, fructose, sorbose, and tagatose.

[0155] A pyranose is a monosaccharide having a six-membered ring composed of 5 carbon atoms and 1 oxygen atom. Specific examples of pyranoses include pyranose ribose, arabinopyranose, xylopyranose, lyxopyranose, allopyranose, altropyranose, glucopyranose, manopyranose, and gulopyranose.

[0156] A furanose is a monosaccharide having a five-membered ring composed of 4 carbon atoms and 1 oxygen atom. Specific examples of furanoses include erythrofuranose, threofuranose, ribofuranose, arabinofuranose, xylofuranose, and lyxofuranose.

[0157] The modified natural compound can be prepared by reacting a modifier with the hydroxyl group of a natural product. Examples of the method of reacting a modifier with a hydroxyl group include, as examples of the synthesis methods for realizing the reaction of the modifier, the method of forming a urethane bond, the method of forming an ester bond, and the method of forming an ether bond.

[0158] The modifier is preferably a compound having a hydrocarbon group, and particularly preferably a compound having an aliphatic hydrocarbon group. Examples of the modifier are as follows:

[0159] An aliphatic isocyanate and / or an aromatic isocyanate (Z―N=C=O),

[0160] Aliphatic isothiocyanate and / or aromatic isothiocyanate (Z-N=C=S),

[0161] Fatty acid (Z-C(=O)-OH),

[0162] Acyl halide compound (Z-C(=O)-X),

[0163] Acid anhydride (Z-[C=O]-O-[C=O]-Z),

[0164] Halogenated alkyl compound (Z-X),

[0165] Epoxy compound (Z-CHOCH2),

[0166] Acrylate (Z-CH2=CH),

[0167] Amine (Z-NH2),

[0168] Aliphatic alcohol (Z-OH),

[0169] In the formula, X is a halogen atom (e.g., chlorine atom, bromine atom or iodine atom), and Z is a hydrocarbon group or polysiloxane having 1 to 40 carbon atoms which may have a substituent.

[0170] The hydroxyl substitution rate of the modifier can be 1 to 100% (0.01 to 1.00). The substitution rate is preferably 1% or more, 3% or more, 5% or more or 10% or more, for example preferably 15% or more, 20%, 30% or more, 40%, 45% or 50% or more, preferably 100% or less, 99% or less, 90% or less or 80% or less, for example preferably 70% or less, 60% or less or 50% or less. The "substitution rate" means the ratio (%) of the hydroxyl groups present in the structure of the modified natural product (modified natural compound) being substituted by the modifier.

[0171] The ratio of unmodified hydroxyl groups (i.e., the residual rate of hydroxyl groups) can be 0% or more, 1% or more, 3% or more, 5% or more or 7% or more, for example can be 10% or more or 20% or more, can be 99% or less, 97% or less or 95% or less, for example can be 90% or less, 85% or less, 80% or less or 70% or less.

[0172] <Method for forming urethane bond>

[0173] React an aliphatic isocyanate and / or an aromatic isocyanate (Z-NCO) with a hydroxyl group to form a urethane bond. It is also possible to use an aliphatic isothiocyanate and / or an aromatic isothiocyanate (Z-N=C=S) instead of or in addition to the isocyanate.

[0174] In a synthesis method of replacing the hydrogen atom of a hydroxyl group in a natural product with an aliphatic isocyanate, when a natural product containing a hydroxyl group reacts with an aliphatic isocyanate or an aromatic isocyanate in an organic solvent in the presence of a catalyst such as a tin catalyst or an amine, the hydrogen atom of the hydroxyl group can react with the isocyanate group, and various modifying groups (Z groups) can be introduced via a urethane bond.

[0175] The aliphatic isocyanate is preferably a compound represented by C n H 2n+1 ―NCO, where n = 1 to 40, especially 3 to 18. The aliphatic hydrocarbon group can be straight-chain or branched-chain.

[0176] Specific examples of the aliphatic isocyanate include saturated aliphatic isocyanates such as methyl isocyanate, ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, tert-butyl isocyanate, pentyl isocyanate, neopentyl isocyanate, hexyl isocyanate, heptyl isocyanate, octyl isocyanate, nonyl isocyanate, decyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, etc.; and unsaturated aliphatic isocyanates such as butenyl isocyanate, pentenyl isocyanate, hexenyl isocyanate, octenyl isocyanate, dodecenyl isocyanate, etc.

[0177] Specific examples of the aromatic isocyanate include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenyl ether diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyl diphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethoxy diphenyl-4,4'-diisocyanate.

[0178] In a synthesis method of replacing the hydrogen atom of a hydroxyl group in a natural product with an aliphatic isothiocyanate, when a natural product containing a hydroxyl group reacts with an aliphatic isocyanate or an aromatic isothiocyanate in an organic solvent in the presence of a catalyst such as a tin catalyst or an amine, the hydrogen atom of the hydroxyl group can react with the isothiocyanate group, and various modifying groups (Z groups) can be introduced via a thiourethane bond.

[0179] The aliphatic isothiocyanate is preferably a compound represented by C n H 2n+1 ―NSO, where n = 1 to 40, especially 3 to 18. The aliphatic hydrocarbon group can be straight-chain or branched-chain.

[0180] As specific examples of aliphatic isothiocyanates, saturated aliphatic isothiocyanates such as methyl isothiocyanate, ethyl isothiocyanate, propyl isothiocyanate, isopropyl isothiocyanate, butyl isothiocyanate, pentyl isothiocyanate, hexyl isothiocyanate, heptyl isothiocyanate, octyl isothiocyanate, nonyl isothiocyanate, decyl isothiocyanate, dodecyl isothiocyanate, octadecyl isothiocyanate, etc. can be cited; and unsaturated aliphatic isocyanates such as butenyl isothiocyanate, pentenyl isothiocyanate, hexenyl isothiocyanate, octenyl isothiocyanate, dodecenyl isothiocyanate, etc.

[0181] As specific examples of aromatic isothiocyanates, 4,4'-diphenylmethane diisothiocyanate, 2,4'-diphenylmethane diisothiocyanate, 2,2'-diphenylmethane diisothiocyanate, 2,4-toluene diisothiocyanate, 2,6-toluene diisothiocyanate, 4,4'-diphenyl ether diisothiocyanate, 2,2'-diphenylpropane-4,4'-diisothiocyanate, 3,3'-dimethyl diphenylmethane-4,4'-diisothiocyanate, 4,4'-diphenylpropane diisothiocyanate, 1,2-phenylene diisothiocyanate, 1,3-phenylene diisothiocyanate, 1,4-phenylene diisothiocyanate, 1,4-naphthalene diisothiocyanate, 1,5-naphthalene diisothiocyanate, 3,3'-dimethoxy diphenyl-4,4'-diisothiocyanate can be cited.

[0182] <Method for forming an ester bond>

[0183] React a fatty acid (Z―C(=O)―OH), an acyl halide compound (Z―C(=O)―X), or an acid anhydride (Z―[C=O]―O―[C=O]―Z) with a hydroxyl group to form an ester bond.

[0184] In a synthesis method of substituting a hydrogen atom of a hydroxyl group of a natural product with a saturated aliphatic acyl group, there are methods of reacting a saturated fatty acid acyl halide with a natural product containing a hydroxyl group in the presence of a base such as pyridine; reacting a mixed acid anhydride formed by a saturated fatty acid and a haloacetic acid such as trifluoroacetic acid with a natural product containing a hydroxyl group; reacting a saturated fatty acid anhydride with a natural product containing a hydroxyl group; reacting a saturated fatty acid with a natural product containing a hydroxyl group in the presence of a sulfonate; and reacting a saturated fatty acid with a natural product containing a hydroxyl group in the presence of a dehydration polycondensation agent.

[0185] The saturated fatty acid is preferably a compound represented by C n H 2n+1 ―COOH, where n = 1 to 39. The aliphatic hydrocarbon group may be straight-chain or branched-chain.

[0186] Specific examples of saturated fatty acids are saturated fatty acids having 2 to 26 carbon atoms, such as acetic acid, butyric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, isostearic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid.

[0187] Specific examples of unsaturated fatty acids are palmitoleic acid, oleic acid, elaidic acid, isolenic acid, cis-sinapic acid, linoleic acid, γ-linolenic acid, α-linolenic acid, eicosapentaenoic acid, docosahexaenoic acid, sheep oil fatty acid.

[0188] The acyl halide compound is preferably a compound represented by C n H 2n+1 ―CO―X, wherein n = 1 to 39 and X = Br, Cl, I. The aliphatic hydrocarbon group may be straight-chain or branched-chain.

[0189] Specific examples of acyl halide compounds are valeryl chloride, heptanoyl chloride, octanoyl chloride, nonanoyl chloride, lauroyl chloride, decanoyl chloride, myristoyl chloride, tetradecanoyl chloride, heptadecanoyl chloride, undecanoyl chloride, stearoyl chloride, oleoyl chloride, palmitoyl chloride, linoleoyl chloride, valeryl bromide.

[0190] The acid anhydride is preferably a compound represented by (C n H 2n+1 ―CO)2―O, wherein n = 1 to 19 or 1 to 39. The aliphatic hydrocarbon group may be straight-chain or branched-chain.

[0191] The acid anhydride may form a 5-membered ring structure or a 6-membered ring structure. Specific examples of acid anhydrides forming a 5-membered ring structure include succinic anhydride, methylsuccinic anhydride (4-methylsuccinic anhydride), dimethylsuccinic anhydride (4,4-dimethylsuccinic anhydride, 4,5-dimethylsuccinic anhydride, etc.), 4,4,5-trimethylsuccinic anhydride, 4,4,5,5-tetramethylsuccinic anhydride, 4-vinylsuccinic anhydride, 4,5-divinylsuccinic anhydride, phenylsuccinic anhydride (4-phenylsuccinic anhydride), 4,5-diphenylsuccinic anhydride, 4,4-diphenylsuccinic anhydride, citraconic anhydride, maleic anhydride, methylmaleic anhydride (4-methylmaleic anhydride), 4,5-dimethylmaleic anhydride, phenylmaleic anhydride (4-phenylmaleic anhydride), 4,5-diphenylmaleic anhydride, itaconic anhydride, 5-methylitaconic anhydride, 5,5-dimethylitaconic anhydride, phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride and their analogs, etc.

[0192] Specific examples of acid anhydrides forming a 6-membered ring structure include cyclohexanedicarboxylic anhydride (cyclohexane-1,2-dicarboxylic anhydride, etc.), 4-cyclohexenyl-1,2-dicarboxylic anhydride, glutaric anhydride, gluconic anhydride, 2-phenylglutaric anhydride and their analogs, etc.

[0193] <Method for forming ether bond>

[0194] React a haloalkyl compound (Z―X) or an epoxide (Z―CHOCH2) with a hydroxyl group to form an ether bond.

[0195] Examples of the synthesis method for substituting the hydrogen atom of the hydroxyl group of a natural product with an alkyl group include a method of reacting a natural product containing a hydroxyl group with an aqueous alkaline solution of a haloalkyl compound (e.g., sodium hydroxide, potassium hydroxide); or a method of reacting a natural product containing a hydroxyl group in an organic solvent in which an alkaline compound and a haloalkyl compound are dissolved. Thus, the hydrogen atom of the hydroxyl group is substituted with an alkyl group.

[0196] The haloalkyl compound is preferably a compound represented by C n H 2n+1 ―X, where n = 1 to 40, X = Cl, Br, I.

[0197] Specific examples of the haloalkyl compound include halomethyl, haloethyl, halopropyl, halobutyl, halopentyl, halohexyl, haloheptyl, halooctyl, halononyl, halodecyl, haloundecyl, halododecyl, halotridecyl, halotetradecyl, halopentadecyl, halohexadecyl, haloheptadecyl, halooctadecyl, halononadecyl, haloeicosyl, haloeicosyl, halodocosyl, halotricosyl, etc.

[0198] By reacting a natural product containing a hydroxyl group (natural compound containing a hydroxyl group) with an epoxide, a natural product having an ether bond is obtained.

[0199] The epoxide is preferably a compound represented by C n H 2n+1 ―CHOCH2, where n = 1 to 40.

[0200] The epoxide is preferably a monofunctional epoxide having one three-membered ring ether structure. Specific examples of the epoxide include ethylene oxide, propylene oxide, 1-butylene oxide, 2-butylene oxide, stearyl glycidyl ether, cetyl glycidyl ether, etc.

[0201] <Substituents other than the R group>

[0202] The hydrogen atom of the hydroxyl group of the natural product can also be substituted by an ionic substituent other than R. The ionic group is an anionic group and / or a cationic group.

[0203] As the anionic group, monomers having a carboxyl group, a sulfonic acid group, or a phosphoric acid group can be cited.

[0204] As salts of the anionic group, alkali metal salts, alkaline earth metal salts or ammonium salts can be cited. For example, methylammonium salts, ethanolammonium salts, triethanolammonium salts, etc. can be cited.

[0205] As the cationic group, it is an amino group, preferably a tertiary amino group and a quaternary ammonium group. In the tertiary amino group, the two groups bonded to the nitrogen atom may be the same or different, and are preferably aliphatic groups having 1 to 5 carbon atoms (especially alkyl groups), aromatic groups having 6 to 20 carbon atoms (aryl groups) or araliphatic groups having 7 to 25 carbon atoms (especially aralkyl groups, such as benzyl (C6H5―CH2―)). In the quaternary ammonium group, the three groups bonded to the nitrogen atom may be the same or different, and are preferably aliphatic groups having 1 to 5 carbon atoms (especially alkyl groups), aromatic groups having 6 to 20 carbon atoms (aryl groups) or araliphatic groups having 7 to 25 carbon atoms (especially aralkyl groups, such as benzyl (C6H5―CH2―)). In the tertiary amino group and the quaternary ammonium group, the remaining group bonded to the nitrogen atom may be a carbon-carbon double bond. The cationic group may also appear in the form of a salt.

[0206] The cationic group of the salt is a salt formed with an acid (organic acid or inorganic acid). The organic acid is preferably a carboxylic acid having 1 to 20 carbon atoms, especially a monocarboxylic acid such as acetic acid, propionic acid, butyric acid, stearic acid, etc.

[0207] <Treatment agent (oil-resistant agent)>

[0208] The treatment agent (oil-resistant agent) includes modified natural products. The oil-resistant agent has oil resistance and may further have water resistance, water repellency, and oil repellency. In addition to the modified natural products, the oil-resistant agent may also contain a liquid medium (water, organic solvent or a mixed solution thereof). The oil-resistant agent may further contain at least one selected from surfactants, blocked isocyanate compounds, and additives.

[0209] The amount of the modified natural product may be 0.1% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, or 30% by weight or more relative to the oil-resistant agent. The amount of the modified natural product relative to the oil-resistant agent may be 100% by weight or less, 75% by weight or less, 50% by weight or less, or 40% by weight or less.

[0210] The oil-resistant agent may contain an aqueous medium. The liquid medium may be water alone, an organic solvent alone (such as alcohol, ketone, ester) or a mixture of water and an organic solvent, and is preferably water alone.

[0211] Relative to the oil-resistant agent, the amount of the liquid medium may be 30% by weight or more, 50% by weight or more, 60% by weight or more, 75% by weight or more, or 90% by weight or more, and the amount of the liquid medium may be 99% by weight or less, 95% by weight or less, 75% by weight or less, or 50% by weight or less.

[0212] When the liquid medium is a mixture of water and an organic solvent, the amount of the organic solvent (such as alcohol, ester, ketone) relative to the liquid medium can be 3 wt% or more, 10 wt% or more, 30 wt% or more, 50 wt% or more, or 75 wt% or more. The amount of the organic solvent relative to the liquid medium can be 90 wt% or less, 50 wt% or less, 30 wt% or less, or 10 wt% or less.

[0213] The oil-resistant agent can be a solution (especially an aqueous solution) or a dispersion composition (especially an aqueous dispersion (aqueous dispersion composition)).

[0214] <Surfactant or dispersant>

[0215] The oil-resistant agent can be free of or contain a surfactant (emulsifier) or a dispersant. Generally, for the stabilization of particles in the substitution reaction of hydroxyl groups and the stabilization of the aqueous dispersion after the reaction, a small amount (for example, relative to 100 parts by weight of the natural product, 0.01 to 100 parts by weight or 0.01 to 50 parts by weight, such as 0.1 to 15 parts by weight) of a surfactant or a dispersant can be added during the reaction, or a surfactant or a dispersant can also be added after the reaction.

[0216] Especially when the article to be treated is a fiber product, in the oil-resistant agent, the surfactant or dispersant preferably includes a nonionic surfactant. Moreover, the surfactant preferably includes one or more surfactants selected from cationic surfactants, anionic surfactants, and amphoteric surfactants. A combination of a nonionic surfactant and a cationic surfactant is preferably used.

[0217] The nonionic surfactant, cationic surfactant, and amphoteric surfactant can be used alone or in combinations of two or more.

[0218] The amount of the surfactant or dispersant is 100 parts by weight or less, 50 parts by weight or less, 25 parts by weight or less, 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 relative to 100 parts by weight of the total amount of the natural product (or modified natural product). Generally, after adding the surfactant or dispersant, the stability of the aqueous dispersion, the permeability to penetrate into the fabric, etc. are improved.

[0219] <Blocked isocyanate compound>

[0220] The oil-resistant agent can be free of or contain a blocked isocyanate compound. The blocked isocyanate compound can be added before the substitution reaction of hydroxyl groups or after the reaction (for example, before the curing process).

[0221] The blocked isocyanate compound can be prepared by reacting an isocyanate (as long as it is a compound represented by A(NCO) m is fine) with a blocking agent (as long as it is a compound represented by RH). In the formula, A is the residue remaining after removing the isocyanate group from the isocyanate compound, and m is an integer from 2 to 8; R is a hydrocarbon group that can be substituted by heteroatoms such as nitrogen atoms or oxygen atoms, and H is a hydrogen atom.

[0222] A(NCO) m is, for example, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), etc. Examples of the blocking agent forming the R group are oxime, phenol, alcohol, thiol, amide, imide, imidazole, urea, amine, imine, pyrazole, and active methylene compounds.

[0223] As the blocked isocyanate compound, blocked toluene diisocyanate with oxime, blocked hexamethylene diisocyanate, blocked diphenylmethane diisocyanate and other blocked isocyanates are preferred.

[0224] The amount of the blocked isocyanate compound, relative to 100 parts by weight of the modified natural product, can 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, 2.5 parts by weight or less.

[0225] <Additive>

[0226] The oil-resistant agent may contain additives. Examples of the additives are binder resin, dispersant, water-resistant agent, oil-resistant agent, water-repellent agent, oil-repellent agent, drying speed regulator, crosslinking agent, film-forming aid, compatibilizer, antifreeze, viscosity regulator, ultraviolet absorber, antioxidant, pH regulator, defoaming agent, texture regulator, sliding property regulator, antistatic agent, hydrophilic agent, antibacterial agent, preservative, insect repellent, fragrance, flame retardant, sizing agent, paper strength enhancer. The amount of the additive, relative to 100 parts by weight of the modified natural product, can be 0.1 to 20 parts by weight, for example, 0.1 to 10 parts by weight.

[0227] <Properties of the oil-resistant agent and the modified natural product>

[0228] The contact angle of n-hexadecane with respect to the modified natural product (or the oil-resistant agent) (on a glass substrate) can be 5° or more, 10° or more, 11° or more, 12° or more, or 15° or more, preferably 20° or more, 25° or more, or 30° or more, and more preferably 35° or more, 40° or more, or 45° or more. From the viewpoints such as excellent liquid-repellent property of the oil-resistant agent, especially oil resistance, it is preferred to make the contact angle of n-hexadecane within the above range.

[0229] The surface free energy of the modified natural product is preferably 20 mN / m ﹣1 or more, 25 mN / m﹣1 above or 30 mNm ﹣1 or more, preferably 70 mNm ﹣1 below, 60 mNm ﹣1 below or 50 mNm ﹣1 below.

[0230] The preferred range of the difference in SP value between the modified natural product (or oil-resistant agent) and corn oil can be 3 or more, 5 or more, or 7 or more.

[0231] The melting point of the modified natural product is preferably 40 °C or higher, 50 °C or higher, 60 °C or higher, 70 °C or higher, 80 °C or higher, 90 °C or higher, 100 °C or higher, 110 °C or higher, 120 °C or higher, or 140 °C or higher. In addition, the melting point of the oil-resistant agent is preferably 200 °C or lower, 180 °C or lower, 160 °C or lower.

[0232] From the viewpoints of improving the coating property and temperature tolerance after treating the fiber product, especially oil resistance, etc., the melting point of the oil-resistant agent is preferably within the above range.

[0233] The glass transition temperature of the modified natural product is preferably 30 °C or higher, 40 °C or higher, 50 °C or higher, 60 °C or higher, 70 °C or higher, 80 °C or higher, 90 °C or higher, 100 °C or higher, 110 °C or higher, 120 °C or higher, or 140 °C or higher. Additionally, the glass transition temperature of the modified natural product is preferably 180 °C or lower, 140 °C or lower, 130 °C or lower, 120 °C or lower. From the viewpoints of improving the coating property and temperature tolerance after treating the fiber product, especially oil resistance, etc., the glass transition temperature of the modified natural product is preferably within the above range.

[0234] The viscosity of the polymer (modified natural product) solution of the oil-resistant agent at a 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. In addition, the viscosity of the polymer solution of the oil-resistant agent at a concentration of 14.8 mg / mL is preferably 1000 cP or lower, 500 cP or lower, or 100 cP or lower. From the viewpoint of improving the coating property after treating the fiber product, especially oil resistance, etc., the viscosity of the polymer solution of the oil-resistant agent is preferably within the above range.

[0235] The air permeability of the treated paper is preferably 100 s / 100 cc or more, 200 s / 100 cc or more, 300 s / 100 cc or more, 400 s / 100 cc or more, 500 s / 100 cc or more, 700 s / 100 cc or more, or 1000 s / 100 cc or more. By making the air permeability of the treated paper above the above values, the voids between the fibers are sealed, and particularly the oil resistance is improved. The treated paper for measuring the air permeability is a polymer (modified natural product) of an oil-resistant agent with a solution concentration of 14.8 mg / mL, and the base paper of a paper with a basis weight of 45 g / m2 and a paper density of 0.58 g / cm 3 is made by repeatedly performing three coating and drying operations on the base paper with a beaker applicator set to 0 mil, and annealing at a temperature of 70 °C to 180 °C (for example, 70 °C) for 10 minutes.

[0236] The preferred range of the combination of the contact angle of hexadecane and the air permeability can be 5 degrees or more × 200 s or more, 10 degrees or more × 200 s or more, 30 degrees or more × 200 s or more, or 40 degrees or more × 200 s or more. Alternatively, the preferred range of the combination of the contact angle of hexadecane and the air permeability can be 11 degrees or more × 250 s or more, 15 degrees or more × 250 s or more, 30 degrees or more × 250 s or more, or 40 degrees or more × 250 s or more. Alternatively, the preferred range of the combination of the contact angle of hexadecane and the air permeability can be 11 degrees or more × 300 s or more, 15 degrees or more × 300 s or more, 30 degrees or more × 300 s or more, or 40 degrees or more × 300 s or more. The preferred range of the combination of the contact angle of hexadecane and the air permeability of the alternative can be 11 degrees or more × 350 s or more, 15 degrees or more × 350 s or more, 30 degrees or more × 350 s or more, or 40 degrees or more × 350 s or more.

[0237] The product of the contact angle of hexadecane and the air permeability is preferably 1500 (degree·s) or more, 2000 (degree·s) or more, 2500 (degree·s) or more, 3000 (degree·s) or more, 3500 (degree·s) or more, 4000 (degree·s) or more, 5000 or more (degree·s), 6000 (degree·s) or more, 7000 (degree·s) or more, 8000 (degree·s) or more, 9000 (degree·s) or more, or 10000 (degree·s) or more. The upper limit of the product of the contact angle of hexadecane and the air permeability can be 300000 (degree·s), 200000 (degree·s), or 100000 (degree·s). The product of the contact angle of hexadecane and the air permeability being above the above values means that either the liquid-repellent property or the coating property of the oil-resistant agent is in a state sufficient to exhibit oil resistance.

[0238] <Use of modified natural product>

[0239] The modified natural product can be used as various preparations or their components such as oil-resistant agents, water-resistant agents, water-repellent agents, oil-repellent agents, antifouling agents, dirt removers, release agents or mold release agents. The modified natural product can be used as an external treatment agent (surface treatment agent) or an internal treatment agent or its component.

[0240] By treating a substrate with the modified natural product, the modified natural product can form a surface coating structure on the surface of the substrate.

[0241] In order to make the treated object (substrate) exhibit liquid repellency, it is preferably dried, preferably heated at a temperature above the Tg of the modified natural product, for example, at a temperature of 100°C to 200°C. By treating at a temperature above the Tg of the modified natural product, the surface of the substrate can be coated with the modified natural product and side chain orientation can be induced. Thereby, a surface coating structure with excellent hydrophobicity can be formed.

[0242] The surface coating structure can be formed by applying the modified natural product to the object to be treated (substrate) by known methods and attaching it to the surface of the substrate. Generally, the method of dispersing the modified natural product in an organic solvent or water and diluting it, and then attaching the modified natural product to the surface of the object to be treated and drying it by known methods such as dip coating, spraying, and foam coating is adopted. In addition, if necessary, it can be applied together with a suitable crosslinking agent (such as a blocked isocyanate compound) for curing. In addition, a repellent, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a coating fixing agent, an anti-wrinkle agent, a sizing agent, a paper strength enhancer, etc. can also be added and used in the modified natural product.

[0243] Examples of the object to be treated with the preparation containing the modified natural product include fiber products, stones, filters (such as electrostatic filters), dust masks, components of fuel cells (such as gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, coated surfaces, and gypsum.

[0244] As fiber products, various examples can be cited, such as fabric products, paper products, etc.

[0245] Examples of fabric products include natural fibers of animals and plants 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 mixed fibers of the above fibers. Fabric products include textiles, knitted fabrics, and non-woven fabrics, fabrics in the form of clothing fabrics and carpets, but fibers, yarns, and intermediate fiber products (such as flakes or rovings, etc.) in the state before forming a fabric can also be treated.

[0246] As examples of paper products, mention may be made of paper formed from bleached or unbleached chemical pulp such as kraft pulp or sulfate pulp, wastepaper pulp such as waste newspapers, old magazines, old corrugated boards or deinked wastepaper, high-yield pulp such as bleached or unbleached groundwood pulp, mechanical pulp or thermomechanical pulp, containers that can be made of paper, molded bodies that can be formed from paper, etc. Specific examples of paper products include food wrapping paper, base paper for gypsum board, base paper for coating, medium paper, ordinary liners and cores, neutral pure white roll paper, neutral liners, rust-proof liners and metal separator paper, kraft paper, neutral printing and writing paper, neutral base paper for coating, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc. Since the modified natural product of the present invention has excellent oil resistance (for example, high-temperature oil resistance), it can be applied to uses that require oil resistance, and is particularly suitable for food packaging materials and food containers.

[0247] The modified natural product can be applied to fibrous substrates (such as fibrous products, etc.) by any known method of treating fibrous products with a liquid. When the fibrous product is cloth, the cloth can be immersed in a solution, or the solution can be attached or sprayed onto the cloth. The treatment can be an external application treatment or an internal mixing treatment. When the fibrous product is paper, it can be coated on the paper, or the solution can be attached or sprayed onto the paper, or it can also be treated by mixing with the pulp before papermaking. The treatment can be an external application treatment or an internal mixing treatment.

[0248] The modified natural product can be applied to pre-formed fibrous products (especially paper, cloth, etc.), or applied at various stages of papermaking, for example, it can be applied during the drying of the paper. The modified natural product can be applied to fibrous products by a cleaning method, for example, applied to fibrous products during washing application or in dry cleaning methods, etc.

[0249] Alternatively, the fibrous substrate can be leather. To impart hydrophobicity and oleophobicity to the leather, the modified natural product can be applied to the leather from an aqueous solution or an aqueous emulsion at various stages of leather processing, such as during the wet processing of the leather or during the finishing of the leather.

[0250] The modified natural product can also be used as an external mold release agent. It can enable the surface of a substrate to be easily peeled off from other surfaces (other surfaces on the substrate or surfaces on other substrates).

[0251] In the case of paper products, there is, for example, a method of spraying a solution of the natural modified product into a paper pulp mold and heating and drying it.

[0252] Alternatively, the natural modified product dispersed in a paper pulp slurry solution using an emulsifier, etc. can also be mixed, followed by dehydration molding and hot pressing. Crosslinking agents, paper strength enhancers, fixing agents, etc. can be added to the paper pulp slurry.

[0253] Alternatively, the paper can also be impregnated into the natural modifier dispersion solution and then heated and dried.

[0254] In the case of fabric products, there is a method of impregnating the fabric into the natural modifier dispersion solution or spraying the solution onto the fabric, followed by dehydration and then heating and drying.

[0255] "Treatment" means applying a treatment agent to an object to be treated by means such as impregnation, spraying, coating, etc. Through treatment, the modified natural product, which is the active ingredient of the treatment agent, penetrates into the interior of the object to be treated and / or adheres to the surface of the object to be treated.

[0256] <Paper Additive>

[0257] The modified natural product can be suitably used as a paper additive. The paper additive containing the modified natural product can be used as a water-resistant agent, an oil-resistant agent, a water-repellent agent, and / or an oil-repellent agent. The paper additive is preferably in the form of a solution (especially a solution of an organic solvent), an emulsion (especially an aqueous emulsion), or an aerosol. The paper additive contains a modified natural product and a medium (such as a liquid medium like an organic solvent and water). The paper additive is preferably an aqueous dispersion of the modified natural product. In the paper additive, the concentration of the modified natural product can be, for example, 0.01 to 50% by weight. The paper additive may not contain a surfactant.

[0258] The removal of the organic solvent contained in the paper additive can be achieved by heating the modified natural product solution (preferably under reduced pressure) (for example, at 30°C or higher, for example, 50 to 120°C).

[0259] The paper additive can be used to treat (such as surface-treat) a paper substrate. The paper additive can be applied to the object to be treated by known methods. Generally, a method (surface treatment) is adopted in which the paper additive is dispersed in an organic solvent or water and diluted, and then the paper additive is attached to the surface of the object to be treated and dried by known methods such as dip coating, spraying, foam coating, etc. As the paper substrate as the object to be treated, paper, a container made of paper, a molded body made of paper (such as a pulp mold), etc. can be cited. The modified natural product of the present invention can adhere well to the paper substrate. In this specification, adhesion means physical bonding or chemical bonding. By attaching the modified natural product to the paper substrate, an oil-resistant paper can be obtained.

[0260] The above describes the embodiments, but it should be understood that various changes can be made to the embodiments and details without departing from the gist and scope of the present invention.

[0261] Examples

[0262] Next, examples are given to specifically illustrate the present invention. However, these descriptions do not limit the present invention. Hereinafter, unless otherwise specified, "parts", "%", or "ratio" represent parts by weight, % by weight, or weight ratio.

[0263] The test methods used below are described as follows.

[0264] Preparation of treated paper

[0265] As the wood pulp, a pulp slurry with a weight ratio of 60 wt% of LBKP (bleached hardwood kraft pulp) and 40 wt% of NBKP (bleached softwood kraft pulp) and a drainage degree of 400 ml (Canadian Standard Freeness) was prepared. A wet strength agent and a sizing agent were added to the pulp slurry, and a paper with a basis weight of 45 g / m2 and a paper density of 0.58 g / cm3 was used as the base paper for external coating treatment (sizing treatment) through a Fourdrinier paper machine. The oil resistance (KIT value) of this base paper was 0, and the water resistance (Cobb value) was 52 g / m2.

[0266] The base paper was repeatedly coated three times with a polymer solution (chloroform, toluene, or acetone) of 14.9 mg / cm 3 using a Baker applicator with a gap set to 0 mil and then dried, and annealed at 70 °C for 10 minutes to produce a treated paper.

[0267] KIT test (oil resistance)

[0268] Measurement was carried out by the 3M Kit Test Method (TAPPI T-559cm-02). The 3M Kit Test Method is to place a test oil containing castor oil, toluene, and heptane on the surface of the treated paper, wipe off the test oil after 15 seconds, and evaluate whether there is an oil stain on the treated paper at this time. Tests were carried out using the test oils numbered 1 - 6 in the kit, and the largest kit number for which no oil stain was observed was used as the oil resistance evaluation result.

[0269] Evaluation of corn oil tolerance (oil resistance)

[0270] Corn oil was placed on the surface of the treated paper, wiped off the test oil after 15 seconds, and evaluated whether there was an oil stain on the treated paper at this time. The case without an oil stain was marked as "○", and the case with an observed oil stain was marked as "×".

[0271] Liquid repellency (static contact angle)

[0272] The liquid repellency was measured by spin-coating a solution with a solid component 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) on the coated film and measuring the contact angle 1 second after dropping.

[0273] Air permeability

[0274] The air permeability (air resistance) of the treated paper was measured according to JIS P8117 (2009) using an automatic Gurley - type electric tester (product model: No.323 - AUTO, ventilation hole diameter 28.6 ± 0.1 mm) manufactured by Yasuda Seiki Seisakusho Co., Ltd.

[0275] Substitution rate

[0276] By 1 1H NMR or elemental analysis, the substitution rate of the oil - resistant agent was determined.

[0277] Example 1

[0278] A stir bar, 4.0 g of cellulose (20 - μm powder), and 4.0 g of LiCl were added to a reaction vessel equipped with a reflux condenser and a nitrogen inlet tube, and dried under reduced pressure at 80 °C for 4 hours. Then, 40 mL of dimethylformamide was added, and the mixture was stirred at 150 °C for 1 hour. Then, it was returned to room temperature, and 0.1 g of dibutyltin dilaurate was added. The temperature was adjusted to 120 °C, 22.2 g of octadecyl isocyanate (3 equivalents relative to the OH of the repeating unit) and 10 mL of dimethylformamide were added, and the mixture was stirred for 12 hours. After 1 confirming the disappearance of octadecyl isocyanate by 1H NMR, the reaction vessel was cooled to room temperature, and the reaction mixture was dropped into water to precipitate solids. The precipitated solids were recovered by suction filtration, washed once with methanol and once with acetone. The recovered solids were reprecipitated using chloroform as a good solvent and hexane as a poor solvent to obtain a derivative of cellulose modified with octadecyl isocyanate as an oil - resistant agent. The substitution rate of this derivative was 100%. The liquid - repellency, KIT test, corn oil tolerance, and air permeability were evaluated using this derivative. The results are shown in Table 1.

[0279] Example 2

[0280] A stir bar and 1.6 g of hydroxypropyl cellulose (molecular weight 80,000) synthesized from cellulose were added to a reaction vessel equipped with a reflux condenser and a nitrogen inlet tube, and dried under reduced pressure at 80 °C for 4 hours. 25 mL of chloroform was added, and the mixture was stirred at 60 °C for 1 hour. Then, 0.1 g of dibutyltin dilaurate, 4.4 g of octadecyl isocyanate (3 equivalents relative to the OH of the repeating unit), and 5 mL of chloroform were added, and the mixture was stirred at 60 °C for 7 hours. After 1After confirming the disappearance of octadecyl isocyanate by \(^1\)H NMR, the reaction vessel was cooled to room temperature, and the reaction mixture was concentrated using a rotary evaporator. Reprecipitation was carried out using ethyl acetate as a poor solvent to obtain a derivative of propyl cellulose modified with octadecyl isocyanate as an oil-resistant agent. The substitution rate of this derivative was 100%. The liquid repellency, KIT test, corn oil tolerance, and air permeability were evaluated using this derivative. The results are shown in Table 1.

[0281] Example 3

[0282] As an oil-resistant agent, cellulose acetate (1.14 eq modified body, substitution rate: 38%) synthesized from cellulose was used, and the liquid repellency, KIT test, corn oil tolerance, and air permeability were evaluated. The results are shown in Table 1.

[0283] Comparative Example 1

[0284] As an oil-resistant agent, cellulose (20 μm powder) was used, and the liquid repellency, KIT test, corn oil tolerance, and air permeability were evaluated. The results are shown in Table 1.

[0285] Comparative Example 2

[0286] As an oil-resistant agent, polyglycerol (average molecular weight 500) was used to evaluate the liquid repellency. The result was 0 points for the KIT test, × for the corn oil tolerance, and 136 s / 100 cc for the air permeability.

[0287] Example 4

[0288] A magnetic stir bar, 5.0 g of polyglycerol (average molecular weight 500), 20 mL of pyridine, 25 g of octadecyl isocyanate, and 1 drop of dibutyltin dilaurate were added to a reaction vessel, and the mixture was stirred at 60 °C for 1 hour. After 1 confirming the disappearance of octadecyl isocyanate by \(^1\)H NMR, it was dropped into hexane to precipitate a solid. The precipitated solid was recovered by suction filtration to obtain a derivative of polyglycerol modified with octadecyl isocyanate as an oil-resistant agent. The substitution rate of this derivative was 100%. The evaluation of the liquid repellency of this oil-resistant agent was 4 points for the KIT test, ○ for the corn oil tolerance, and 289 s / 100 cc for the air permeability.

[0289] Example 5

[0290] The same procedure as in Example 4 was carried out except that the amount of octadecyl isocyanate was changed to 12 g.

[0291] The substitution rate of this derivative was 54%. The evaluation of the liquid repellency of this oil-resistant agent was 4 points for the KIT test, ○ for the corn oil tolerance, and 232 s / 100 cc for the air permeability.

[0292] Example 6

[0293] 0.1 g of the derivative obtained in Example 5 was made into an emulsion with 0.1 g of polyoxyethylene oleyl ether and 9.8 g of water, and coating was carried out in the same manner. The liquid repellency evaluation of this oil-resistant agent was 4 points in the KIT test, ○ for corn oil tolerance, and the air permeability was 185 s / 100 cc.

[0294] Example 7

[0295] The procedure was the same as in Example 4 except that the amount of octadecyl isocyanate was changed to 6.3 g.

[0296] The substitution rate of this derivative was 25%. The liquid repellency evaluation of this oil-resistant agent was 5 points in the KIT test, ○ for corn oil tolerance, and the air permeability was 231 s / 100 cc.

[0297] Example 8

[0298] The procedure was the same as in Example 4 except that octadecyl isocyanate was changed to 6.2 g of octadecyl isocyanate and 4.5 g of dodecyl isocyanate.

[0299] The substitution rate of this derivative was 100%. The liquid repellency evaluation of this oil-resistant agent was 4 points in the KIT test, ○ for corn oil tolerance, and the air permeability was 224 s / 100 cc.

[0300] Example 9

[0301] A magnetic stir bar, 2.5 g of polyglycerol (average molecular weight 750), 20 mL of pyridine, and 10.6 g of octadecyl isocyanate were added to a reaction vessel, and 1 drop of dibutyltin dilaurate was added dropwise. The mixture was stirred at 60 °C for 1 hour. After 1 confirming the disappearance of octadecyl isocyanate by 1H NMR, it was dropped into hexane to precipitate a solid. The precipitated solid was recovered by suction filtration to obtain a derivative of polyglycerol modified with octadecyl isocyanate as an oil-resistant agent. The substitution rate of this derivative was 100%. The liquid repellency evaluation of this oil-resistant agent was 4 points in the KIT test, ○ for corn oil tolerance, and the air permeability was 286 s / 100 cc.

[0302] Example 10

[0303] A magnetic stir bar, 2.5 g of polyglycerol (average molecular weight 750), 20 mL of pyridine, and 0.89 g of octadecyl isocyanate were added to a reaction vessel, and 1 drop of dibutyltin dilaurate was added dropwise. The mixture was stirred at 60 °C for 1 hour. After 1After confirming the disappearance of octadecyl isocyanate by \(^1H\) NMR, the solvent was removed by distillation to obtain a derivative of polyglycerol modified with octadecyl isocyanate as an oil-resistant agent. The substitution rate of this derivative was 8%. The liquid repellency evaluation of this oil-resistant agent was 5 points in the KIT test, ○ for corn oil tolerance, and the air permeability was 277 s / 100 cc.

[0304] Example 11 (MS379P)

[0305] The compound obtained in Example 10 was formulated into a 1% aqueous solution for coating. The liquid repellency evaluation of this oil-resistant agent was 5 points in the KIT test, ○ for corn oil tolerance, and the air permeability was 269 s / 100 cc.

[0306] Example 12

[0307] A magnetic stir bar, 2.5 g of polyglycerol (average molecular weight 750), 20 mL of pyridine, and 0.44 g of octadecyl isocyanate were added to a reaction vessel, and 1 drop of dibutyltin dilaurate was added dropwise. The mixture was stirred at 60 °C for 1 hour. After 1 confirming the disappearance of octadecyl isocyanate by \(^1H\) NMR, the solvent was removed by distillation to obtain a derivative of polyglycerol modified with octadecyl isocyanate as an oil-resistant agent. The substitution rate of this derivative was 4%.

[0308] This compound was formulated into a 1% aqueous solution for coating. The liquid repellency evaluation of this oil-resistant agent was 3 points in the KIT test, ○ for corn oil tolerance, and the air permeability was 225 s / 100 cc.

[0309] Example 13

[0310] A magnetic stir bar, 0.46 g of glycerol, 10 mL of pyridine, and 4.4 g of octadecyl isocyanate were added to a reaction vessel, and 1 drop of dibutyltin dilaurate was added dropwise. The mixture was stirred at 60 °C for 1 hour. After 1 confirming the disappearance of octadecyl isocyanate by \(^1H\) NMR, it was dropped into hexane to precipitate a solid. The precipitated solid was recovered by suction filtration to obtain a derivative of glycerol modified with octadecyl isocyanate as an oil-resistant agent. The substitution rate of this derivative was 100%. The liquid repellency evaluation of this oil-resistant agent was 4 points in the KIT test, ○ for corn oil tolerance.

[0311] Example 14

[0312] A magnetic stir bar, 0.92 g of glycerol, 10 mL of pyridine, and 4.4 g of octadecyl isocyanate were added to a reaction vessel, and 1 drop of dibutyltin dilaurate was added dropwise. The mixture was stirred at 60 °C for 1 hour. After 1After confirming the disappearance of octadecyl isocyanate by \(^1\)H NMR, it was dropped into hexane to precipitate a solid. The precipitated solid was recovered by suction filtration to obtain a derivative of glycerol modified with octadecyl isocyanate as an oil-resistant agent. The substitution rate of this derivative was 50%. The drainage property evaluation of this oil-resistant agent was 4 points in the KIT test and ○ for corn oil tolerance.

[0313] Example 15

[0314] A stir bar, 1.7 g of diglycerol, 20 mL of pyridine, and 11.8 g of octadecyl isocyanate were added to a reaction vessel, and 1 drop of dibutyltin dilaurate was added dropwise. The mixture was stirred at 60 °C for 1 hour. After 1 confirming the disappearance of octadecyl isocyanate by \(^1\)H NMR, it was dropped into hexane to precipitate a solid. The precipitated solid was recovered by suction filtration to obtain a derivative of diglycerol modified with octadecyl isocyanate as an oil-resistant agent. The substitution rate of this derivative was 100%. The drainage property evaluation of this oil-resistant agent was 4 points in the KIT test and ○ for corn oil tolerance.

[0315] Example 16

[0316] A stir bar, 1.7 g of diglycerol, 20 mL of pyridine, and 3.0 g of octadecyl isocyanate were added to a reaction vessel, and 1 drop of dibutyltin dilaurate was added dropwise. The mixture was stirred at 60 °C for 1 hour. After 1 confirming the disappearance of octadecyl isocyanate by \(^1\)H NMR, it was dropped into hexane to precipitate a solid. The precipitated solid was recovered by suction filtration to obtain a derivative of diglycerol modified with octadecyl isocyanate as an oil-resistant agent. The substitution rate of this derivative was 25%. The drainage property evaluation of this oil-resistant agent was 4 points in the KIT test and ○ for corn oil tolerance.

[0317] Example 17

[0318] A stir bar, 0.5 g of maltitol, 15 mL of DMSO, and 4.0 g of octadecyl isocyanate were added to a reaction vessel, and 1 drop of dibutyltin dilaurate was added dropwise. The mixture was stirred at 60 °C for 1 hour. After 1 confirming the disappearance of octadecyl isocyanate by \(^1\)H NMR, it was washed with hexane and water to obtain a derivative of maltitol modified with octadecyl isocyanate as an oil-resistant agent. The substitution rate of this derivative was 100%. The drainage property evaluation of this oil-resistant agent was 4 points in the KIT test, ○ for corn oil tolerance, and the air permeability was 1243 s / 100 cc.

[0319] Example 18

[0320] Except for changing octadecyl isocyanate to 2.0 g, the procedure was the same as in Example 17 to obtain a derivative of maltitol modified with octadecyl isocyanate. The substitution rate of this derivative was 60%. The liquid repellency evaluation of this oil-resistant agent showed a score of 3 in the KIT test, ○ for corn oil tolerance, and a gas permeability of 400 s / 100 cc.

[0321] Example 19

[0322] A stir bar, 1.8 g of sorbitol, 20 mL of DMF, and 18 g of octadecyl isocyanate were added to a reaction vessel, and 1 drop of dibutyltin dilaurate was added dropwise. The mixture was stirred at 60 °C for 1 hour. After 1 confirming the disappearance of octadecyl isocyanate by 1H NMR, it was washed with hexane and acetone to obtain a derivative of sorbitol modified with octadecyl isocyanate as an oil-resistant agent. The substitution rate of this derivative was 100%. The liquid repellency evaluation of this oil-resistant agent showed a score of 5 in the KIT test and ○ for corn oil tolerance.

[0323] Example 20

[0324] A stir bar, 1.8 g of sorbitol, 20 mL of DMF, and 8.9 g of octadecyl isocyanate were added to a reaction vessel, and 1 drop of dibutyltin dilaurate was added dropwise. The mixture was stirred at 60 °C for 1 hour. After 1 confirming the disappearance of octadecyl isocyanate by 1H NMR, it was washed with hexane and acetone to obtain a derivative of sorbitol modified with octadecyl isocyanate as an oil-resistant agent. The substitution rate of this derivative was 50%. The liquid repellency evaluation of this oil-resistant agent showed a score of 5 in the KIT test, ○ for corn oil tolerance, and a gas permeability of 729 s / 100 cc.

[0325] Example 21

[0326] A stir bar, 1.8 g of sorbitol, 20 mL of DMF, and 4.4 g of octadecyl isocyanate were added to a reaction vessel, and 1 drop of dibutyltin dilaurate was added dropwise. The mixture was stirred at 60 °C for 1 hour. After 1 confirming the disappearance of octadecyl isocyanate by 1H NMR, it was washed with hexane and acetone to obtain a derivative of sorbitol modified with octadecyl isocyanate as an oil-resistant agent. The substitution rate of this derivative was 25%. The liquid repellency evaluation of this oil-resistant agent showed a score of 5 in the KIT test, ○ for corn oil tolerance, and a gas permeability of 449 s / 100 cc.

[0327] Example 22

[0328] A stir bar, 1.8 g of sorbitol, 20 mL of DMF, and 2.9 g of octadecyl isocyanate were added to a reaction vessel, and 1 drop of dibutyltin dilaurate was added dropwise. The mixture was stirred at 60 °C for 1 hour. After 1After confirming the disappearance of octadecyl isocyanate by \(^1H\) NMR, it was washed with hexane and acetone to obtain a derivative of sorbitol modified with octadecyl isocyanate as an oil-resistant agent. The substitution rate of this derivative was 16%. The drainage property evaluation of this oil-resistant agent was 4 points in the KIT test, ○ for corn oil tolerance, and the air permeability was 897 s / 100 cc.

[0329] Example 23

[0330] A stir bar, 1.8 g of sorbitol, 20 mL of pyridine, and 9.1 g of \(C_{17}H_{35}COCl\) were added to a reaction vessel and stirred overnight at a temperature of 60 °C. It was washed with hexane and acetone to obtain a derivative of sorbitol modified with \(C_{17}H_{35}\) ester as an oil-resistant agent.

[0331] The substitution rate of this derivative was 50%. The drainage property evaluation of this oil-resistant agent was 4 points in the KIT test and ○ for corn oil tolerance.

[0332] Example 24

[0333] A stir bar, 1.8 g of mannitol, 20 mL of DMF, and 8.9 g of octadecyl isocyanate were added to a reaction vessel, and 1 drop of dibutyltin dilaurate was added dropwise. It was stirred at a temperature of 60 °C for 1 hour. After 1 confirming the disappearance of octadecyl isocyanate by \(^1H\) NMR, it was washed with hexane and acetone to obtain a derivative of mannitol modified with octadecyl isocyanate as an oil-resistant agent. The substitution rate of this derivative was 50%. The drainage property evaluation of this oil-resistant agent was 5 points in the KIT test and ○ for corn oil tolerance.

[0334] Example 25

[0335] A stir bar, 0.40 g of dextrin, and 10 mL of DMSO were added to a reaction vessel and heated to 60 °C. After dissolving the dextrin, 1 drop of dibutyltin dilaurate, 2.2 g of octadecyl isocyanate, and 2 mL of \(CHCl_3\) were added dropwise, and it was stirred at a temperature of 60 °C. The solid was recovered with a weak solvent to obtain a derivative. The substitution rate of this derivative was 70%. The drainage property evaluation of this oil-resistant agent was 3 points in the KIT test, ○ for corn oil tolerance, and the air permeability was 1281.7 s / 100 cc.

[0336] Example 26

[0337] As an oil-resistant agent, decaglycerol tristearate was used to evaluate the drainage property, KIT test, corn oil tolerance, and air permeability. The HD contact angle of this oil-resistant agent was 41.1°, the KIT test was 4 points, the corn oil tolerance was ○, and the air permeability was 252.1 s / 100 cc.

[0338] Example 27

[0339] As an oil-resistant agent, hexaglycerol tristearate was used, and liquid repellency, KIT test, corn oil tolerance, and air permeability were evaluated. The HD contact angle of this oil-resistant agent was 40.6°, the KIT test score was 4, the corn oil tolerance was ○, and the air permeability was 230.4 s / 100 cc.

[0340] Example 28

[0341] As an oil-resistant agent, hexaglycerol pentastearate was used, and liquid repellency, KIT test, corn oil tolerance, and air permeability were evaluated. The HD contact angle of this oil-resistant agent was 41.9°, the KIT test score was 4, the corn oil tolerance was ○, and the air permeability was 230.6 s / 100 cc.

[0342] Example 29

[0343] As an oil-resistant agent, decaglycerol heptabehenate was used, and liquid repellency, KIT test, corn oil tolerance, and air permeability were evaluated. The HD contact angle of this oil-resistant agent was 40.5°, the KIT test score was 5, the corn oil tolerance was ○, and the air permeability was 604.0 s / 100 cc.

[0344] Example 30

[0345] As an oil-resistant agent, decaglycerol decabehenate was used, and liquid repellency, KIT test, corn oil tolerance, and air permeability were evaluated. The HD contact angle of this oil-resistant agent was 40.5°, the KIT test score was 5, the corn oil tolerance was ○, and the air permeability was 236.6 s / 100 cc.

[0346] Example 31

[0347] As an oil-resistant agent, hexaglycerol monostearate was used, and liquid repellency, KIT test, corn oil tolerance, and air permeability were evaluated. The HD contact angle of this oil-resistant agent was 41.1°, the KIT test score was 5, the corn oil tolerance was ○, and the air permeability was 237.6 s / 100 cc.

[0348] Example 32

[0349] 5.8 g of sheep oil fatty acid was mixed in 30 ml of pyridine and heated to 50 °C. 8.85 g of BOP reagent was added, and 0.46 g of glycerol was added after 1 hour, followed by heating overnight. The resulting solid was washed with dilute hydrochloric acid and acetone, and the derivative of glycerol modified with sheep oil fatty acid was obtained by suction filtration as an oil-resistant agent. The substitution rate of this derivative was 100%. The oil resistance evaluation of this oil-resistant agent was a KIT test score of 3.

[0350] Example 33

[0351] 4.35 g of a carboxylic acid-modified polyorganosiloxane (functional group equivalent: 1,450 g / mol), 10 ml of pyridine, and 1.77 g of BOP reagent were stirred for 1 hour. Then, 4.35 g of glycerol was added, and the mixture was stirred at 60°C for one day. After cooling, the product was extracted with chloroform, washed with water, and the solvent was removed by distillation. A derivative modified with a carboxylic acid-modified polyorganosiloxane was obtained. The substitution rate of this derivative was 100%. The oil resistance evaluation of this oil-resistant agent was 3 points in the KIT test.

[0352] The results of Examples 1 to 33 and Comparative Examples 1 to 2 are shown in Table 1.

[0353] Table 1

[0354]

[0355] Industrial Applicability

[0356] The modified natural product of the present invention can be used as an oil-resistant agent, a water-resistant agent, a water-repellent agent, an oil-repellent agent, an antifouling agent, a dirt remover, a release agent, or a mold release agent, and particularly can be used as an oil-resistant agent. The modified natural product can be applied to uses that require oil resistance, and particularly to food uses such as food packaging materials and food containers.

Claims

1. An oil-resistant agent, characterized in that: The oil-resistant agent contains a modified natural product in which at least one hydrogen atom of a hydroxyl group in a natural product having at least one hydroxyl group is replaced by an R group at a substitution rate of 30% or more. The natural product does not include starch. The oil-resistant agent satisfies one or more of the following (1) to (3). The modified natural product is not a composite esterification product synthesized from three components of a polyhydric alcohol having a valence of 2 or more and 6 or less, an aromatic dicarboxylic acid, and a monobasic acid. The R group is a group represented by -Y-Z. In the formula, Y is a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-, where R' is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Z is a saturated aliphatic hydrocarbon group having 7 to 40 carbon atoms which may have a substituent, or a polysiloxane. (1) The natural product is cellulose, dextrin, glycerol, or polyglycerol. (2) Y is a direct bond, -C(=O)-NR'-, or -C(=S)-NR'-, where R' is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. (3) Z is a polysiloxane.

2. The oil-resistant agent according to claim 1, characterized in that: The substitution rate of the hydrogen atom of the hydroxyl group replaced by R is 30 to 100%.

3. The oil-resistant agent according to claim 1 or 2, characterized in that: The contact angle of the oil-resistant agent with n-hexadecane shows 10 degrees or more.

4. The oil-resistant agent according to claim 1 or 2, characterized in that: The melting point of the modified natural product is 40 degrees or more or there is no melting point.

5. The oil-resistant agent according to claim 1 or 2, characterized in that: The viscosity of the oil-resistant agent with a solution concentration of 14.8 mg / mL is 5 cP or more and 100 cP or less.

6. The oil-resistant agent according to claim 1 or 2, characterized in that: The oil-resistant agent is a water-dispersed composition.

7. The oil-resistant agent according to claim 1 or 2, characterized in that: The oil-resistant agent is an oil-resistant agent for paper.

8. A fiber product, characterized in that: An oil-resistant agent according to any one of claims 1 to 7 is attached.

9. An oil-resistant paper, characterized in that: Containing an oil-resistant agent according to any one of claims 1 to 7.

10. The oil-resistant paper according to claim 9, characterized in that: The oil-resistant paper is a food packaging material or a food container.

11. A treatment method for externally applying or internally mixing paper with an oil-resistant agent according to any one of claims 1 to 7.

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