Modified natural products and their uses

Abstract

The present invention relates to an oil-proofing agent that is in harmony with the environment and uses natural materials as biomass materials to impart sufficient oil resistance. In the oil-proofing agent of the present invention, the hydrogen atom of the hydroxyl group in the natural material having at least one hydroxyl group is substituted by an R group. The R group is a group represented by -Y-Z, wherein Y is a direct bond, -C(=O)-, -C(=O)-NR'- or -C(=S)-NR'-, wherein R' is a hydrogen atom or an alkyl group having C1 to C4 carbon atoms, and Z is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a polysiloxane. The natural material is preferably a monosaccharide, a polysaccharide, glycerol or a polyglycerol.

Description

Technical Field

[0001] The present invention relates to a modified natural product obtained by modifying a natural product and its application, and in particular to an oil resistant agent. Background Art

[0002] Paper containers are expected to replace 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 mixing oil-proof agents into the paper or applying them to the paper surface. In addition, from the perspective of environmental considerations, the demand for biodegradable materials and bio-based materials is also increasing.

[0003] Patent document 1 (Japanese Patent Publication No. 2019-99953) discloses a technology for achieving oil resistance by combining oxidized starch or hydrophobic starch with an epichlorohydrin-modified fatty acid-based sizing agent. However, in order to prevent the acetic acid odor, the pH value of the mixture needs to be adjusted. Moreover, the compatibility of modified starch and fatty acid sizing agents is very important, and it is difficult to adjust the composition.

[0004] Patent Document 2 (Japanese Patent Application Laid-Open No. 2020-066805) discloses an oil-proofing agent using modified starch, clay, a styrene-butadiene copolymer, and a defoaming agent.

[0005] Patent document 3 (Japanese Patent Publication No. 2019-70202) discloses an oil-resistant paper composed of a fluorine-containing polymer that does not contain a perfluoroalkyl group with 7 or more carbon atoms and a water-soluble or water-dispersible cellulose derivative.

[0006] Patent Document 4 (International Publication No. 2015 / 162787) discloses that cellulose having a long-chain alkyl group (having 12 to 18 carbon atoms) is used for optical film applications by acetylation of cellulose acetate. Although water resistance is described, oil resistance is not disclosed.

[0007] Patent document 5 (Japanese Patent Application Laid-Open No. 2002-012258) discloses that cellulose acetate coating can be used to impart oil resistance, water resistance, heat resistance, etc. to food containers. However, in the examples, only water resistance and heat resistance were evaluated, and oil resistance was not evaluated.

[0008] Prior Art Literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Publication No. 2019-99953

[0011] Patent Document 2: Japanese Patent Application Publication No. 2020-066805

[0012] Patent Document 3: Japanese Patent Application Publication No. 2019-70202

[0013] Patent Document 4: International Publication No. 2015 / 162787

[0014] Patent Document 5: Japanese Patent Application Publication No. 2002-012258 Summary of the invention

[0015] Problems to be solved by the invention

[0016] An object of the present invention is to provide an oil-proofing agent which is harmonious with the environment and can impart sufficient oil resistance using a natural substance as a biomass material.

[0017] Technical solutions to solve problems

[0018] The present invention relates to a modified natural product (modified natural compound) in which a natural product (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, an aliphatic hydrocarbon group having 1 to 40 carbon atoms and a substituent, or polysiloxane.

[0019] Modified natural substances can be used as oil repellents.

[0020] Preferred embodiments of the present invention are as follows.

[0021] First option:

[0022] An oil-proofing agent, comprising a modified natural product containing at least one hydroxyl group in which the hydrogen atom of the hydroxyl group is replaced by an R group,

[0023] The R group is a group represented by -Y-Z,

[0024] In the formula, Y is a direct bond, -C(=O)-, -C(=O)-NR'- or -C(=S)-NR'-, wherein R' is a hydrogen atom or an alkyl group having carbon atoms of C1 to C4,

[0025] Z is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or polysiloxane.

[0026] Second option:

[0027] The oil repellent according to the first aspect, wherein the natural product is a natural product other than starch.

[0028] The third option:

[0029] The oil repellent 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.

[0030] The fourth option:

[0031] The oil resistant agent according to any one of the first to third aspects, wherein the natural product is a monosaccharide or polysaccharide, glycerin, or polyglycerin.

[0032] Fifth option:

[0033] The oil resistant agent according to any one of the first to fourth aspects, wherein

[0034] The natural product is at least one selected from a high molecular weight natural product and a low molecular weight natural product.

[0035] The natural high molecular weight substance is at least one selected from cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, K-type carrageenan, I-type carrageenan, polyglycerol, isomaltodextrin, xanthan gum, gellan gum, tamarind seed gum and cyclostranded starch,

[0036] The low molecular weight natural substance is at least one selected from glucose, sucrose, mannitol, sorbitol, sorbitan, maltitol, stevioside, cyclodextrin, glycerol, menthol, xylitol, glucosamine, catechins, anthocyanins and quercetin, gluconic acid, malic acid, xylose, inositol, phytic acid, menthol, sucralose, fructose, maltose, trehalose, lactulose, erythritol, erythritol, ascorbic acid, kojic acid, cholesterol, vanillin, lactic acid, tartaric acid, citric acid and chlorogenic acid.

[0037] The sixth option:

[0038] The oil resistant agent according to any one of the first to fifth aspects, wherein the substitution rate of hydrogen atoms of the hydroxyl group with R is 3 to 100%.

[0039] The seventh option:

[0040] The oil resistant agent according to any one of the first to sixth embodiments, 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, a (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 C1 to C4 carbon atoms.

[0041] The eighth option:

[0042] 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 is 11 degrees or more.

[0043] Ninth Plan:

[0044] 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 more or has no melting point.

[0045] The tenth option:

[0046] The oil resistant agent according to any one of the first to ninth aspects, wherein the viscosity of the solution of the oil resistant agent at a concentration of 14.8 mg / mL is 5 cP or more and 100 cP or less.

[0047] Eleventh Plan:

[0048] The oil resistant agent according to any one of the first to tenth aspects, wherein the oil resistant agent is a water-dispersible composition.

[0049] The twelfth plan:

[0050] 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.

[0051] The Thirteenth Plan:

[0052] A textile product, to which the oil-proofing agent according to any one of the first to twelfth aspects is attached.

[0053] The fourteenth plan:

[0054] An oil-proof paper comprising the oil-proof agent according to any one of the first to twelfth aspects.

[0055] The fifteenth plan:

[0056] The oil-resistant paper according to the fourteenth embodiment is a food packaging material or a food container.

[0057] The sixteenth plan:

[0058] A method for treating paper by external application or internal mixing using the oil resistant agent described in any one of the first to twelfth embodiments.

[0059] Effects of the Invention

[0060] 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 derived from a bio-based material, and therefore does not burden the ecological environment and has excellent biodegradability. DETAILED DESCRIPTION

[0061] The present invention provides a modified natural product (modified natural compound), wherein the hydrogen atom of the hydroxyl group in the natural product having at least one hydroxyl group is replaced by an R group,

[0062] The R group is a group represented by the formula -Y-Z,

[0063] In the formula, Y is a direct bond, -C(=O)-, -C(=O)-NR'- or -C(=S)-NR'-, wherein R' is a hydrogen atom or an alkyl group having carbon atoms of C1 to C4,

[0064] Z is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or polysiloxane.

[0065] Examples of the substituent include a hydroxyl group, an ester group, an R'3Si group, a (R'O)3Si group, a carboxyl group or a salt of a carboxyl group, wherein R' is independently a hydrogen atom or an alkyl group having C1 to C4 carbon atoms.

[0066] Any two of R can combine to form a ring.

[0067] Modified natural substances (modified natural compounds) have -O-R groups that do not exist in natural substances.

[0068] 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 of different structures.

[0069] Examples of the R group are -Z, -C(=O)-Z, -C(=O)-NH-Z, -C(=O)-NR'-Z and -C(=S)-NR'-Z, wherein Z and R' have the same meanings as above.

[0070] Z is a monovalent group.

[0071] Z is a hydrocarbon group having 1 to 40 carbon atoms, or a hydrocarbon group having 1 to 40 carbon atoms which has a substituent.

[0072] Z can 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) or a cyclic hydrocarbon group having 4 or more carbon atoms. The hydrocarbon group is preferably an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group, and particularly preferably an alkyl group. Compared with -CH2-, the -CH3 group has a lower surface free energy and is more likely to exhibit liquid repellency. Therefore, a structure with many branches and many -CH3 groups is preferred. On the other hand, a long-chain alkyl group of a certain length exhibits high liquid repellency due to its crystallinity.

[0073] 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, a long-chain alkyl group having a certain length (for example, 16 to 40 carbon atoms) exhibits high water repellency due to its crystallinity. Therefore, it is preferred to be a branched hydrocarbon group (for example, a branched (for example, 3 to 10 or 4 to 8 carbon atoms) alkyl group), such as tert-butyl and neopentyl, or a hydrocarbon group with a multi-branched structure of 5 to 30 carbon atoms, or a long-chain hydrocarbon group (or a long-chain straight-chain hydrocarbon group), such as an alkyl group with 16 to 40 carbon atoms or 16 to 26 carbon atoms, especially 18 to 22 carbon atoms. The long-chain hydrocarbon group is preferably a stearyl group, an eicosyl group or a behenyl group.

[0074] The number of carbon atoms in the hydrocarbon group may 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, and preferably 10 or more or 12 or more. The number of carbon atoms in 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.

[0075] The hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an aromatic aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group. The hydrocarbon group may be linear, branched or cyclic, preferably linear or branched, more preferably linear. The hydrocarbon group may be an unsaturated (e.g., monovalent unsaturated, divalent unsaturated, trivalent unsaturated, tetravalent unsaturated or polyvalent unsaturated) hydrocarbon group or a saturated hydrocarbon group, such as an alkyl group.

[0076] Specific examples of hydrocarbon groups include alkyl groups such as n-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, lauryl, tridecyl, tetradecyl, pentadecyl, palmityl, heptadecanyl, stearyl, nonadecanyl, behenyl, 2-ethylhexyl, and isostearyl; alkenyl groups such as oleyl, palmityl, and eicosyl; and cycloalkyl groups such as cyclohexyl.

[0077] Z may be a hydrocarbon group substituted by a carboxyl group.

[0078] The hydrocarbon group which may 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.

[0079] Z may be a hydrocarbon group substituted by a salt of a carboxyl group, that is, may be a hydrocarbon group substituted by a salt of a carboxyl group and a base.

[0080] The hydrocarbon group substituted by 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.

[0081] As the base, ammonia, an organic amine or an alkali metal hydroxide is preferably used.

[0082] Examples of the organic amine include methylamine, ethylamine, diethylamine, dimethylethanolamine, diethanolamine, triethanolamine, etc. Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. These bases may be used alone or in combination of two or more.

[0083] By neutralizing with an alkali, the modified natural product has good dispersibility in the aqueous dispersion medium, and an aqueous dispersion of a high-quality oil-proofing agent can be obtained.

[0084] Z may be a polysiloxane group. The polysiloxane group may be, for example, of the formula:

[0085] ―B―[―Si(R 21 )2―O―] a ―[―Si(R 22 )(R 21 )―O―] b ―A is a group,

[0086] Where A is -Si(R 21 )3 or -X 1 ,

[0087] B is ―[―(R 24 )―O―] q ―R 23 ―[―Si(R 21 )2―O―] p ―, where p and q are 0 or 1,

[0088] X 1 It 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 an acryloyloxy group) and / or a carboxyl group,

[0089] 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,

[0090] 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,

[0091] R 23 represents a hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by an oxygen atom,

[0092] R 24 represents a hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by an oxygen atom,

[0093] a represents an integer greater than or equal to 0, b represents an integer greater than or equal to 1, and (a+b) is 3-200.

[0094] R 21 It may have an epoxy ring, a hydroxyl group, a (meth)acryloyl group (or an acryloyloxy group) and / or a carboxyl group.

[0095] p and q are 0 or 1. Preferably, p and q are both 0 or both 1.

[0096] Examples of polysiloxane groups may be of the formula

[0097] -(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

[0098] or

[0099] -(R 24 )-O-(R 23 )-Si(R 21 )2-O-[-Si(R 2 1)2-O-] a -[-Si(R 22 )(R 21 )-O-] b -X 1

[0100] or

[0101] -R 23 -[-Si(R 21 )2-O-] a -[-Si(R 22 )(R 21 )-O-] b -Si(R 21 )3

[0102] or

[0103] -R 23 -[-Si(R 21 )2-O-] a -[-Si(R 22 )(R 21 )-O-] b -X 1 The groups shown,

[0104] Where, X 1 It 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 an acryloyloxy group) and / or a carboxyl group,

[0105] 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,

[0106] 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,

[0107] R 23 represents a hydrocarbon group having 1 to 20 carbon atoms,

[0108] R 24 represents a hydrocarbon group having 1 to 20 carbon atoms,

[0109] a represents an integer greater than or equal to 0, b represents an integer greater than or equal to 1, and (a+b) is 3-200.

[0110] R 21 and R 22 It may be a hydrocarbon group having 1 to 40 carbon atoms.

[0111] X 1 Examples include a hydrocarbon group having 1 to 40 carbon atoms (e.g., tert-butyl group), 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 oxirane 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 a (meth)acryloyloxy group), and a hydrocarbon group having 1 to 40 carbon atoms having a carboxyl group.

[0112] In the present specification, a (meth)acryloyl group means an acryloyl group and a methacryloyl group.

[0113] Another example of Z of the polysiloxane group may be a polysiloxane group having the formula:

[0114] ―(R 3 )2Si―O―[―Si(R 1 )2―O―] a ―[―Si(R 1 )(R 2 )―O―] b ―Si(R 3 )3 represents a group,

[0115] In the formula, R 1 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,

[0116] R 2 each independently represents a saturated hydrocarbon group having 1 to 40 carbon atoms,

[0117] R 3each 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,

[0118] a represents an integer greater than or equal to 0, b represents an integer greater than or equal to 1, and (a+b) is 3-200.

[0119] In polysiloxane groups (such as R 21 , R 22 , R 1 and R 3 ) in which the alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms may be unsubstituted or may have a substituent.

[0120] An alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms (e.g., R 21 , R 22 , R 1 and R 3 Specific examples of R 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 some or all of the hydrogen atoms bonded to these groups are replaced by halogen atoms, amino groups, cyano groups, etc. 21 , R 22 , R 1 and R 3 Preferred is methyl or ethyl.

[0121] R 21 , R 22 , R 1 and R 3 It may have an alkyl group having 3 to 22 carbon atoms or an unsaturated hydrocarbon group having 8 to 40 carbon atoms (for example, a hydrocarbon group having an aromatic ring), but preferably has no such groups.

[0122] In R 21 , R 22 , R 1 and R 3 In the above, 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, ethoxy, propoxy, and butoxy.

[0123] Based on the consideration of easy industrial manufacturing and easy availability, R 21 , R 22 , R 1 and R 3 It is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

[0124] The polysiloxane group has at least one hydrocarbon group having 1 to 40 carbon atoms, particularly a saturated hydrocarbon group.

[0125] Regarding the hydrocarbon group having 1 to 40 carbon atoms in the polysiloxane group, the same explanation as that in the case where Z is a hydrocarbon group having 1 to 40 carbon atoms can be applied.

[0126] The number of carbon atoms in the hydrocarbon group may also be 7 to 40, for example, 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 are methyl (carbon number 1), ethyl (carbon number 2), lauryl (carbon number 12), stearyl (carbon number 18), tricosyl (carbon number 23), carnauba (tetracosyl, carbon number 24), ceryl (hexacosyl, carbon number 26), montanyl (octacosyl, carbon number 28), myristyl (triacontyl, carbon number 30), dotriacontyl (carbon number 32).

[0127] a is an integer greater than or equal to 0. From the viewpoint of ease of industrial production and availability, a is preferably 40 or less, and more preferably 30 or less.

[0128] The total of a and b is 3 to 200 or 5 to 200. From the viewpoint of ease of industrial production, easy availability, and easy handling, the total of a and b is preferably 10 to 100, more preferably 40 to 60. a can be 0 to 150, for example 1 to 100. The lower limit of b can be 1, 2 or 3, and the upper limit of b can be 150, 10 or 5.

[0129] When a or b is 2 or more, there are multiple R 1 and R 2 Each R 1 and R 2 Can be the same or different.

[0130] Preferred R 1 , R 2 Group, R 3 50 mol% or more of the total of the groups are methyl groups.

[0131] The order of the repeating units enclosed in brackets by a or b is not limited to the order represented by the chemical formula, and may be any order. That is, the polysiloxane group may be a random copolymer or a block copolymer.

[0132] Examples of the polysiloxane group are shown below.

[0133]

[0134] In the formula, a represents an integer of 0 to 150, b represents an integer of 1 to 150, (a+b) is 5 to 200, and n is an integer of 0 to 36.

[0135] A natural substance (natural compound) is a naturally occurring compound having at least one hydroxyl group (hydroxyl-containing natural compound).

[0136] Natural products can be low molecules (for example, weight average molecular weight is less than 1000 or less than 500) and / or macromolecules. The weight average molecular weight of macromolecules can be more than 1000, more than 3000, more than 5000, more than 10000, more than 30000, more than 100000, more than 300000, more than 500000. The weight average molecular weight of macromolecules can be less than 1000000, less than 7500000, less than 500000, less than 3000000, less than 100000, less than 75000, less than 50000. The weight average molecular weight can be measured by gel permeation chromatography (GPC) with pullulan conversion.

[0137] Natural products can be high molecular weight natural products, low molecular weight natural products or their derivatives. Natural products also include compounds transformed by microorganisms.

[0138] Examples of high molecular weight natural products include starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, and chitosan. Other examples include locust bean gum, K-type carrageenan, I-type carrageenan, polyglycerol, isomaltodextrin, xanthan gum, gellan gum, tamarind seed gum, and cyclostranded starch. Natural products are preferably products other than starch.

[0139] Examples of low molecular weight natural substances include glucose, sucrose, mannitol, sorbitol, sorbitan, maltitol, stevioside, cyclodextrin, glycerol, menthol, xylitol, glucosamine, catechins, anthocyanidins, quercetin, gluconic acid and malic acid, xylose, inositol, phytic acid, menthol, sucralose, fructose, maltose, trehalose, lactulose, erythritol, erythritol, ascorbic acid, kojic acid, cholesterol, vanillin, lactic acid, tartaric acid, citric acid, and chlorogenic acid.

[0140] Natural products can be compounds of natural products themselves or compounds derived from natural products. That is, natural products also include derivatives of natural products. For example, as derivatives of starch, they include oxidized starch, hydrophobic starch, acetic starch, phosphated starch, acetylated starch, etherified starch, cationized starch, formic acid starch, hydroxymethylated starch, hydroxyethylated starch, and hydroxypropylated starch. As derivatives of cellulose, they include hydroxypropyl cellulose, methyl cellulose, carboxymethyl cellulose (CMC), cellulose monoacetate, cellulose triacetate, hydroxyethyl cellulose (HEC), hydroxypropyl methyl cellulose (HPMC), hydroxyethyl methyl cellulose (HEMC), cellulose TEAE (triethylaminoethyl cellulose), and chlorinated o-[2-hydroxy-3-(trimethylamino)propyl]hydroxyethyl cellulose.

[0141] When the derivative of a natural product has high oil resistance, it can be used as an oil repellent without modification. That is, the derivative of a natural product may be a modified natural product (modified natural compound).

[0142] Natural products can also be monosaccharides or polysaccharides (such as disaccharides and trisaccharides). Examples of monosaccharides include glucose, galactose, fructose, aldose, aldol, ketose, pyranose, furanose, aldonic acid, uronic acid and uronic acid. Polysaccharides are compounds formed by the combination of multiple (more than 3, for example, 3 to 4) monosaccharides such as glucose, galactose, and fructose. Polysaccharides can also be oligosaccharides formed by the combination of 3 to 10 monosaccharides.

[0143] Specific examples of polysaccharides include 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, isomaltodextrin, xanthan gum, gellan gum, tamarind seed gum, curdlan, pullulan, and cyclostranded starch.

[0144] The natural product may be starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, and cellulose is particularly preferred.

[0145] When the natural product is cellulose, the modified cellulose has a repeating unit structure shown in the following formula, for example,

[0146] Mode:

[0147]

[0148] In the formula, at least one R group is a -Y-Z group, and the remaining R groups are hydrogen atoms. Alternatively, all three R groups may be -Y-Z groups. The Y group and the Z group have the same meanings as above. n is a number greater than 2, for example, a number greater than 100 or greater than 500.

[0149] The natural substance may be, for example, an aldose, an aldol, a ketose, a pyranose, a furanose, an aldonic acid, a uronic acid, and a aldehyde acid.

[0150] Aldose is a sugar with C m H 2m O m A monosaccharide of the chemical formula (m is 3 or more, and the upper limit of m is usually 100, 20 or 10). Specific examples of aldose include erythrose, threose, ribose, arabinose, xylose, lyxose, allose, arabinose, glucose, mannose, gulose, idose, galactose and talose.

[0151] Alditol is a monosaccharide formed by reducing the aldehyde group of an aldose to a hydroxymethyl group, and is a monosaccharide having 3 or more carbon atoms (the upper limit of the number of carbon atoms is usually 100, 20 or 10). Specific examples of alditol include erythritol, threitol, ribitol, arabitol, xylitol, arabitol, allitol, altritol, sorbitol (glucitol), mannitol, sorbitol (glucitol), iditol, galactitol and altritol.

[0152] Ketose is a monosaccharide having a ketone group (keto carbonyl group) in a chain structure (the upper limit of the number of carbon atoms is usually 100, 20 or 10). Specific examples of ketose (specific examples of carbon atoms of 3 to 6) include dihydroxyacetone, erythrulose, ribose, xylose, psicose, fructose, sorbose and tagatose.

[0153] Pyranose is a monosaccharide having a six-membered ring consisting of five carbon atoms and one oxygen atom. Specific examples of pyranose include ribopyranose, arabinopyranose, xylopyranose, lyxopyranose, allopyranose, altropyranose, glucopyranose, mannopyranose, and gulopyranose.

[0154] Furanose is a monosaccharide having a five-membered ring composed of four carbon atoms and one oxygen atom. Specific examples of furanose include erythrofuranose, threofuranose, ribofuranose, arabinofuranose, xylofuranose, and lyxofuranose.

[0155] The modified natural compound can be prepared by reacting a modifying agent with a hydroxyl group of the natural product. Examples of the method for reacting a modifying agent with a hydroxyl group include a method for forming a urethane bond, a method for forming an ester bond, and a method for forming an ether bond.

[0156] 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 shown below:

[0157] Aliphatic isocyanate and / or aromatic isocyanate (Z-N=C=O),

[0158] Aliphatic isothiocyanates and / or aromatic isothiocyanates (Z-N=C=S),

[0159] Fatty acids (Z―C(=O)―OH),

[0160] Acyl halide compounds (Z-C(=O)-X),

[0161] Acid anhydride (Z―[C=O]―O―[C=O]―Z),

[0162] Halogenated alkyl compounds (Z-X),

[0163] Epoxides (Z-CHOCH2),

[0164] Acrylate (Z-CH2=CH),

[0165] Amine (Z―NH2),

[0166] Aliphatic alcohol (Z-OH),

[0167] In the formula, X is a halogen atom (eg, a chlorine atom, a bromine atom, or an iodine atom), and Z is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a polysiloxane.

[0168] 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, 15% or more, 20%, 30% or more, 40%, 45% or more, or 50% or more, and is preferably 100% or less, 99% or less, 90% or less, or 80% or less, for example, 70% or less, 60% or less, or 50% or less. "Substitution rate" refers to the proportion (%) of hydroxyl groups present in the structure of the modified natural product (modified natural compound) replaced by the modifier.

[0169] The ratio of unmodified hydroxyl groups (i.e., the residual rate of hydroxyl groups) may be greater than 0%, greater than 1%, greater than 3%, greater than 5%, or greater than 7%, for example, greater than 10% or greater than 20%, and may be less than 99%, less than 97%, or less than 95%, for example, less than 90%, less than 85%, less than 80%, or less than 70%.

[0170] <Method for forming urethane bond>

[0171] Aliphatic isocyanate and / or aromatic isocyanate (Z-NCO) is reacted with a hydroxyl group to form a urethane bond. Aliphatic isothiocyanate and / or aromatic isothiocyanate (Z-N=C=S) may be used instead of or in addition to isocyanate.

[0172] In the synthesis method of replacing the hydrogen atoms of the hydroxyl group of a natural product with an aliphatic isocyanate, when the hydroxyl-containing natural product is reacted with an aliphatic isocyanate or an aromatic isocyanate in an organic solvent in the presence of a tin catalyst or an amine or the like, the hydrogen atoms of the hydroxyl group can react with the isocyanate group to introduce various modified groups (Z groups) via an urethane bond.

[0173] The aliphatic isocyanate is preferably C n H 2n+1 -NCO, wherein n = 1 to 40, particularly 3 to 18. The aliphatic hydrocarbon group may be a straight chain or a branched chain.

[0174] Specific examples of aliphatic isocyanates include saturated aliphatic isocyanates such as methyl isocyanate, ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, tert-butyl isocyanate, amyl isocyanate, neopentyl isocyanate, hexyl isocyanate, heptyl isocyanate, octyl isocyanate, nonyl isocyanate, decyl isocyanate, dodecyl isocyanate, and octadecyl isocyanate; and unsaturated aliphatic isocyanates such as butenyl isocyanate, pentenyl isocyanate, hexenyl isocyanate, octenyl isocyanate, and dodecenyl isocyanate.

[0175] Specific examples of aromatic isocyanates 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'-diphenyl propane-4,4'-diisocyanate, Cyanate, 3,3'-dimethyldiphenylmethane-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'-dimethoxydiphenyl-4,4'-diisocyanate.

[0176] In the synthesis method of replacing the hydrogen atoms of the hydroxyl group of a natural product with an aliphatic isothiocyanate, when the hydroxyl-containing natural product is reacted with an aliphatic isocyanate or an aromatic isothiocyanate in an organic solvent in the presence of a tin catalyst or an amine or the like, the hydrogen atoms of the hydroxyl group can be reacted with the isothiocyanate group to introduce various modified groups (Z groups) via a thiourethane bond.

[0177] Aliphatic isothiocyanate is preferably C n H 2n+1 -NSO, wherein n=1 to 40, particularly 3 to 18. The aliphatic hydrocarbon group may be a straight chain or a branched chain.

[0178] Specific examples of aliphatic isothiocyanates include saturated aliphatic isothiocyanates such as methyl isothiocyanate, ethyl isothiocyanate, propyl isothiocyanate, isopropyl isothiocyanate, butyl isothiocyanate, amyl isothiocyanate, hexyl isothiocyanate, heptyl isothiocyanate, octyl isothiocyanate, nonyl isothiocyanate, decyl isothiocyanate, dodecyl isothiocyanate, and octadecyl isothiocyanate; and unsaturated aliphatic isocyanates such as butenyl isothiocyanate, pentenyl isothiocyanate, hexenyl isothiocyanate, octenyl isothiocyanate, and dodecenyl isothiocyanate.

[0179] Specific examples of the aromatic isothiocyanate include 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'-diphenyl propane-4,4'-diisothiocyanate. cyanate, 3,3'-dimethyldiphenylmethane-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'-dimethoxydiphenyl-4,4'-diisothiocyanate.

[0180] <Method of forming ester bond>

[0181] A fatty acid (Z-C(=O)-OH), an acyl halide compound (Z-C(=O)-X), an acid anhydride (Z-[C=O]-O-[C=O]-Z) is reacted with a hydroxyl group to form an ester bond.

[0182] Among the synthetic methods for replacing the hydrogen atoms of the hydroxyl groups of natural products with saturated aliphatic acyl groups, there are methods for reacting saturated fatty acid acyl halides with hydroxyl-containing natural products in the presence of a base such as pyridine; methods for reacting a mixed acid anhydride produced by a saturated fatty acid and a halogenated acetic acid such as trifluoroacetic acid with a hydroxyl-containing natural product; methods for reacting a saturated fatty acid anhydride with a hydroxyl-containing natural product; methods for reacting a saturated fatty acid with a hydroxyl-containing natural product in the presence of a sulfonate; and methods for reacting a saturated fatty acid with a hydroxyl-containing natural product in the presence of a dehydrating condensation agent.

[0183] Saturated fatty acids are preferably C n H 2n+1 A compound represented by -COOH, wherein n = 1 to 39. The aliphatic hydrocarbon group may be a straight chain or a branched chain.

[0184] Specific examples of saturated fatty acids are saturated fatty acids having 2 to 26 carbon atoms, such as acetic acid, butyric acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, isostearic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, and behenic acid.

[0185] Specific examples of the unsaturated fatty acid include palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, erucic acid, linoleic acid, γ-linolenic acid, α-linolenic acid, eicosapentaenoic acid, docosahexaenoic acid, and lanolin fatty acid.

[0186] The acyl halide compound is preferably C n H 2n+1 A compound represented by -CO-X, wherein n=1 to 39, and X=Br, Cl, I. The aliphatic hydrocarbon group may be a straight chain or a branched chain.

[0187] Specific examples of the acid halide compound include 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, and valeryl bromide.

[0188] The acid anhydride is preferably (C n H 2n+1 A compound represented by ―CO)2―O, wherein n=1 to 19 or 1 to 39. The aliphatic hydrocarbon group may be a straight chain or a branched chain.

[0189] The acid anhydride may form a 5-membered ring structure or a 6-membered ring structure. Specific examples of the acid anhydride 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, etc. and their analogs.

[0190] Specific examples of the acid anhydride 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 the like.

[0191] <Method for forming ether bond>

[0192] React a haloalkyl compound (Z-X) or an epoxide (Z-CH₂O) with a hydroxyl group to form an ether bond.

[0193] Examples of the synthesis method for substituting a hydrogen atom of a hydroxyl group in a natural product with an alkyl group include reacting a natural product containing a hydroxyl group with an aqueous alkaline solution of a haloalkyl compound (e.g., sodium hydroxide, potassium hydroxide); or 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.

[0194] The haloalkyl compound is preferably a compound represented by C n H 2n+1 -X, where n = 1-40, X = Cl, Br, I.

[0195] 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.

[0196] 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.

[0197] The epoxide is preferably a compound represented by C n H 2n+1 -CHOCH₂, where n = 1-40.

[0198] 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-epoxybutane, 2-epoxybutane, stearyl glycidyl ether, cetyl glycidyl ether, etc.

[0199] <Substituents other than the R group>

[0200] The hydrogen atom of the hydroxyl group in 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.

[0201] Examples of the anionic group include monomers having a carboxyl group, a sulfonic acid group, or a phosphoric acid group.

[0202] Examples of the salt of the anionic group include alkali metal salts, alkaline earth metal salts, and ammonium salts, such as methylammonium salts, ethanolammonium salts, and triethanolammonium salts.

[0203] The cationic group 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 (especially alkyl groups) having 1 to 5 carbon atoms, aromatic groups (aryl groups) having 6 to 20 carbon atoms, or aromatic aliphatic groups (especially aralkyl groups, such as benzyl (C6H5-CH2-)) having 7 to 25 carbon atoms. In the quaternary ammonium group, the three groups bonded to the nitrogen atom may be the same or different, and are preferably aliphatic groups (especially alkyl groups) having 1 to 5 carbon atoms, aromatic groups (aryl groups) having 6 to 20 carbon atoms, or aromatic aliphatic groups (especially aralkyl groups, such as benzyl (C6H5-CH2-)) having 7 to 25 carbon atoms. In the tertiary amino group and the quaternary ammonium group, the remaining one 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.

[0204] The cationic group as a 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, particularly a monocarboxylic acid such as acetic acid, propionic acid, butyric acid, or stearic acid.

[0205] <Treatment agent (oil resistant agent)>

[0206] The treatment agent (oil-proofing agent) includes modified natural products. The oil-proofing agent has oil resistance and can further have water resistance, water repellency, and oil repellency. In addition to the modified natural products, the oil-proofing agent can also contain a liquid medium (water, an organic solvent, or a mixed solution thereof). The oil-proofing agent can further contain at least one selected from a surfactant, a blocked isocyanate compound, and an additive.

[0207] 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 may be 100% by weight or less, 75% by weight or less, 50% by weight or less, or 40% by weight or less relative to the oil resistant agent.

[0208] The oil-proofing agent may contain an aqueous medium. The liquid medium may be water alone, an organic solvent (such as alcohol, ketone, ester) alone, or a mixture of water and an organic solvent, preferably water alone.

[0209] Relative to the oil resistant agent, the amount of the liquid medium can be more than 30 weight %, more than 50 weight %, more than 60 weight %, more than 75 weight % or more than 90 weight %, and the amount of the liquid medium can be less than 99 weight %, less than 95 weight %, less than 75 weight % or less than 50 weight %.

[0210] When the liquid medium is a mixture of water and an organic solvent, the amount of the organic solvent (e.g., alcohol, ester, ketone) relative to the liquid medium may be 3% by weight or more, 10% by weight or more, 30% by weight or more, 50% by weight or more, or 75% by weight or more. The amount of the organic solvent relative to the liquid medium may be 90% by weight or less, 50% by weight or less, 30% by weight or less, or 10% by weight or less.

[0211] The oil-proofing agent may be a solution (particularly an aqueous solution) or a dispersion composition (particularly an aqueous dispersion (aqueous dispersion composition)).

[0212] <Surfactant or dispersant>

[0213] The oil-proofing agent may or may not contain a surfactant (emulsifier) ​​or a dispersant. Generally, in order to stabilize the particles in the substitution reaction of the hydroxyl group and stabilize the aqueous dispersion after the reaction, a small amount (for example, 0.01 to 100 parts by weight or 0.01 to 50 parts by weight, for example 0.1 to 15 parts by weight relative to 100 parts by weight of the natural product) of a surfactant or a dispersant may be added during the reaction, or a surfactant or a dispersant may be added after the reaction.

[0214] In particular, when the treated product is a fiber product, in the oil-resistant agent, the surfactant or dispersant preferably includes a nonionic surfactant. Furthermore, the surfactant preferably includes one or more surfactants selected from cationic surfactants, anionic surfactants and amphoteric surfactants. It is preferred to use a combination of a nonionic surfactant and a cationic surfactant.

[0215] The nonionic surfactant, the cationic surfactant and the amphoteric surfactant may be used alone or in combination of two or more.

[0216] The amount of surfactant or dispersant is, relative to 100 weight parts of the total amount of natural product (or modified natural product), can be below 100 weight parts, below 50 weight parts, below 25 weight parts, below 15 weight parts, below 10 weight parts, below 7.5 weight parts, below 5 weight parts or below 2.5 weight parts. Usually, after adding surfactant or dispersant, the stability of aqueous dispersion, the permeability to fabric penetration, etc. are improved.

[0217] <Blocked isocyanate compound>

[0218] The oil-proofing agent may contain or not contain a blocked isocyanate compound. The blocked isocyanate compound may be added before the substitution reaction of the hydroxyl group or after the reaction (for example, before the curing step).

[0219] Blocked isocyanate compounds can be prepared by making isocyanate (as long as it is A(NCO) m A is prepared by reacting a compound represented by RH with a blocking agent (any compound represented by RH), wherein A is the group remaining after removing the isocyanate group from the isocyanate compound, m is an integer from 2 to 8; R is any hydrocarbon group that can be substituted by heteroatoms such as nitrogen atoms or oxygen atoms, and H is a hydrogen atom.

[0220] A(NCO) m Examples include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), etc. Examples of the blocking agent for forming the R group are oxime, phenol, alcohol, thiol, amide, imide, imidazole, urea, amine, imine, pyrazole and active methylene compound.

[0221] As the blocked isocyanate compound, blocked isocyanates such as oxime blocked tolylene diisocyanate, blocked hexamethylene diisocyanate, and blocked diphenylmethane diisocyanate are preferred.

[0222] 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, based on 100 parts by weight of the modified natural product.

[0223] <Additives>

[0224] The oil-proofing agent may contain additives. Examples of additives include binder resins, dispersants, water-proofing agents, oil-proofing agents, water-repellent agents, oil-repellent agents, drying speed regulators, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity regulators, ultraviolet absorbers, antioxidants, pH regulators, defoamers, texture regulators, slip regulators, antistatic agents, hydrophilic agents, antibacterial agents, preservatives, insect repellents, fragrances, flame retardants, sizing agents, and paper strength enhancers. The amount of the additives may be 0.1 to 20 parts by weight, for example 0.1 to 10 parts by weight, relative to 100 parts by weight of the modified natural product.

[0225] <Characteristics of oil-resistant agents and modified natural products>

[0226] The contact angle (on a glass substrate) of n-hexadecane with respect to the modified natural product (or oil-resistant agent) may 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 perspective of excellent liquid repellency of the oil-resistant agent, particularly oil resistance, etc., it is preferred that the contact angle of n-hexadecane be within the above range.

[0227] The surface free energy of the modified natural product is preferably 20 mNm ﹣1 Above, 25mNm﹣1 Above or 30mNm ﹣1 Above, preferably 70mNm ﹣1 Below, 60mNm ﹣1 Below or 50mNm ﹣1 the following.

[0228] The preferred range of the difference in SP value between the modified natural product (or oil resistance agent) and corn oil may be 3 or more, 5 or more, or 7 or more.

[0229] 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, or 160° C. or lower.

[0230] The melting point of the oil-proofing agent is preferably within the above range from the viewpoints of the coating properties of the treated fiber product, the improvement of the temperature resistance, and particularly the oil resistance.

[0231] The glass transition temperature of the modified natural product is preferably 30°C or more, 40°C or more, 50°C or more, 60°C or more, 70°C or more, 80°C or more, 90°C or more, 100°C or more, 110°C or more, 120°C or more, or 140°C or more. In addition, the glass transition temperature of the modified natural product is preferably 180°C or less, 140°C or less, 130°C or less, or 120°C or less. From the viewpoint of the coating property of the fiber product after treatment, the improvement of temperature resistance, and particularly oil resistance, the glass transition temperature of the modified natural product is preferably within the above range.

[0232] The viscosity of the polymer (modified natural product) solution of the oil resistant agent when the concentration is 14.8 mg / mL is preferably 3 cP or more, 5 cP or more, 7 cP or more, or 10 cP or more. In addition, the viscosity of the polymer solution of the oil resistant agent when the concentration is 14.8 mg / mL is preferably 1000 cP or less, 500 cP or less, or 100 cP or less. From the perspective of improving the coating properties of the treated fiber product, especially oil resistance, the viscosity of the polymer solution of the oil resistant agent is preferably within the above range.

[0233] 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 gaps between the fibers are closed, and in particular, the oil resistance is improved. The treated paper used for measuring the air permeability is a polymer (modified natural product) of an oil-resistant agent having a solution concentration of 14.8 mg / mL, and a paper density of 0.58 g / cm is applied with a Baker applicator set to 0 mil. 3 A product is prepared by repeatedly performing coating and drying operations three times on a base paper having a grammage of 45 g / m2, and annealing at a temperature of 70°C to 180°C (eg, 70°C) for 10 minutes.

[0234] The preferred range of the contact angle and air permeability combination of hexadecane may be 5 degrees or more × 200s or more, 10 degrees or more × 200s or more, 30 degrees or more × 200s or more, or 40 degrees or more × 200s or more. Alternatively, the preferred range of the contact angle and air permeability combination of hexadecane may be 11 degrees or more × 250s or more, 15 degrees or more × 250s or more, 30 degrees or more × 250s or more, or 40 degrees or more × 250s or more. Alternatively, the preferred range of the contact angle and air permeability combination of hexadecane may be 11 degrees or more × 300s or more, 15 degrees or more × 300s or more, 30 degrees or more × 300s or more, or 40 degrees or more × 300s or more. The preferred range of the contact angle and air permeability combination of the alternative hexadecane may be 11 degrees or more × 350s or more, 15 degrees or more × 350s or more, 30 degrees or more × 350s or more, or 40 degrees or more × 350s or more.

[0235] The product of the contact angle of hexadecane and the air permeability is preferably 1500 (degrees·s) or more, 2000 (degrees·s) or more, 2500 (degrees·s) or more, 3000 (degrees·s) or more, 3500 (degrees·s) or more, 4000 (degrees·s) or more, 5000 (degrees·s) or more, 6000 (degrees·s) or more, 7000 (degrees·s) or more, 8000 (degrees·s) or more, 9000 (degrees·s) or more, or 10000 (degrees·s) or more. The upper limit of the product of the contact angle of hexadecane and the air permeability may be 300000 (degrees·s), 200000 (degrees·s) or 100000 (degrees·s). The product of the contact angle of hexadecane and the air permeability being above the above values ​​means that any of the properties of the oil repellency or the coating property of the oil resistant agent is in a state sufficient to exhibit oil resistance.

[0236] <Uses of modified natural products>

[0237] Modified natural products can be used as various preparations or components thereof such as oil-proofing agents, water-proofing agents, water-repellent agents, oil-repellent agents, antifouling agents, dirt removers, stripping agents or mold release agents. Modified natural products can be used as external treatment agents (surface treatment agents) or internal treatment agents or components thereof.

[0238] By treating the substrate with the modified natural material, the modified natural material can form a surface coating structure on the surface of the substrate.

[0239] In order to make the treated object (substrate) show 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 the side chain orientation can be induced. Thus, a surface coating structure with excellent hydrophobicity can be formed.

[0240] The surface coating structure can be applied to the treated object (substrate) by the existing known method by the modified natural substance, and formed by being attached to the substrate surface. Usually, the modified natural substance is dispersed in an organic solvent or water and diluted, and the modified natural substance is attached to the surface of the treated object and the method of drying by known methods such as immersion coating, spraying, and foam coating. In addition, if necessary, it can be applied together with a suitable cross-linking agent (for example, a blocked isocyanate compound) for curing. In addition, insect repellent, softener, antibacterial agent, flame retardant, antistatic agent, coating fixative, wrinkle-proof agent, sizing agent, paper strength enhancer, etc. can also be added and used in the modified natural substance.

[0241] Examples of the objects to be treated with preparations containing modified natural substances include fiber products, stone materials, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, coated surfaces, and gypsum.

[0242] As the fiber product, various examples can be given as the fiber product, for example, cloth products, paper products, etc. can be given.

[0243] Examples of cloth products include natural fibers of plants and animals 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 mixed fibers of the above fibers. Cloth products include textiles, knitted fabrics and non-woven fabrics, cloth in the form of clothing fabrics, and carpets, but fibers, yarns, and intermediate fiber products (such as sheets or rovings, etc.) in the state before being made into cloth can also be processed.

[0244] As examples of paper products, bleached or unbleached chemical pulps such as kraft pulp or sulfate pulp, bleached or unbleached high-yield pulps such as wood pulp, mechanical pulp or thermomechanical pulp, old newspapers, old magazines, waste paper pulps such as old corrugated boards or deinked waste paper, paper, containers made of paper, molded bodies formed of paper, etc. can be cited. As a specific example of paper products, food packaging paper, gypsum board base paper, coated base paper, medium-quality paper, ordinary lining and core, neutral pure white roll paper, neutral lining, rust-proof lining and metal isolation paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded container), etc. are included. Since the modified natural product of the present invention has excellent oil resistance (for example, high temperature oil resistance), it can be applied to the purposes requiring oil resistance, particularly suitable for food packaging materials and food containers.

[0245] The modified natural product can be applied to a fibrous substrate (e.g., a fiber product, etc.) by any known method for treating a fiber product with a liquid. When the fiber product is a cloth, the cloth can be immersed in the solution, or the solution can be attached to or sprayed on the cloth. The treatment can be an external treatment or an internal mixing treatment. When the fiber product is paper, it can be coated on the paper, or the solution can be attached to or sprayed on the paper, or it can also be treated by mixing with pulp before papermaking. The treatment can be an external treatment or an internal mixing treatment.

[0246] The modified natural product can be applied to preformed fiber products (especially paper, cloth, etc.), or applied at various stages of papermaking, such as during paper drying. The modified natural product can be applied to fiber products by cleaning methods, such as in washing applications or in dry cleaning methods, etc.

[0247] Alternatively, the fibrous substrate may be leather. To render the leather hydrophobic and oleophobic, the modified natural substance may be applied to the leather from an aqueous solution or an aqueous emulsion at various stages of leather processing, for example during the wet processing of the leather or during the finishing of the leather.

[0248] The modified natural substances can also be used as external release agents, enabling, for example, the surface of a substrate to be easily released from other surfaces (other surfaces on the substrate or surfaces on other substrates).

[0249] In the case of paper products, there is a method of, for example, spraying a natural modified substance solution onto a pulp mold and then heating and drying it.

[0250] Alternatively, the natural modified substance dispersed in a pulp slurry solution by an emulsifier or the like may be mixed, dehydrated, molded, and hot pressed. A crosslinking agent, a paper strength enhancer, a fixing agent, and the like may be added to the pulp slurry.

[0251] Alternatively, the paper may be immersed in the natural modified substance dispersion solution and then heated and dried.

[0252] In the case of cloth products, there is a method of immersing the cloth in a dispersion solution of the natural modified substance or spraying the solution onto the cloth, dehydrating the cloth, and then heating and drying the cloth.

[0253] "Treatment" means applying a treatment agent to the treated object by dipping, spraying, coating, etc. Through the treatment, the modified natural substance as an effective component of the treatment agent penetrates into the treated object and / or adheres to the surface of the treated object.

[0254] <Paper Additives>

[0255] Modified natural products can be appropriately used as paper additives. Paper additives containing modified natural products can be used as water-resistant agents, oil-resistant agents, water-repellent agents and / or oil-repellent agents. Paper additives are preferably in the form of solutions (especially solutions of organic solvents), emulsions (especially aqueous emulsions) or aerosols. Paper additives contain modified natural products and media (such as liquid media such as organic solvents and water). Paper additives are preferably aqueous dispersions of modified natural products. In paper additives, the concentration of modified natural products can be, for example, 0.01 to 50% by weight. Paper additives may not contain surfactants.

[0256] 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.).

[0257] Paper additives can be used to treat (e.g., surface treat) paper substrates. Paper additives can be applied to the treated object by existing known methods. Usually, the paper additive is dispersed in an organic solvent or water and diluted, and the paper additive is attached to the surface of the treated object and dried by known methods such as immersion coating, spraying, and foam coating (surface treatment). Paper substrates of the treated object include paper, containers that can be made of paper, and molded bodies that can be made of paper (such as pulp molds). The modified natural product of the present invention can be well attached to the paper substrate. In this specification, attachment refers to physical bonding or chemical bonding. By attaching the modified natural product to the paper substrate, oil-resistant paper can be obtained.

[0258] Although the embodiments are described above, it should be understood that various changes may be made to the embodiments and details without departing from the spirit and scope of the present invention.

[0259] Example

[0260] Next, the present invention is specifically described with reference to the following examples. However, these examples do not limit the present invention. In the following, unless otherwise specified, "part", "%" or "ratio" means part by weight, weight % or weight ratio.

[0261] The test methods used hereinafter are as follows.

[0262] Preparation of treated paper

[0263] As wood pulp, a pulp slurry was prepared with a weight ratio of LBKP (bleached kraft pulp of broadleaf trees) and NBKP (bleached kraft pulp of coniferous trees) of 60% by weight and 40% by weight, and a pulp water filterability of 400 ml (Canadian Standard Freeness), a wetting paper strength agent and a sizing agent were added to the pulp slurry, and a paper density of 0.58 g / cm3 and a grammage of 45 g / m2 were used as a base paper for external coating treatment (sizing treatment) through a Fourdrinier papermaking machine. The base paper had an oil resistance (KIT value) of 0 and a water resistance (Cobb value) of 52 g / m2.

[0264] The base paper was repeatedly coated with 14.9 mg / cm3 three times using a Baker applicator with a gap setting of 0 mil. 3 The treated paper is prepared by mixing a polymer solution (chloroform, toluene or acetone) and drying it, and annealing it at 70°C for 10 minutes.

[0265] KIT test (oil resistance)

[0266] The test was conducted using the 3M test kit method (TAPPI T-559cm-02). The 3M test kit method involves placing a test oil containing castor oil, toluene, or heptane on the surface of the treated paper, wiping off the test oil after 15 seconds, and evaluating whether there is oil stain on the treated paper at this time. The test was conducted using test oils from kit numbers 1 to 6, and the largest kit number where no oil stain was observed was used as the oil resistance evaluation result.

[0267] Corn oil tolerance evaluation (oil resistance)

[0268] Corn oil was placed on the surface of the treated paper, and the test oil was wiped off after 15 seconds. Evaluation was performed based on whether there was oil stain on the treated paper at this time. The case where there was no oil stain was marked as "○", and the case where oil stain was observed was marked as "×".

[0269] Liquid repellency (static contact angle)

[0270] Liquid repellency is measured by spin coating a solution of 1.0% solid component concentration of the modified natural product on a glass substrate with a celluloid film, and measuring the static contact angle. The static contact angle is obtained by dropping 2 μL of hexadecane (HD) on the coating film and measuring the contact angle 1 second after the drop.

[0271] Breathability

[0272] The air permeability (air resistance) of the treated paper was measured according to JIS P8117 (2009) using an automatic Gurley electric tester manufactured by Yasuda Seiki Co., Ltd. (product model: No. 323-AUTO, air pore diameter 28.6±0.1 mm).

[0273] Replacement rate

[0274] pass 1 The substitution rate of the oil resistant agent was determined by H NMR or elemental analysis.

[0275] Example 1

[0276] In a reaction vessel equipped with a reflux cooler and a nitrogen inlet tube, add a stirring bar, 4.0 g of cellulose (20 μm powder), and 4.0 g of LiCl, and dry under reduced pressure at 80°C for 4 hours. Then add 40 mL of dimethylformamide, and stir at 150°C for 1 hour. Then, return to room temperature, and add 0.1 g of dibutyltin dilaurate. Adjust the temperature to 120°C, add 22.2 g of octadecyl isocyanate (3 equivalents relative to the OH of the repeating unit) and 10 mL of dimethylformamide, and stir for 12 hours. 1 After H NMR confirmed the disappearance of octadecyl isocyanate, the reaction vessel was cooled to room temperature, and the reaction mixture was dripped into water to precipitate solids. The precipitated solids were recovered by suction filtration, washed once with methanol, and washed once with acetone. Chloroform as a good solvent and hexane as a weak solvent were used to reprecipitate the recovered solids to obtain a derivative of cellulose modified with octadecyl isocyanate as an oil-resistant agent. The substitution rate of the derivative was 100%. The derivative was used to evaluate liquid repellency, KIT test, corn oil tolerance, and air permeability. The results are shown in Table 1.

[0277] Example 2

[0278] A stirring 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 cooler and a nitrogen inlet tube, and the mixture was 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. 1After H NMR confirmed the disappearance of octadecyl isocyanate, the reaction vessel was cooled to room temperature, the reaction mixture was concentrated by a rotary evaporator, and reprecipitated with ethyl acetate as a weak solvent to obtain a derivative of propyl cellulose modified with octadecyl isocyanate as an oil-resistant agent. The substitution rate of the derivative was 100%. The derivative was used to evaluate liquid repellency, KIT test, corn oil tolerance, and air permeability. The results are shown in Table 1.

[0279] Example 3

[0280] As an oil-proofing agent, cellulose acetate (1.14 eq modified product, substitution rate: 38%) synthesized from cellulose was used, and evaluations of liquid repellency, KIT test, corn oil resistance, and air permeability were performed. The results are shown in Table 1.

[0281] Comparative Example 1

[0282] Cellulose (20 μm powder) was used as an oil-proofing agent, and evaluations of liquid repellency, KIT test, corn oil resistance, and air permeability were performed. The results are shown in Table 1.

[0283] Comparative Example 2

[0284] The liquid repellency was evaluated by using polyglycerol (average molecular weight 500) as an oil-proof agent. The results showed that the KIT test was 0 points, the corn oil resistance was ×, and the air permeability was 136 s / 100 cc.

[0285] Example 4

[0286] A stirring 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 the reaction container, and the mixture was stirred at 60°C for 1 hour. 1 After H NMR confirmed the disappearance of octadecyl isocyanate, the mixture was dripped into hexane to precipitate solids. The precipitated solids were recovered by suction filtration to obtain a derivative of polyglycerol modified with octadecyl isocyanate as an oil resistant agent. The substitution rate of the derivative was 100%. The liquid repellency of the oil resistant agent was evaluated as 4 points in the KIT test, ○ in corn oil tolerance, and 289s / 100cc in air permeability.

[0287] Example 5

[0288] The same procedure as in Example 4 was carried out except that the amount of octadecyl isocyanate used was changed to 12 g.

[0289] The substitution rate of the derivative was 54%. The liquid repellency of the oil-proofing agent was evaluated as 4 points in the KIT test, ○ in corn oil resistance, and 232 s / 100 cc in air permeability.

[0290] Example 6

[0291] 0.1 g of the derivative obtained in Example 5 was emulsified with 0.1 g of polyoxyethylene oleyl ether and 9.8 g of water and applied in the same manner. The oil repellency of the oil resistant agent was 4 points in the KIT test, ○ in corn oil resistance, and 185 s / 100 cc in air permeability.

[0292] Example 7

[0293] The same procedure as in Example 4 was carried out except that the amount of octadecyl isocyanate used was changed to 6.3 g.

[0294] The substitution rate of the derivative was 25%. The liquid repellency of the oil-proofing agent was evaluated as 5 points in the KIT test, ○ in corn oil resistance, and 231 s / 100 cc in air permeability.

[0295] Example 8

[0296] The same procedure as in Example 4 was carried out except that octadecyl isocyanate was changed to 6.2 g of octadecyl isocyanate and 4.5 g of dodecyl isocyanate.

[0297] The substitution rate of the derivative was 100%. The liquid repellency of the oil-proofing agent was evaluated as 4 points in the KIT test, ○ in corn oil resistance, and 224 s / 100 cc in air permeability.

[0298] Example 9

[0299] A stirring bar, 2.5 g of polyglycerol (average molecular weight 750), 20 mL of pyridine, and 10.6 g of octadecyl isocyanate were added to the reaction container, and 1 drop of dibutyltin dilaurate was added, followed by stirring at 60°C for 1 hour. 1 After H NMR confirmed the disappearance of octadecyl isocyanate, the mixture was dripped into hexane to precipitate solids. The precipitated solids were recovered by suction filtration to obtain a derivative of polyglycerol modified with octadecyl isocyanate as an oil resistant agent. The substitution rate of the derivative was 100%. The liquid repellency of the oil resistant agent was evaluated as 4 points in the KIT test, ○ in corn oil tolerance, and 286s / 100cc in air permeability.

[0300] Example 10

[0301] A stirring bar, 2.5 g of polyglycerol (average molecular weight 750), 20 mL of pyridine, and 0.89 g of octadecyl isocyanate were added to the reaction container, and 1 drop of dibutyltin dilaurate was added, followed by stirring at 60°C for 1 hour. 1After H NMR confirmed the disappearance of octadecyl isocyanate, the solvent was distilled off to obtain a derivative of polyglycerol modified with octadecyl isocyanate as an oil resistant agent. The substitution rate of the derivative was 8%. The liquid repellency of the oil resistant agent was evaluated as 5 points in the KIT test, ○ in corn oil tolerance, and 277s / 100cc in air permeability.

[0302] Example 11 (MS379P)

[0303] The compound obtained in Example 10 was prepared into a 1% aqueous solution and applied. The liquid repellency of the oil-proof agent was evaluated as 5 points in the KIT test, ○ in corn oil resistance, and 269 s / 100 cc in air permeability.

[0304] Example 12

[0305] A stirring bar, 2.5 g of polyglycerol (average molecular weight 750), 20 mL of pyridine, and 0.44 g of octadecyl isocyanate were added to the reaction container, and 1 drop of dibutyltin dilaurate was added, followed by stirring at 60°C for 1 hour. 1 After confirming the disappearance of octadecyl isocyanate by H NMR, the solvent was distilled off to obtain a derivative of polyglycerol modified with octadecyl isocyanate as an oil-proofing agent. The substitution rate of the derivative was 4%.

[0306] The compound was prepared into a 1% aqueous solution and applied. The liquid repellency of the oil-proof agent was evaluated as 3 points in the KIT test, ○ in corn oil resistance, and 225 s / 100 cc in air permeability.

[0307] Embodiment 13

[0308] A stirring bar, 0.46 g of glycerol, 10 mL of pyridine, and 4.4 g of octadecyl isocyanate were added to the reaction container, and 1 drop of dibutyltin dilaurate was added, followed by stirring at 60°C for 1 hour. 1 After H NMR confirmed the disappearance of octadecyl isocyanate, the mixture was added dropwise to hexane to precipitate solids. The precipitated solids were recovered by suction filtration to obtain a derivative of glycerol modified with octadecyl isocyanate as an oil resistant agent. The substitution rate of the derivative was 100%. The liquid repellency of the oil resistant agent was 4 points in the KIT test and ○ in corn oil tolerance.

[0309] Embodiment 14

[0310] A stirring bar, 0.92 g of glycerol, 10 mL of pyridine, and 4.4 g of octadecyl isocyanate were added to the reaction container, and 1 drop of dibutyltin dilaurate was added, followed by stirring at 60°C for 1 hour. 1After H NMR confirmed the disappearance of octadecyl isocyanate, the mixture was added dropwise to hexane to precipitate solids. The precipitated solids were recovered by suction filtration to obtain a derivative of glycerol modified with octadecyl isocyanate as an oil resistant agent. The substitution rate of the derivative was 50%. The liquid repellency of the oil resistant agent was 4 points in the KIT test and ○ in corn oil tolerance.

[0311] Embodiment 15

[0312] A stirring bar, 1.7 g of diglycerol, 20 mL of pyridine, and 11.8 g of octadecyl isocyanate were added to the reaction container, and 1 drop of dibutyltin dilaurate was added, followed by stirring at 60°C for 1 hour. 1 After H NMR confirmed the disappearance of octadecyl isocyanate, the mixture was added dropwise to hexane to precipitate solids. The precipitated solids were recovered by suction filtration to obtain a derivative of diglycerol modified with octadecyl isocyanate as an oil resistant agent. The substitution rate of the derivative was 100%. The liquid repellency of the oil resistant agent was 4 points in the KIT test and ○ in corn oil tolerance.

[0313] Example 16

[0314] A stirring bar, 1.7 g of diglycerol, 20 mL of pyridine, and 3.0 g of octadecyl isocyanate were added to the reaction container, and 1 drop of dibutyltin dilaurate was added, followed by stirring at 60°C for 1 hour. 1 After H NMR confirmed the disappearance of octadecyl isocyanate, the mixture was added dropwise to hexane to precipitate solids. The precipitated solids were recovered by suction filtration to obtain a derivative of diglycerol modified with octadecyl isocyanate as an oil resistant agent. The substitution rate of the derivative was 25%. The liquid repellency of the oil resistant agent was 4 points in the KIT test and ○ in corn oil tolerance.

[0315] Embodiment 17

[0316] A stirring bar, 0.5 g of maltitol, 15 mL of DMSO, and 4.0 g of octadecyl isocyanate were added to the reaction container, and 1 drop of dibutyltin dilaurate was added, followed by stirring at 60° C. for 1 hour. 1 After H NMR confirmed the disappearance of octadecyl isocyanate, the mixture 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 the derivative was 100%. The liquid repellency of the oil resistant agent was evaluated as 4 points in the KIT test, ○ in corn oil tolerance, and 1243 s / 100 cc in air permeability.

[0317] Embodiment 18

[0318] The same method as in Example 17 was used except that the amount of octadecyl isocyanate was changed to 2.0 g to obtain a derivative of maltitol modified with octadecyl isocyanate. The substitution rate of the derivative was 60%. The liquid repellency of the oil-resistant agent was evaluated as 3 points in the KIT test, ○ in corn oil tolerance, and 400 s / 100 cc in air permeability.

[0319] Embodiment 19

[0320] A stirring bar, 1.8 g of sorbitol, 20 mL of DMF, and 18 g of octadecyl isocyanate were added to the reaction container, and 1 drop of dibutyltin dilaurate was added dropwise, followed by stirring at 60° C. for 1 hour. 1 After H NMR confirmed the disappearance of octadecyl isocyanate, washing with hexane and acetone gave a derivative of sorbitol modified with octadecyl isocyanate as an oil-resistant agent. The substitution rate of the derivative was 100%. The liquid repellency of the oil-resistant agent was 5 points in the KIT test and ○ in corn oil tolerance.

[0321] Embodiment 20

[0322] A stirring bar, 1.8 g of sorbitol, 20 mL of DMF, and 8.9 g of octadecyl isocyanate were added to the reaction container, and 1 drop of dibutyltin dilaurate was added, followed by stirring at 60° C. for 1 hour. 1 After H NMR confirmed the disappearance of octadecyl isocyanate, washing with hexane and acetone gave a derivative of sorbitol modified with octadecyl isocyanate as an oil resistant agent. The substitution rate of the derivative was 50%. The liquid repellency of the oil resistant agent was evaluated as 5 points in the KIT test, ○ in corn oil tolerance, and 729s / 100cc in air permeability.

[0323] Embodiment 21

[0324] A stirring bar, 1.8 g of sorbitol, 20 mL of DMF, and 4.4 g of octadecyl isocyanate were added to the reaction container, and 1 drop of dibutyltin dilaurate was added, followed by stirring at 60° C. for 1 hour. 1 After H NMR confirmed the disappearance of octadecyl isocyanate, washing with hexane and acetone gave a derivative of sorbitol modified with octadecyl isocyanate as an oil resistant agent. The substitution rate of the derivative was 25%. The liquid repellency of the oil resistant agent was evaluated as 5 points in the KIT test, ○ in corn oil tolerance, and 449s / 100cc in air permeability.

[0325] Embodiment 22

[0326] A stirring bar, 1.8 g of sorbitol, 20 mL of DMF, and 2.9 g of octadecyl isocyanate were added to the reaction container, and 1 drop of dibutyltin dilaurate was added, followed by stirring at 60° C. for 1 hour. 1After H NMR confirmed the disappearance of octadecyl isocyanate, washing with hexane and acetone gave a derivative of sorbitol modified with octadecyl isocyanate as an oil resistant agent. The substitution rate of the derivative was 16%. The liquid repellency of the oil resistant agent was 4 points in the KIT test, ○ in corn oil tolerance, and 897s / 100cc in air permeability.

[0327] Embodiment 23

[0328] A stirring bar, 1.8 g of sorbitol, 20 mL of pyridine, and 9.1 g of C17H35COCl were added to the reaction container, and the mixture was stirred overnight at 60° C. The mixture was washed with hexane and acetone to obtain a C17H35 ester-modified sorbitol derivative as an oil-resistant agent.

[0329] The substitution rate of the derivative was 50%. The liquid repellency of the oil-proofing agent was evaluated as 4 points in the KIT test and ○ in corn oil resistance.

[0330] Embodiment 24

[0331] A stirring bar, 1.8 g of mannitol, 20 mL of DMF, and 8.9 g of octadecyl isocyanate were added to the reaction container, and 1 drop of dibutyltin dilaurate was added, followed by stirring at 60° C. for 1 hour. 1 After H NMR confirmed the disappearance of octadecyl isocyanate, washing with hexane and acetone gave a derivative of mannitol modified with octadecyl isocyanate as an oil-resistant agent. The substitution rate of the derivative was 50%. The liquid repellency of the oil-resistant agent was 5 points in the KIT test and ○ in corn oil tolerance.

[0332] Embodiment 25

[0333] Add a stirrer, 0.40g of dextrin, and 10mL of DMSO to a reaction vessel and heat to 60°C. After dissolving the dextrin, add 1 drop of dibutyltin dilaurate, 2.2g of octadecyl isocyanate, and 2ml of CHCl3, and stir at 60°C. Recover the solid with a weak solvent to obtain a derivative. The substitution rate of the derivative is 70%. The liquid repellency evaluation of the oil-resistant agent is 3 points in the KIT test, ○ in corn oil tolerance, and 1281.7s / 100cc in air permeability.

[0334] Embodiment 26

[0335] As an oil-proofing agent, tristearate decaglycerol was used, and liquid repellency, KIT test, corn oil resistance, and air permeability were evaluated. The HD contact angle of the oil-proofing agent was 41.1°, the KIT test was 4 points, the corn oil resistance was ○, and the air permeability was 252.1 s / 100 cc.

[0336] Embodiment 27

[0337] Hexaglycerol tristearate was used as an oil repellent, and liquid repellency, KIT test, corn oil resistance, and air permeability were evaluated. The oil repellent had a HD contact angle of 40.6°, a KIT test of 4 points, a corn oil resistance of ○, and an air permeability of 230.4 s / 100 cc.

[0338] Embodiment 28

[0339] As an oil-proofing agent, hexaglycerol pentastearate was used, and liquid repellency, KIT test, corn oil resistance, and air permeability were evaluated. The HD contact angle of the oil-proofing agent was 41.9°, the KIT test was 4 points, the corn oil resistance was ○, and the air permeability was 230.6 s / 100 cc.

[0340] Embodiment 29

[0341] Decaglyceryl heptabehenate was used as an oil repellent, and liquid repellency, KIT test, corn oil resistance, and air permeability were evaluated. The oil repellent had a HD contact angle of 40.5°, a KIT test of 5 points, corn oil resistance of ○, and an air permeability of 604.0 s / 100 cc.

[0342] Embodiment 30

[0343] Decabehenate was used as an oil repellent, and liquid repellency, KIT test, corn oil resistance, and air permeability were evaluated. The oil repellent had a HD contact angle of 40.5°, a KIT test of 5 points, corn oil resistance of ○, and an air permeability of 236.6 s / 100 cc.

[0344] Embodiment 31

[0345] Hexaglycerol monostearate was used as an oil repellent, and liquid repellency, KIT test, corn oil resistance, and air permeability were evaluated. The oil repellent had a HD contact angle of 41.1°, a KIT test of 5 points, a corn oil resistance of ○, and an air permeability of 237.6 s / 100 cc.

[0346] Embodiment 32

[0347] 5.8 g of lanolin 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, and heated overnight. The generated solid was washed with dilute hydrochloric acid and acetone, and a derivative of glycerol modified with lanolin fatty acid was obtained by suction filtration as an oil-resistant agent. The substitution rate of the derivative was 100%. The oil resistance evaluation of the oil-resistant agent was 3 points in the KIT test.

[0348] Embodiment 33

[0349] 4.35g of carboxylic acid-modified polyorganosiloxane (functional group equivalent 1,450g / mol), 10ml of pyridine, and 1.77g of BOP reagent were stirred for 1 hour, 4.35g of glycerol was added, and stirred at 60°C for one day. After cooling, the product was extracted with chloroform and washed with water, and the solvent was distilled off. A derivative modified with carboxylic acid-modified polyorganosiloxane was obtained. The substitution rate of the derivative was 100%. The oil resistance evaluation of the oil resistant agent was 3 points in the KIT test.

[0350] Table 1 shows the results of Examples 1 to 33 and Comparative Examples 1 and 2.

[0351] Table 1

[0352]

[0353] Industrial Applicability

[0354] The modified natural product of the present invention can be used as an oil-proofing agent, a water-proofing agent, a water-repelling agent, an oil-repelling agent, an antifouling agent, a dirt remover, a stripping agent or a mold release agent, and can be used as an oil-proofing agent in particular. The modified natural product can be used for applications requiring oil resistance, in particular for food applications such as food packaging materials and food containers.

Claims

1. An oil resistant agent, characterized in that: The oil-proofing agent contains a modified natural product having at least one hydroxyl group, wherein the hydrogen atom of the hydroxyl group in the natural product is replaced by an R group at a substitution rate of 30% or more. Natural products do not include starch. The oil resistant agent satisfies one or more of the following (1) to (3): 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'-, wherein R' is a hydrogen atom or an alkyl group having carbon atoms of C1 to C4, Z is a saturated aliphatic hydrocarbon group having 7 to 40 carbon atoms which may have a substituent, or polysiloxane, (1) the natural product is at least one selected from a high-molecular-weight natural product and a low-molecular-weight natural product, The natural high molecular weight substance is at least one selected from cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, K-type carrageenan, I-type carrageenan, polyglycerol, isomaltodextrin, xanthan gum, gellan gum, tamarind seed gum and cyclostranded starch, The low molecular weight natural substance is at least one selected from glucose, sucrose, mannitol, sorbitol, maltitol, stevioside, cyclodextrin, glycerol, menthol, xylitol, glucosamine, catechin, anthocyanidin and quercetin, gluconic acid, malic acid, xylose, inositol, phytic acid, sucralose, fructose, maltose, trehalose, lactulose, erythritol, ascorbic acid, kojic acid, cholesterol, vanillin, lactic acid, tartaric acid, citric acid and chlorogenic acid, (2) Y is a direct bond, -C(=O)-NR'- or -C(=S)-NR'-, wherein R' is a hydrogen atom or an alkyl group having a carbon number of 1 to 4. (3) Z is polysiloxane.

2. The oil resistant agent according to claim 1, characterized in that: Natural substances are compounds that are natural substances themselves or compounds that are derived from natural substances.

3. The oil resistant agent according to claim 1 or 2, characterized in that: Natural products are monosaccharides or polysaccharides, glycerol, and polyglycerol.

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

5. The oil resistant agent according to claim 1 or 2, characterized in that: Z is a saturated aliphatic hydrocarbon group having 7 to 40 carbon atoms which may have a substituent, or polysiloxane, wherein the substituent is a hydroxyl group, an ester group, an R'3Si group, a (R'O)3Si group, a carboxyl group or a carboxyl salt, wherein R' is independently a hydrogen atom or an alkyl group having C1 to C4 carbon atoms.

6. The oil resistant agent according to claim 1 or 2, characterized in that: The contact angle of n-hexadecane, which is an oil-proof agent, is 10 degrees or more.

7. The oil resistant agent according to claim 1 or 2, characterized in that: The melting point of the modified natural product is above 40 degrees or has no melting point.

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

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

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

11. A fiber product, characterized in that: The oil resistant agent according to any one of claims 1 to 10 is attached.

12. An oil-resistant paper, characterized in that: Contains the oil resistant agent according to any one of claims 1 to 10.

13. The oil-resistant paper according to claim 12, characterized in that: The oil-resistant paper is a food packaging material or a food container.

14. A method for treating paper by external application or internal mixing using the oil resistant agent according to any one of claims 1 to 10.

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