Modified natural product and use thereof

Abstract

To provide an oil resistant agent that imparts sufficient oil resistance using a natural product that is a biomass material while harmonizing with an environment.SOLUTION: An oil resistant agent is obtained by replacing a hydrogen atom of a hydroxy group of a natural product that has at least one hydroxy group with an R group, where the R group is -Y-Z [in the formula, Y is a direct coupling, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'- (R' is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), and Z is a hydrocarbon group having 1 to 40 carbon atoms that may include a substituent group, or polysiloxane]. The natural product preferably includes monosaccharide, polysaccharide, glycerin, or polyglycerol.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a modified natural product obtained by modifying a natural product, and its use, particularly an oil-resistant agent.

Background Art

[0002] Paper containers are expected as an alternative to disposable plastic containers. Paper food packaging materials and food containers are required to prevent the leakage of moisture and oil from food, and an oil-resistant agent is applied to the paper either internally or externally. Also, from the perspective of environmental consideration, the need for biodegradable materials and bio-based materials is increasing.

[0003] Patent Document 1 (Japanese Unexamined Patent Application Publication No. 2019-99953) discloses that oil resistance is exhibited by a combination of oxidized starch or hydrophobized starch and an epichlorohydrin-modified fatty acid-based sizing agent. However, in order to prevent acetic acid odor, pH adjustment of the mixture is necessary. Furthermore, the compatibility between the modified starch and the fatty acid sizing agent is important, and it is difficult to adjust the composition.

[0004] Patent Document 2 (Japanese Unexamined Patent Application Publication No. 2020-066805) discloses an oil-resistant agent using modified starch, clay, a styrene-butadiene copolymer, and an antifoaming agent.

[0005] Patent Document 3 (Japanese Unexamined Patent Application Publication No. 2019-70202) discloses an oil-resistant paper that is a combination of a fluorine-containing polymer having no 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 the use of cellulose having a long-chain alkyl group (12 to 18 carbon atoms) for optical film applications by acetylating 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 an oil-resistant, water-resistant, heat-resistant, etc. property is imparted to a food container by a cellulose acetate film. However, in the examples, water resistance and heat resistance are evaluated, and oil resistance is not evaluated.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0009] An object of the present disclosure is to provide an oil-resistant agent that can impart sufficient oil resistance while being environmentally friendly and using natural products, which are biomass materials.

Means for Solving the Problems

[0010] The present disclosure relates to a modified natural product (modified natural compound) in which a natural product (natural compound) is modified to have an organic modifying group. Examples of the organic modifying group are an aliphatic hydrocarbon group having 1 to 40 carbon atoms, a substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms, or polysiloxane. The modified natural product can be used as an oil-resistant agent.

[0011] Preferred embodiments of the present disclosure are as follows. Embodiment 1: An oil-resistant agent comprising a modified natural product in which a hydrogen atom of a hydroxy group of a natural product having at least one hydroxy group is substituted with an R group. R group: -Y-Z [In the formula, Y is a direct bond, -C(=O)-, -C(=O)-NR'- or -C(=S)-NR'-(R' is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Z is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a polysiloxane.] It is a group represented by. Aspect 2: The oil-resistant agent according to Aspect 1, wherein the natural product is a natural product other than starch. Aspect 3: The oil-resistant agent according to Aspect 1 or 2, wherein the natural product is a natural product as it is or a compound derived from a natural product. Aspect 4: The oil-resistant agent according to any one of Aspects 1 to 3, wherein the natural product is a monosaccharide or a polysaccharide, glycerin, or polyglycerin. Aspect 5: The natural product is at least one selected from high-molecular natural products and low-molecular natural products, 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, polyglycerin, isomalto-dextrin, xanthan gum, gellan gum, tamarind seed gum, and cycloamylose, The oil-resistant agent according to any one of Aspects 1 to 4, wherein the low-molecular natural product is at least one selected from glucose, sucrose, mannitol, sorbitol, sorbitan, maltitol, stevioside, cyclodextrin, glycerin, 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. Aspect 6: The oil-resistant agent according to any one of Aspects 1 to 5, wherein the substitution rate of the hydrogen atom of the hydroxy group by R is 3 to 100%. Aspect 7: The oil-resistant agent according to any one of Aspects 1 to 6, wherein Z is an aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or polysiloxane, and the substituent is a hydroxy group, an ester group, an R’3Si group, an (R’O)3Si group, a carboxyl group, or a salt of a carboxyl group (R’ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Aspect 8: The oil-resistant agent according to any one of Aspects 1 to 7, wherein the contact angle of the oil-resistant agent with n-hexadecane is 11 degrees or more. Aspect 9: The oil-resistant agent according to any one of Aspects 1 to 8, wherein the melting point of the modified natural product is 40 degrees or more or does not exist. Aspect 10: The oil-resistant agent according to any one of Aspects 1 to 9, wherein the viscosity of the oil-resistant agent at a solution concentration of 14.8 mg / mL is 5 cP or more and 100 cP or less. Aspect 11: The oil-resistant agent according to any one of Aspects 1 to 10, which is a water-dispersed composition. Aspect 12: The oil-resistant agent according to any one of Aspects 1 to 11, which is for paper. Aspect 13: A fiber product to which the oil-resistant agent according to any one of Aspects 1 to 12 is attached. Aspect 14: Oil-resistant paper containing the oil-resistant agent according to any one of Aspects 1 to 12. Aspect 15: The oil-resistant paper described in Aspect 14, which is a food packaging material or a food container. Aspect 16: A treatment method of externally adding or internally adding an oil-resistant agent to paper, the oil-resistant agent being described in any one of Aspects 1 to 12.

Advantages of the Invention

[0012] The modified natural product of the present disclosure exhibits excellent oil resistance. Since the oil-resistant agent containing the modified natural product of the present disclosure is derived from a bio-based source, it is excellent in biodegradability without imposing a burden on the ecological environment.

Modes for Carrying Out the Invention

[0013] The present disclosure provides a modified natural product (modified natural compound) in which a hydrogen atom of a hydroxy group of a natural product having at least one hydroxy group is substituted with an R group. The R group has the formula: -Y-Z [wherein, Y is a direct bond, -C(=O)-, -C(=O)-NR'- or -C(=S)-NR'-(R' is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).), Z is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a polysiloxane.] It is preferably a group represented by. Examples of the substituent are a hydroxy group, an ester group, an R'3Si group, an (R'O)3Si group, a carboxyl group, or a salt of a carboxyl group (each of R' is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Any two of the Rs may be bonded to each other to form a ring. The modified natural product (modified natural compound) has an -O-R group that does not exist in the natural product. 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.

[0014] Examples of the R group include -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 described above).

[0015] Z is a monovalent group. Z is a hydrocarbon group having 1 to 40 carbon atoms, or a hydrocarbon group having 1 to 40 carbon atoms with substituents. 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, especially an alkyl group. The -CH3 group has a lower surface free energy and is more likely to exhibit liquid repellency than the -CH2- group. 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.

[0016] 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 of a certain length (for example, having 16 to 40 carbon atoms) exhibits high water repellency due to its crystallinity. Therefore, a branched hydrocarbon group (for example, a branched (for example, having 3 to 10 or 4 to 8 carbon atoms) alkyl group), for example, a t-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), for example, 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.

[0017] The number of carbon atoms of 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, preferably 10 or more or 12 or more. The number of carbon atoms of the hydrocarbon group may be 40 or less, 35 or less, 30 or less, 25 or less, 22 or less, 20 or less, or 18 or less. Preferably it is 30 or less.

[0018] The hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group. The hydrocarbon group may be linear, branched, or cyclic, preferably linear or branched, and more preferably linear. The hydrocarbon group may be unsaturated (e.g., monounsaturated, diunsaturated, triunsaturated, tetraunsaturated, or polyunsaturated) or saturated, for example, an alkyl group.

[0019] Specific examples of the hydrocarbon group include alkyl groups such as n-butyl group, t-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, palmitoyl group, eicosenyl group, etc.; cycloalkyl groups such as cyclohexyl, etc.

[0020] Z may be a hydrocarbon group substituted with a carboxyl group. The hydrocarbon group substituted with a carboxyl group is preferably a group represented by the formula: -A-C(=O)-OH (A is a direct bond or a hydrocarbon group having 1 to 40 or 1 to 10 carbon atoms, for example, an alkylene group).

[0021] Z may be a hydrocarbon group substituted with a salt of a carboxyl group. That is, it may be a hydrocarbon group substituted with a salt of a carboxyl group and a base. 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 (A is a direct bond or a hydrocarbon group having 1 to 40 or 1 to 10 carbon atoms, for example, an alkylene group). As the base, ammonia, an organic amine, or an alkali metal hydroxide is preferably used.

[0022] 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 thereof.

[0023] By neutralizing with a base, the modified natural product has good dispersibility in an aqueous dispersion medium, and an aqueous dispersion of an oil-resistant agent can be suitably obtained.

[0024] Z may be a polysiloxane group. The polysiloxane group is, for example, of the formula: -B-[-Si(R 21 )2-O-] a -[-Si(R 22 )(R 21 )-O-] b -A [In the formula, A is -Si(R 21 )3 or -X 1 , and B is -[-(R 24 )-O-]q-R 23 -[-Si(R 21 )2-O-]p- (p and q are 0 or 1.), and X 1 may be interrupted by an oxygen atom and may have an epoxy ring, a hydroxy group, a (meth)acrylic group (or acryloyloxy group) and / or a carboxyl group, and is a linear or branched hydrocarbon group having 1 to 20 (or 1 to 40) carbon atoms, Each of R 21 independently represents a hydrogen atom, an alkyl group having 1 to 20 (or 1 to 40) carbon atoms, an aryl group having 6 to 20 (or 6 to 40) carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, Each of R 22 independently represents a hydrogen atom, an alkyl group having 1 to 20 (or 1 to 40) carbon atoms, an aryl group having 6 to 20 (or 6 to 40) carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, R 23represents a hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by an oxygen atom, R 24 represents a hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by an oxygen atom, a represents an integer of 0 or more, b represents an integer of 1 or more, and (a + b) is 3 to 200.] and may be a group represented by.

[0025] R 21 may have an epoxy ring, a hydroxy group, a (meth)acrylic group (or acryloyloxy group) and / or a carboxyl group. p and q are 0 or 1. It is preferable that both p and q are 0 or 1.

[0026] Examples of the polysiloxane group include the formula: -(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 or -(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 or -R 23 -[-Si(R 21 )2-O-] a -[-Si(R 22 )(R 21 )-O-] b -Si(R 21 )3 or -R 23 -[-Si(R 21)2 - O - a -[-Si(R 22 )(R 21 ) - O - b -X 1 [wherein, X 1 may be interrupted by an oxygen atom and is a linear or branched hydrocarbon group having 1 to 20 (or 1 to 40) carbon atoms which may have an epoxy ring, a hydroxy group, a (meth)acrylic group (or acryloyloxy group) and / or a carboxyl group, Each of R 21 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, Each of R 22 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, R 23 represents a hydrocarbon group having 1 to 20 carbon atoms, R 24 represents a hydrocarbon group having 1 to 20 carbon atoms, a represents an integer of 0 or more, b represents an integer of 1 or more, and (a + b) is 3 to 200.] It may be a group represented by R 21 and R 22 may be a hydrocarbon group having 1 to 40 carbon atoms.

[0027] Examples of X 1 are a hydrocarbon group having 1 to 40 carbon atoms (e.g., t - 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 hydroxy 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 hydroxy group (e.g., one or two hydroxy groups), a hydrocarbon group having 1 to 40 carbon atoms having a (meth)acrylic group (or (meth)acryloyloxy group), and A hydrocarbon group having 1 to 40 carbon atoms and a carboxyl group is. In the present specification, the (meth)acrylic group means an acrylic group and a methacrylic group.

[0028] Another example of Z which is a polysiloxane group is the formula: -(R 3 )2Si-O-[-Si(R 1 )2-O-] a -[-Si(R 1 )(R 2 )-O-] b -Si(R 3 )3 [wherein each of 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, each of R 2 independently represents a saturated hydrocarbon group having 1 to 40 carbon atoms, each of 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, a represents an integer of 0 or more, b represents an integer of 1 or more, and (a + b) is 3 to 200.] It may be a group represented by.

[0029] In the polysiloxane group (for example, 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 or may be substituted. The alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms (for example, R 21 , R 22 , R 1 and R 3Specific examples of [[ID=]] are a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group; a cyclopentyl group, a cyclohexyl group, a cycloheptyl group; a phenyl group, a tolyl group, a naphthyl group, or a group in which some or all of the hydrogen atoms bonded to these groups are substituted with a halogen atom, an amino group, a cyano group, etc. R 21 , R 22 , R 1 and R 3 are preferably a methyl group or an ethyl group. 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 (for example, a hydrocarbon group having an aromatic ring), but preferably do not have these groups. R 21 , R 22 , R 1 and R 3 In, 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 are a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

[0030] In terms of being easy to manufacture industrially and being easily available, R 21 , R 22 , R 1 and R 3 are preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

[0031] The polysiloxane group has at least one hydrocarbon group having 1 to 40 carbon atoms, particularly a saturated hydrocarbon group. Regarding the hydrocarbon group having 1 to 40 carbon atoms in the polysiloxane group, the same explanation as in the case where Z is a hydrocarbon group having 1 to 40 carbon atoms can be made. The number of carbon atoms in the hydrocarbon group may 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 include a methyl group (1 carbon atom), an ethyl group (2 carbon atoms), a lauryl group (12 carbon atoms), a stearyl group (18 carbon atoms), a tricosyl group (23 carbon atoms), a lignoceryl group (tetracosyl group, 24 carbon atoms), a cerotyl group (hexacosyl group, 26 carbon atoms), a montyl group (octacosyl group, 28 carbon atoms), a melissyl group (triacontane group, 30 carbon atoms), and a dotriacontane group (32 carbon atoms).

[0032] 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.

[0033] 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, for example 1 to 100. The lower limit of b may be 1 or 2 or 3, and the upper limit of b may be 150, 10, or 5.

[0034] When a or b is 2 or more, R present in plural 1 and R 2 may each be the same or different. R 1 and R 2 groups and R 3 It is preferable that 50 mol% or more of the total of the groups is a methyl group. The order of existence of the repeating units enclosed by a or b is not limited to the order of existence shown in the chemical formula, and is arbitrary. That is, the polysiloxane group may be a random polymer or a block polymer.

[0035] Examples of the polysiloxane group are as follows. JPEG2025096398000001.jpg2064[wherein, a represents an integer from 0 to 150, b represents an integer from 1 to 150, (a + b) is from 5 to 200, and n is an integer from 0 to 36.]

[0036] A natural product (natural compound) is a compound that exists in nature and has at least one hydroxy group (hydroxy group-containing natural compound). The natural product may be low molecular weight (e.g., weight average molecular weight less than 1000, or 500 or less) and / or high molecular weight. The weight average molecular weight of the high molecular weight may 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 may 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) in terms of pullulan. The natural product may be a high molecular weight natural product, a low molecular weight natural product or derivatives thereof. Compounds converted from microorganisms are also included in the natural product.

[0037] Examples of high molecular weight natural products include starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan. Other examples include locust bean gum, kappa carrageenan, iota carrageenan, polyglycerin, isomalto dextrin, xanthan gum, gellan gum, tamarind seed gum, cycloamylose. It is preferred that the natural product is other than starch. Examples of low-molecular-weight natural products include glucose, sucrose, mannitol, sorbitol, sorbitan, maltitol, stevioside, cyclodextrin, glycerin, menthol, xylitol, glucosamine, catechin, anthocyanin, quercetin, gluconic acid and malic acid, xylose, inositol, phytic acid, menthol, sucralose, fructose, maltose, trehalose, lactulose, erythritol, ascorbic acid, kojic acid, cholesterol, vanillin, lactic acid, tartaric acid, citric acid, and chlorogenic acid.

[0038] The natural product may be the natural product itself as a compound or a compound derived from the natural product. That is, the natural product includes derivatives of the natural product. For example, derivatives of starch include oxidized starch, hydrophobized starch, acetic acid starch, phosphoric acid esterified starch, acetylated starch, etherified starch, cationized starch, carbamic acid starch, hydroxymethylated starch, hydroxyethylated starch, and hydroxypropylated starch. Derivatives of cellulose include 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-(trimethylammonio)propyl] hydroxyethyl cellulose chloride. When the derivative of the natural product has high oil resistance, it can be used as an oil-resistant agent without modification. That is, the derivative of the natural product may be a modified natural product (modified natural compound).

[0039] The natural product may be a monosaccharide or a polysaccharide (such as a disaccharide or a trisaccharide). Examples of monosaccharides include glucose, galactose, fructose, aldose, alditol, ketose, pyranose, furanose, aldonic acid, uronic acid, and aldaric acid. A polysaccharide is a compound in which a plurality (3 or more, for example 3 to) of monosaccharides such as glucose, galactose, and fructose are bonded. The polysaccharide may be an oligosaccharide in which 3 to 10 monosaccharides are bonded.

[0040] 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, isomaltooligosaccharide, xanthan gum, gellan gum, tamarind seed gum, curdlan, pullulan, and cyclodextrin.

[0041] The natural product may be starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, or chitosan, but cellulose is particularly preferred.

[0042] When the natural product is cellulose, the modified cellulose is, for example, Formula: JPEG2025096398000002.jpg3341[wherein at least one R group is a -Y-Z group and the remaining R groups are hydrogen atoms. All three R groups may be -Y-Z groups. The Y group and the Z group have the same meanings as described above. n is a number of 2 or more, for example 100 or more or 500 or more.] It has a repeating structure represented by

[0043] The natural product may be, for example, aldose, alditol, ketose, pyranose, furanose, aldonic acid, uronic acid, and aldaric acid.

[0044] Aldose is C m H 2m O mIt is a monosaccharide having a chemical formula of (m is 3 or more, and the upper limit of m is generally 100, 20, or 10). Specific examples of aldose include erythrose, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, and talose. An alditol is a monosaccharide in which the aldehyde group of aldose is reduced to a hydroxymethyl group, and is a monosaccharide having 3 or more carbon atoms (the upper limit of the number of carbon atoms is generally 100, 20, or 10). Specific examples of alditol include erythritol, threitol, ribitol, arabinitol, xylitol, arabitol, allitol, altitol, sorbitol (glucitol), mannitol, sorbitol (glucitol), iditol, galactitol, and altitol. A ketose is a monosaccharide containing one keto group (ketonic carbonyl group) inside a chain structure (the upper limit of the number of carbon atoms is generally 100, 20, or 10). Specific examples of ketose (specific examples having 3 to 6 carbon atoms) include dihydroxyacetone, erythrulose, ribulose, xylulose, psicose, fructose, sorbose, and tagatose.

[0045] Pyranose is a monosaccharide having a six-membered ring composed of five carbon atoms and one oxygen atom. Specific examples of pyranose include ribopyranose, arabinopyranose, xylopyranose, lyxopyranose, allopyranose, altropyranose, glucopyranose, mannopyranose, and glucopyranose. 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.

[0046] Modified natural compounds can be produced by reacting a modifying agent with the hydroxy groups of natural products. Examples of methods for reacting a modifying agent with a hydroxy group include methods for forming urethane bonds, methods for forming ester bonds, and methods for forming ether bonds as examples of synthetic methods for reacting a modifying agent. The modifying agent is preferably a compound having a hydrocarbon group, particularly a compound having an aliphatic hydrocarbon group. Examples of the modifying agent are as follows. Aliphatic isocyanates and / or aromatic isocyanates (Z-N=C=O), Aliphatic isothiocyanates and / or aromatic isothiocyanates (Z-N=C=S), Fatty acids (Z-C(=O)-OH), Acid halogen compounds (Z-C(=O)-X), Acid anhydrides (Z-[C=O]-O-[C=O]-Z), Alkyl halide compounds (Z-X), Epoxy compounds (Z-CHOCH2), Acrylic esters (Z-CH2=CH), Amines (Z-NH2), Aliphatic alcohols (Z-OH), [Wherein, X is a halogen atom (for example, a chlorine atom, a bromine atom or an iodine atom), Z is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a polysiloxane.]

[0047] The substitution rate of the hydroxy group by the modifying agent may be 1 to 100% (0.01 to 1.00). It 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 50% or more, and 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" means the ratio (%) of the hydroxy groups present in the structure of the modified natural product (modified natural compound) that are substituted by the modifying agent.

[0048] The ratio of unmodified hydroxy groups (i.e., the residual ratio of hydroxyl groups) may be 0% or more, 1% or more, 3% or more, 5% or more, or 7% or more, for example, 10% or more or 20% or more, and may be 99% or less, 97% or less, or 95% or less, for example, 90% or less, 85% or less, 80% or less, or 70% or less.

[0049] <Method for forming urethane bond> An aliphatic isocyanate and / or an aromatic isocyanate (Z-NCO) is reacted with a hydroxy group to form a urethane bond. Instead of or in addition to the isocyanate, an aliphatic isothiocyanate and / or an aromatic isothiocyanate (Z-N=C=S) may be used.

[0050] In the synthetic method of substituting the hydrogen atom of the hydroxy group of a natural product with an aliphatic isocyanate, in an organic solvent, in the presence of a catalyst such as a tin catalyst or an amine, when the hydroxy group-containing natural product is reacted with an aliphatic isocyanate or an aromatic isocyanate, the hydrogen atom of the hydroxy group reacts with the isocyanate group, and various modifying groups (Z groups) can be introduced via a urethane bond. The aliphatic isocyanate is C n H 2n+1 -NCO (n = 1 to 40, particularly 3 to 18). The aliphatic hydrocarbon group may be linear or branched.

[0051] Specific examples of the aliphatic isocyanate include saturated aliphatic isocyanates such as methyl isocyanate, ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, t-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.

[0052] 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'-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.

[0053] In the synthesis method of substituting the hydrogen atom of the hydroxy group of a natural product with an aliphatic isothiocyanate, in an organic solvent, in the presence of a catalyst such as a tin catalyst or an amine, reacting a hydroxy group-containing natural product with an aliphatic isocyanate or an aromatic isothiocyanate enables the hydrogen atom of the hydroxy group to react with the isothiocyanate group, and various modifying groups (Z groups) can be introduced via a thiourethane bond. The aliphatic isothiocyanate is preferably a compound represented by C n H 2n+1 -NSO (n = 1 to 40, particularly 3 to 18). The aliphatic hydrocarbon group may be linear or branched.

[0054] Specific examples of the aliphatic isothiocyanate include 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; and Examples of unsaturated aliphatic isocyanates include butenyl isothiocyanate, pentenyl isothiocyanate, hexenyl isothiocyanate, octenyl isothiocyanate, dodecenyl isothiocyanate, and the like.

[0055] Specific examples of aromatic isothiocyanates 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'-diphenylpropane-4,4'-diisothiocyanate, 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.

[0056] <Method for forming an ester bond> A fatty acid (Z-C(=O)-OH), an acid halogen compound (Z-C(=O)-X), or an acid anhydride (Z-[C=O]-O-[C=O]-Z) is reacted with a hydroxy group to form an ester bond.

[0057] Synthetic methods for substituting a hydrogen atom of a hydroxy group of a natural product with a saturated aliphatic acyl group include a method of reacting a hydroxy group-containing natural product with a saturated fatty acid halide in the presence of a base such as pyridine, a method of reacting a hydroxy group-containing natural product with a mixed acid anhydride formed from a saturated fatty acid and a haloacetic acid such as trifluoroacetic acid, a method of reacting a hydroxy group-containing natural product with an anhydride of a saturated fatty acid, a method of reacting a hydroxy group-containing natural product with a saturated fatty acid in the presence of a sulfonate, a method of reacting a hydroxy group-containing natural product with a saturated fatty acid in the presence of a dehydration condensing agent, and the like.

[0058] The saturated fatty acid is Cn H 2n+1 It is preferably a compound represented by -COOH (n = 1 to 39). The aliphatic hydrocarbon group may be linear or branched. 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, and behenic acid.

[0059] Specific examples of unsaturated fatty acids are palmitolinoleic 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. The acid halogen compound is C n H 2n+1 It is preferably a compound represented by -CO-X (n = 1 to 39, X = Br, Cl, I). The aliphatic hydrocarbon group may be linear or branched.

[0060] Specific examples of acid halogen 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, and valeryl bromide.

[0061] The acid anhydride is preferably a compound represented by (C n H 2n+1 -CO)2-O (n = 1 to 19 or 1 to 39). The aliphatic hydrocarbon group may be linear or branched.

[0062] 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.

[0063] Specific examples of the acid anhydride forming a 6-membered ring structure include cyclohexanedicarboxylic anhydride (such as cyclohexane-1,2-dicarboxylic anhydride), 4-cyclohexene-1,2-dicarboxylic anhydride, glutaric anhydride, glutaconic anhydride, 2-phenylglutaric anhydride, etc., and their analogs.

[0064] <Method for forming an ether bond> An alkyl halide compound (Z-X) or an epoxy compound (Z-CHOCH2) is reacted with a hydroxy group to form an ether bond. Synthetic methods for substituting a hydrogen atom of a hydroxy group of a natural product with an alkyl group include reacting a hydroxy group-containing natural product with an alkaline aqueous solution of an alkyl halide compound (e.g., sodium hydroxide, potassium hydroxide), or reacting in an organic solvent in which a basic compound and an alkyl halide are dissolved. Thereby, the hydrogen atom of the hydroxy group is substituted with an alkyl group.

[0065] The alkyl halide compound is preferably a compound represented by C n H 2n+1 -X (n = 1 to 40, X = Cl, Br, I). Specific examples of the alkyl halide compound include methyl halide, ethyl halide, propyl halide, butyl halide, pentyl halide, hexyl halide, heptyl halide, octyl halide, nonyl halide, decyl halide, undecyl halide, dodecyl halide, tridecyl halide, tetradecyl halide, pentadecyl halide, hexadecyl halide, heptadecyl halide, octadecyl halide, nonadecyl halide, icosyl halide, henicosyl halide, docosyl halide, tricosyl halide, and the like.

[0066] By reacting a hydroxy group-containing natural product (hydroxy group-containing natural compound) with an epoxy compound, a natural product having an ether bond can be obtained.

[0067] The epoxy compound is preferably a compound represented by C n H 2n+1 -CHOCH2 (n = 1 to 40). The epoxy compound is preferably a monofunctional epoxy compound having one three-membered ring ether structure. Specific examples of the epoxy compound include ethylene oxide, propylene oxide, 1-butene oxide, 2-butene oxide, stearyl glycidyl ether, cetyl glycidyl ether, and the like.

[0068] <Substituents other than the R group> The hydrogen atom of the hydroxy group of the natural product may be substituted with a substituent having ionic properties other than R. The ion-donating group is an anionic group and / or a cationic group.

[0069] Examples of the anionic group include monomers having a carboxyl group, a sulfonic acid group, or a phosphoric acid group.

[0070] Examples of the salt of the anionic group include alkali metal salts, alkaline earth metal salts, or ammonium salts, such as methylammonium salts, ethanolammonium salts, triethanolammonium salts, and the like.

[0071] Examples of the cationic group include amino groups, preferably tertiary amino groups and quaternary amino groups. In the tertiary amino group, the two groups bonded to the nitrogen atom are the same or different and are preferably an aliphatic group having 1 to 5 carbon atoms (especially an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (especially an aralkyl group, such as a benzyl group (C6H5-CH2-)). In the quaternary amino group, the three groups bonded to the nitrogen atom are the same or different and are preferably an aliphatic group having 1 to 5 carbon atoms (especially an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (especially an aralkyl group, such as a benzyl group (C6H5-CH2-)). In the tertiary amino group and the quaternary amino group, the remaining one group bonded to the nitrogen atom may have a carbon-carbon double bond. The cationic group may be in the form of a salt.

[0072] The cationic group which is a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, such as carboxylic acids having 1 to 20 carbon atoms (especially monocarboxylic acids such as acetic acid, propionic acid, butyric acid, stearic acid, etc.) are preferred.

[0073] <Treatment agent (oil-resistant agent)> The treatment agent (oil-resistant agent) comprises a modified natural product. The oil-resistant agent has oil resistance and may further have water resistance, water repellency, and oil repellency. The oil-resistant agent may contain a liquid medium (water, organic solvent, or a mixed solution thereof) in addition to the modified natural product. The oil-resistant agent may further contain at least one selected from surfactants, blocked isocyanate compounds, and additives.

[0074] 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 with respect 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 with respect to the oil-resistant agent.

[0075] The oil-resistant agent may contain an aqueous medium. The liquid medium is water alone, an organic solvent (e.g., alcohol, ketone, ester) alone, or a mixture of water and an organic solvent, and preferably water alone.

[0076] With respect 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.

[0077] When the liquid medium is a mixture of water and an organic solvent, the amount of the organic solvent (e.g., alcohol, ester, and ketone) 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 with respect to the liquid medium. The amount of the organic solvent may be 90% by weight or less, 50% by weight or less, 30% by weight or less, or 10% by weight or less with respect to the liquid medium.

[0078] The oil-resistant agent may be a solution (especially, an aqueous solution) or a dispersion composition (especially, an aqueous dispersion (aqueous dispersion composition)).

[0079] <Surfactant or dispersant> The oil-resistant agent may or may not contain a surfactant (emulsifier) or a dispersant. Generally, for the stabilization of particles during the substitution reaction of hydroxyl groups and the stabilization of the aqueous dispersion after the reaction, a small amount of a surfactant or a dispersant (e.g., 0.01 to 100 parts by weight or 0.01 to 50 parts by weight, for example, 0.1 to 15 parts by weight with respect to 100 parts by weight of the natural product) may be added during the reaction, or a surfactant or a dispersant may be added after the reaction.

[0080] Particularly when the object to be treated is a textile product, in the oil-resistant agent, the surfactant or dispersant preferably contains a nonionic surfactant. Further, the surfactant preferably contains one or more surfactants selected from cationic surfactants, anionic surfactants, and amphoteric surfactants. It is preferable to use a combination of a nonionic surfactant and a cationic surfactant.

[0081] Each of the nonionic surfactant, cationic surfactant, and amphoteric surfactant may be one kind or a combination of two or more kinds. The amount of the surfactant or dispersant may be 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 with respect to a total of 100 parts by weight of the natural product (or modified natural product). Generally, when a surfactant or dispersant is added, the stability of the aqueous dispersion and the permeability to the fabric are improved.

[0082] <Block isocyanate compound> The oil-resistant agent may or may not contain a block isocyanate compound. The block isocyanate compound may be added before the substitution reaction of the hydroxyl group or after the reaction (for example, before the curing step).

[0083] The block isocyanate compound can be produced by reacting an isocyanate (A(NCO) m [wherein A is a group remaining after the isocyanate group is removed from the isocyanate compound, and m is an integer of 2 to 8]) with a blocking agent (RH [wherein R may be a hydrocarbon group optionally substituted by a heteroatom such as a nitrogen atom or an oxygen atom, and H is a hydrogen atom]).

[0084] A(NCO) mThey are, for example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), etc. Examples of the blocking agent forming the R group are oxime, phenol, alcohol, mercaptan, amide, imide, imidazole, urea, amine, imine, pyrazole and active methylene compounds.

[0085] As the blocked isocyanate compound, blocked isocyanates such as oxime-blocked toluene diisocyanate, blocked hexamethylene diisocyanate, and blocked diphenylmethane diisocyanate are preferred.

[0086] 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, 2.5 parts by weight or less based on 100 parts by weight of the modified natural product.

[0087] <Additive> The oil-resistant agent may contain an additive. Examples of the additive are binder resin, dispersant, water-resistant agent, oil-resistant agent, water-repellent agent, oil-repellent agent, drying rate regulator, crosslinking agent, film-forming aid, compatibilizer, antifreezing agent, viscosity regulator, ultraviolet absorber, antioxidant, pH regulator, defoaming agent, texture regulator, lubricity regulator, antistatic agent, hydrophilizing agent, antibacterial agent, preservative, insect repellent, fragrance, flame retardant, sizing agent, paper strength enhancer. The amount of the additive may be 0.1 to 20 parts by weight, for example 0.1 to 10 parts by weight based on 100 parts by weight of the modified natural product.

[0088] <Properties of the oil-resistant agent and the modified natural product> The contact angle of n-hexadecane with respect to the modified natural product (or the oil-resistant agent) (on a glass substrate) 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, more preferably 35° or more, 40° or more, or 45° or more. When the contact angle of n-hexadecane is within the above range, the oil-resistant agent has excellent liquid repellency, which is preferable particularly from the viewpoint of oil resistance and the like.

[0089] The surface free energy of the modified natural product is 20 mN / m -1 or more, 25 mN / m -1 or more, or 30 mN / m -1 or more is preferable, and 70 mN / m -1 or less, 60 mN / m -1 or less or 50 mN / m -1 or less is preferable.

[0090] The preferable range of the difference between the SP value of the modified natural product (or oil-resistant agent) and that of corn oil may be 3 or more, 5 or more, or 7 or more.

[0091] 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. Also, the melting point of the oil-resistant agent is preferably 200°C or lower, 180°C or lower, or 160°C or lower. When the melting point of the oil-resistant agent is within the above range, the coating property and the resistance to temperature when treating fiber products are improved, which is preferable especially from the viewpoint of oil resistance.

[0092] 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. Also, the glass transition temperature of the modified natural product is preferably 180°C or lower, 140°C or lower, 130°C or lower, or 120°C or lower. When the glass transition temperature of the modified natural product is within the above range, the coating property and the resistance to temperature when treating fiber products are improved, which is preferable especially from the viewpoint of oil resistance.

[0093] 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. Also, 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. When the viscosity of the polymer solution of the oil-resistant agent is within the above range, the coating property when treating fiber products is improved, which is preferable especially from the viewpoint of oil resistance.

[0094] 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. When the air permeability of the treated paper is at or above the above values, the voids between the fibers are blocked, and particularly the oil resistance may be improved. The treated paper for measuring the air permeability is prepared by coating a base paper of paper with a basis weight of 45 g / m2 and a paper density of 0.58 g / cm 3 with a polymer (modified natural product) solution of an oil-resistant agent at a concentration of 14.8 mg / mL using a Baker applicator set at 0 mil, and repeating the operations of coating and drying three times, and annealing at 70°C to 180°C (for example, 70°C) for 10 minutes.

[0095] The preferable range of the combination of the contact angle of hexadecane and the air permeability may 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 preferable range of the combination of the contact angle of hexadecane and the air permeability may 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. Or, the preferable range of the combination of the contact angle of hexadecane and the air permeability may 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. Alternatively, the preferable range of the combination of the contact angle of hexadecane and the air permeability may 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.

[0096] It is preferable that the product of the contact angle and air permeability of hexadecane is 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 and air permeability of hexadecane may be 300000 (degree·s), 200000 (degree·s) or 100000 (degree·s). The product of the contact angle and air permeability of hexadecane being not less than the above numerical value means that either the liquid repellency or coating property of the oil-resistant agent is in a sufficient state to exhibit oil resistance.

[0097] <Use of Modified Natural Product> The modified natural product can be used as various agents such as oil-resistant agents, water-resistant agents, water-repellent agents, oil-repellent agents, antifouling agents, soil release agents, release agents or mold release agents, or their components. The modified natural product can be used as an external treatment agent (surface treatment agent) or an internal treatment agent or their components.

[0098] When the substrate is treated with the modified natural product, the modified natural product can form a surface coating structure on the substrate surface.

[0099] The treated object (substrate) is dried in order to exhibit liquid repellency, and preferably, for example, heated at a temperature not lower than the Tg of the modified natural product, for example, 100°C to 200°C. By treating at a temperature not lower than the Tg of the modified natural product, the substrate surface is coated with the modified natural product, and further the arrangement of the side chains is induced. Thereby, a surface coating structure excellent in hydrophobicity can be formed.

[0100] The surface coating structure can be formed by applying a modified natural product to an object to be treated (substrate) by a conventionally known method and attaching it to the surface of the substrate. Usually, the modified natural product is dispersed and diluted in an organic solvent or water, and then attached to the surface of the object to be treated and dried by a known method such as dip coating, spray coating, or foam coating. If necessary, it may be applied together with a suitable cross-linking agent (for example, a blocked isocyanate compound) and cured. Furthermore, it is also possible to add and use together with the modified natural product an insect repellent, a softening agent, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent, a sizing agent, a paper strength enhancer, etc.

[0101] Examples of objects to be treated with an agent containing a modified natural product include textile products, stone, filters (for example, electrostatic filters), dust masks, parts of fuel cells (for example, gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster, etc.

[0102] As for textile products, various examples can be given. For example, cloth products and paper products can be mentioned.

[0103] Examples of cloth products include animal and plant natural fibers 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 thereof. Cloth products include woven fabrics, knitted fabrics, and non-woven fabrics, cloth in the form of clothing, and carpets. However, the fibers, yarns, and intermediate textile products (for example, sliver or roving, etc.) in the state before being made into cloth may also be treated.

[0104] Examples of paper products include paper made from bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, groundwood pulp, bleached or unbleached high-yield pulp such as mechanical pulp or thermomechanical pulp, waste paper pulp such as newspaper waste paper, magazine waste paper, cardboard waste paper or deinked waste paper, etc., paper containers made of paper, molded bodies made of paper, and the like. Specific examples of paper products include food packaging paper, gypsum board base paper, coated base paper, medium paper, general liner and core, neutral pure white roll paper, neutral liner, rust-proof liner and metal laminated 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, mold paper (mold container), and the like. Since the modified natural product of the present disclosure is excellent in oil resistance (for example, high-temperature oil resistance), it is preferably used for applications that require oil resistance, particularly food packaging materials and food containers.

[0105] The modified natural product can be applied to a fibrous substrate (for example, a fiber product, etc.) by any of the methods known for treating fiber products with a liquid. When the fiber product is cloth, the cloth may be immersed in a solution, or the solution may be adhered or sprayed onto the cloth. The treatment may be an external addition treatment or an internal addition treatment. When the fiber product is paper, it may be coated on the paper, or the solution may be adhered or sprayed onto the paper, or it may be mixed with the pulp slurry before papermaking and treated. The treatment may be an external addition treatment or an internal addition treatment.

[0106] The modified natural product may be applied to a pre-formed fiber product (particularly paper, cloth, etc.), or may be applied at various stages of papermaking, for example, during the drying period of the paper. The modified natural product may be applied to the fiber product by a cleaning method, for example, it may be applied to the fiber product in a washing application or a dry cleaning method, etc.

[0107] Alternatively, the fibrous substrate may be leather. The modified natural product 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 period of the leather or during the finishing period of the leather, in order to make the leather hydrophobic and oleophobic.

[0108] The modified natural product can also be used as an external mold release agent. For example, the surface of the substrate can be easily peeled off from other surfaces (other surfaces on the substrate or surfaces on other substrates).

[0109] In the case of paper products, for example, there is a method of spraying a natural modified product solution onto a pulp mold and heating and drying it. Alternatively, a natural modified product dispersed by an emulsifier or the like may be mixed into a pulp slurry solution, followed by dehydration molding and heat pressing. Cross-linking agents, paper strength enhancers, fixing agents, etc. may be added to this pulp slurry. Alternatively, paper may be immersed in a natural modified product dispersion solution and heated and dried. In the case of fabric products, there is a method of immersing or spraying the fabric in a natural modified product dispersion solution, dehydrating, and then heating and drying.

[0110] "Treatment" means applying a treatment agent to an object to be treated by means such as immersion, spraying, or coating. By the 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.

[0111] <Paper additive> 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 repellent, oil repellent, water repellent agent, and / or oil repellent agent. The paper additive is preferably in the form of a solution (especially a solution in an organic solvent), an emulsion (especially an aqueous emulsion), or an aerosol. The paper additive comprises a modified natural product and a medium (e.g., a liquid medium such as 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 may be, for example, 0.01 to 50% by weight. The paper additive may not contain a surfactant.

[0112] The removal of the organic solvent contained in the paper additive can be carried out by heating the modified natural product solution (preferably under reduced pressure) (e.g., to 30°C or higher, e.g., 50 to 120°C).

[0113] The paper additive can be used to treat a paper substrate (for example, surface treatment). The paper additive can be applied to the object to be treated by a conventionally known method. Usually, the paper additive is dispersed and diluted in an organic solvent or water, and then adhered to the surface of the object to be treated and dried by a known method such as dip coating, spray coating, foam coating, etc. (surface treatment). Examples of the paper substrate of the object to be treated include paper, a container made of paper, a molded body made of paper (for example, a pulp mold), etc. The modified natural product of the present disclosure adheres well to the paper substrate. Here, adhesion means physical bonding or chemical bonding. By adhering the modified natural product to the paper substrate, oil-resistant paper can be obtained.

[0114] As described above, although the embodiments have been described, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

Examples

[0115] Next, the present disclosure will be specifically described with reference to examples. However, these descriptions do not limit the present disclosure. In the following, parts, % or ratios represent parts by weight, % by weight or weight ratios, unless otherwise specified.

[0116] The test methods used below are as follows.

[0117] Creation of processing paper As the wood pulp, the weight ratio of LBKP (hardwood bleached kraft pulp) and NBKP (softwood bleached kraft pulp) is 60% by weight and 40% by weight, and the drainage degree of the pulp is 400 ml (Canadian Standard Freeness) A pulp slurry was prepared, and a wet paper strength agent and a sizing agent were added to this pulp slurry, and paper having a basis weight of 45 g / m2 and a paper density of 0.58 g / cm3 was used as the base paper for external sizing treatment (size press treatment) by 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. For this base paper, 14.9 mg / cm 3The polymer solution (chloroform or toluene or acetone) was applied using a baker-type applicator with a gap set to 0 mil, and the operations of drying by repetition were performed three times, followed by annealing at 70 °C for 10 minutes to create the treated paper.

[0118] KIT test (oil resistance) It was measured by the 3M kit test (TAPPI T-559cm-02). The 3M kit test method was to place a test oil containing castor oil, toluene, and heptane on the surface of the treated paper, and after wiping the test oil 15 seconds later, evaluate it based on the presence or absence of oil stain on the treated paper. The test was carried out using the test oils of kit numbers 1 to 6, and the maximum kit number with no stain was taken as the evaluation result of oil resistance.

[0119] Cone oil resistance evaluation (oil resistance) Corn oil was placed on the surface of the treated paper, and after wiping the test oil 15 seconds later, it was evaluated based on the presence or absence of oil stain on the treated paper. When there was no stain, it was marked as "〇", and when a stain was seen, it was marked as "×".

[0120] Liquid repellency (static contact angle) The liquid repellency was measured by spin-coating a solution with a solid content concentration of 1.0% of the modified natural product on a glass substrate with a cellophane film attached and measuring the static contact angle. The static contact angle was obtained by dropping 2 μL of hexadecane (HD) on the coating film and measuring the contact angle 1 second after droplet deposition.

[0121] Air permeability The air permeability (air resistance) of the treated paper was measured in accordance with JIS P8117 (2009) using an automatic Gurley densitometer (product No. 323-AUTO, ventilation hole diameter 28.6 ± 0.1 mm) manufactured by Yasuda Seiki Seisakusho Co., Ltd.

[0122] Replacement rate The replacement rate of the oil-resistant agent was 1 determined by 1H NMR or elemental analysis.

[0123] Example 1 A stir bar, 4.0 g of cellulose (20μm Powder), and 4.0 g of LiCl were placed in a reaction vessel equipped with a reflux condenser and a nitrogen inlet tube, and dried under reduced pressure at 80°C for 4 hours. 40 mL of dimethylformamide was added, and the mixture was stirred at 150°C for 1 hour. Then, the temperature was returned to room temperature, and 0.1 g of dibutyltin dilaurate was added. The temperature was changed 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. 1 After confirming the disappearance of octadecyl isocyanate by 1H NMR, the reaction vessel was cooled to room temperature, the reaction mixture was dropped into water to precipitate a solid. The precipitated solid was collected by suction filtration, washed once with methanol and once with acetone. The recovered solid was reprecipitated using chloroform as a good solvent and hexane as a poor solvent to obtain a derivative in which cellulose was modified with octadecyl isocyanate as an oil-resistant agent. The substitution rate of this derivative was 100%. Using this derivative, liquid repellency, KIT test, corn oil resistance, and air permeability were evaluated. The results are shown in Table 1.

[0124] Example 2 A stir bar and 1.6 g of hydroxypropyl cellulose (molecular weight 80,000) synthesized from cellulose were placed in 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 was added, 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. 1 After confirming the disappearance of octadecyl isocyanate by 1H NMR, the reaction vessel was cooled to room temperature, the reaction mixture was concentrated with a rotary evaporator, and reprecipitated using ethyl acetate as a poor solvent to obtain a derivative in which hydroxypropyl cellulose was modified with octadecyl isocyanate as an oil-resistant agent. The substitution rate of this derivative was 100%. Using this derivative, liquid repellency, KIT test, corn oil resistance, and air permeability were evaluated. The results are shown in Table 1.

[0125] Example 3 As an oil-resistant agent, cellulose acetate (1.14 eq modified form, substitution rate: 38%) synthesized from cellulose was used to evaluate liquid repellency, KIT test, corn oil resistance, and air permeability. The results are shown in Table 1.

[0126] Comparative Example 1 As an oil-resistant agent, cellulose (20μm Powder) was used to evaluate liquid repellency, KIT test, corn oil resistance, and air permeability. The results are shown in Table 1.

[0127] Comparative Example 2 When the liquid repellency was evaluated using polyglycerin (average molecular weight 500) as an oil-resistant agent, the KIT test score was 0, the corn oil resistance was ×, and the air permeability was 136 s / 100 cc.

[0128] Example 4 Into a reaction vessel, a stir bar, 5.0 g of polyglycerin (average molecular weight 500), 20 mL of pyridine, and 25 g of octadecyl isocyanate were added, 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 1H NMR, it was added dropwise to hexane to precipitate a solid. The solid precipitated by suction filtration was collected to obtain a derivative in which polyglycerin was 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 a KIT test score of 4, corn oil resistance ○, and air permeability of 289 s / 100 cc.

[0129] Example 5 The procedure was the same as in Example 4 except that the amount of octadecyl isocyanate was changed to 12 g. The substitution rate of this derivative was 54%. The liquid repellency evaluation of this oil-resistant agent was a KIT test score of 4, corn oil resistance ○, and air permeability of 232 s / 100 cc.

[0130] Example 6 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 applied in the same manner. The liquid repellency evaluation of this oil-resistant agent was a KIT test score of 4, corn oil resistance ○, and air permeability of 185 s / 100 cc.

[0131] Example 7 The procedure of Example 4 was repeated, except that 6.3 g of octadecyl isocyanate was changed. 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 resistance, and the air permeability was 231 s / 100 cc.

[0132] Example 8 The procedure of Example 4 was repeated, except that octadecyl isocyanate was changed to 6.2 g of octadecyl isocyanate and 4.5 g of dodecyl isocyanate. 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 resistance, and the air permeability was 224 s / 100 cc.

[0133] Example 9 A stir bar, 2.5 g of polyglycerin (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, followed by stirring at 60 °C for 1 hour. 1 After confirming the disappearance of octadecyl isocyanate by 1H NMR, it was added dropwise to hexane to precipitate a solid. The precipitated solid was collected by suction filtration to obtain a derivative in which polyglycerin was 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 resistance, and the air permeability was 286 s / 100 cc.

[0134] Example 10 A stir bar, 2.5 g of polyglycerin (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, followed by stirring at 60 °C for 1 hour. 1After confirming the disappearance of octadecyl isocyanate by \(^1\)H NMR, the solvent was distilled off to obtain a derivative in which polyglycerol was 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 resistance, and the air permeability was 277 s / 100 cc.

[0135] Example 11 (MS379P) The compound obtained in Example 10 was applied as a 1% aqueous solution. The liquid repellency evaluation of this oil-resistant agent was 5 points in the KIT test, ○ for corn oil resistance, and the air permeability was 269 s / 100 cc.

[0136] Example 12 A 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, followed by stirring at 60 °C for 1 hour. 1 After confirming the disappearance of octadecyl isocyanate by \(^1\)H NMR, the solvent was distilled off to obtain a derivative in which polyglycerol was modified with octadecyl isocyanate as an oil-resistant agent. The substitution rate of this derivative was 4%. This compound was applied as a 1% aqueous solution. The liquid repellency evaluation of this oil-resistant agent was 3 points in the KIT test, ○ for corn oil resistance, and the air permeability was 225 s / 100 cc.

[0137] Example 13 A stir bar, 0.46 g of glycerin, 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, followed by stirring at 60 °C for 1 hour. 1 After confirming the disappearance of octadecyl isocyanate by \(^1\)H NMR, it was added dropwise to hexane to precipitate a solid. The precipitated solid was collected by suction filtration to obtain a derivative in which glycerin was 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 and ○ for corn oil resistance.

[0138] Example 14 A stir bar, 0.92 g of glycerin, 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. The mixture was stirred at 60 °C for 1 hour. 1 After confirming the disappearance of octadecyl isocyanate by 1H NMR, the mixture was added dropwise to hexane to precipitate a solid. The precipitated solid was collected by suction filtration to obtain a derivative in which glycerin was 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 was 4 points in the KIT test and ○ for corn oil resistance.

[0139] Example 15 A stir bar, 1.7 g of diglycerin, 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. The mixture was stirred at 60 °C for 1 hour. 1 After confirming the disappearance of octadecyl isocyanate by 1H NMR, the mixture was added dropwise to hexane to precipitate a solid. The precipitated solid was collected by suction filtration to obtain a derivative in which diglycerin was 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 and ○ for corn oil resistance.

[0140] Example 16 A stir bar, 1.7 g of diglycerin, 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. The mixture was stirred at 60 °C for 1 hour. 1 After confirming the disappearance of octadecyl isocyanate by 1H NMR, the mixture was added dropwise to hexane to precipitate a solid. The precipitated solid was collected by suction filtration to obtain a derivative in which diglycerin was 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 was 4 points in the KIT test and ○ for corn oil resistance.

[0141] Example 17 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. The mixture was stirred at 60 °C for 1 hour. 1 After confirming the disappearance of octadecyl isocyanate by 1H NMR, the mixture was washed with hexane and water to obtain a derivative in which maltitol was 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 resistance, and the air permeability was 1243 s / 100 cc.

[0142] Example 18 The procedure was the same as in Example 17 except that the amount of octadecyl isocyanate was changed to 2.0 g, and a derivative in which maltitol was modified with octadecyl isocyanate was obtained. The substitution rate of this derivative was 60%. The liquid repellency evaluation of this oil-resistant agent was 3 points in the KIT test, ○ for corn oil resistance, and the air permeability was 400 s / 100 cc.

[0143] Example 19 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. The mixture was stirred at 60 °C for 1 hour. 1 After confirming the disappearance of octadecyl isocyanate by 1H NMR, the mixture was washed with hexane and acetone to obtain a derivative in which sorbitol was 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 5 points in the KIT test and ○ for corn oil resistance.

[0144] Example 20 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. The mixture was stirred at 60 °C for 1 hour. 1After confirming the disappearance of octadecyl isocyanate by ¹H NMR, it was washed with hexane and acetone to obtain a derivative in which sorbitol was 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 was 5 points in the KIT test, ○ for corn oil resistance, and the air permeability was 729 s / 100 cc.

[0145] Example 21 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, followed by stirring at 60 °C for 1 hour. 1 After confirming the disappearance of octadecyl isocyanate by ¹H NMR, it was washed with hexane and acetone to obtain a derivative in which sorbitol was 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 was 5 points in the KIT test, ○ for corn oil resistance, and the air permeability was 449 s / 100 cc.

[0146] Example 22 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, followed by stirring at 60 °C for 1 hour. 1 After confirming the disappearance of octadecyl isocyanate by ¹H NMR, it was washed with hexane and acetone to obtain a derivative in which sorbitol was modified with octadecyl isocyanate as an oil-resistant agent. The substitution rate of this derivative was 16%. The liquid repellency evaluation of this oil-resistant agent was 4 points in the KIT test, ○ for corn oil resistance, and the air permeability was 897 s / 100 cc.

[0147] Example 23 A stir bar, 1.8 g of sorbitol, 20 mL of pyridine, and 9.1 g of C₁₇H₃₅COCl were added to a reaction vessel, and it was stirred overnight at 60 °C. It was washed with hexane and acetone to obtain a derivative in which sorbitol was modified with C₁₇H₃₅ ester as an oil-resistant agent. The substitution rate of this derivative was 50%. The liquid repellency evaluation of this oil-resistant agent was 4 points in the KIT test and ○ for corn oil resistance.

[0148] Example 24 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. The mixture was stirred at 60 °C for 1 hour. 1 After confirming the disappearance of octadecyl isocyanate by 1H NMR, the product was washed with hexane and acetone to obtain a derivative in which mannitol as an oil-resistant agent was modified with octadecyl isocyanate. The substitution rate of this derivative was 50%. The liquid repellency evaluation of this oil-resistant agent was 5 points in the KIT test and ○ for corn oil resistance.

[0149] Example 25 A stir bar, 0.40 g of dextrin, and 10 mL of DMSO were added to a reaction vessel and heated to 60 °C to dissolve the dextrin. Then, 1 drop of dibutyltin dilaurate, 2.2 g of octadecyl isocyanate, and 2 mL of CHCl3 were added, and the mixture was stirred at 60 °C. The solid was recovered with a poor solvent to obtain a derivative. The substitution rate of this derivative was 70%. The liquid repellency evaluation of this oil-resistant agent was 3 points in the KIT test, ○ for corn oil resistance, and the air permeability was 1281.7 s / 100 cc.

[0150] Example 26 Using decaglycerol tristearate as an oil-resistant agent, the liquid repellency, KIT test, corn oil resistance, and air permeability were evaluated. The HD contact angle of this oil-resistant agent was 41.1°, 4 points in the KIT test, ○ for corn oil resistance, and the air permeability was 252.1 s / 100 cc.

[0151] Example 27 Using hexaglycerol tristearate as an oil-resistant agent, the liquid repellency, KIT test, corn oil resistance, and air permeability were evaluated. The HD contact angle of this oil-resistant agent was 40.6°, 4 points in the KIT test, ○ for corn oil resistance, and the air permeability was 230.4 s / 100 cc.

[0152] Example 28 As an oil-resistant agent, hexaglycerol pentastearyl ester was used to evaluate liquid repellency, KIT test, corn oil resistance, and air permeability. The HD contact angle of this oil-resistant 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.

[0153] Example 29 As an oil-resistant agent, decaglycerol heptabehenyl ester was used to evaluate liquid repellency, KIT test, corn oil resistance, and air permeability. The HD contact angle of this oil-resistant agent was 40.5°, the KIT test was 5 points, the corn oil resistance was ○, and the air permeability was 604.0 s / 100 cc.

[0154] Example 30 As an oil-resistant agent, decaglycerol decabehenyl ester was used to evaluate liquid repellency, KIT test, corn oil resistance, and air permeability. The HD contact angle of this oil-resistant agent was 40.5°, the KIT test was 5 points, the corn oil resistance was ○, and the air permeability was 236.6 s / 100 cc.

[0155] Example 31 As an oil-resistant agent, hexaglycerol monostearyl ester was used to evaluate liquid repellency, KIT test, corn oil resistance, and air permeability. The HD contact angle of this oil-resistant agent was 41.1°, the KIT test was 5 points, the corn oil resistance was ○, and the air permeability was 237.6 s / 100 cc.

[0156] Example 32 5.8 g of lanolin fatty acid was mixed with 30 ml of pyridine and heated to 50°C. 8.85 g of BOP reagent was added. After 1 hour, 0.46 g of glycerin was added and heated overnight. The resulting solid was washed with dilute hydrochloric acid and acetone, and a derivative in which glycerin was modified with lanolin fatty acid was obtained as an oil-resistant agent by suction filtration. The substitution rate of this derivative was 100%. The oil resistance evaluation of this oil-resistant agent was 3 points in the KIT test.

[0157] Example 33 4.35 g of carboxylic acid-modified polyorganosiloxane (functional group equivalent weight: 1,450 g / mol), 10 ml of pyridine, and 1.77 g of BOP reagent were stirred for 1 hour, 4.35 g of glycerin 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 distilled off. A derivative modified with 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.

[0158] The results of Examples 1 to 33 and Comparative Examples 1 and 2 are shown in Table 1.

[0159]

Table 1

Industrial Applicability

[0160] The modified natural product of the present disclosure can be used as an oil-resistant agent, a water-resistant agent, a water-repellent agent, an oil-repellent agent, an antifouling agent, a soil release agent, a release agent, or a mold release agent, and in particular, can be used as an oil-resistant agent. The modified natural product is suitably used in applications where oil resistance is required, particularly in food applications such as food packaging materials and food containers.

Claims

1. An oil-resistant agent comprising a modified natural product in which a hydrogen atom of a hydroxy group of a natural product having at least one hydroxy group is substituted with an R group. R group: -Y-Z [In the formula, Y is a direct bond, -C(=O)-, -C(=O)-NR'- or -C(=S)-NR'- (R' is a hydrogen atom or a group having a carbon number of C １ ~C ４ is an alkyl group represented by the formula: Z is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a polysiloxane. It is a group represented by the following formula:

2. 2. The oil-proofing agent according to claim 1, wherein the natural product is a natural product other than starch.

3. 3. The oil-resistant agent according to claim 1, wherein the natural product is a compound which is a natural product itself or a compound derived from a natural product.

4. 4. The oil-proofing agent according to claim 1, wherein the natural product is a monosaccharide or polysaccharide, glycerin, or polyglycerin.

5. The natural product is at least one selected from a high molecular weight natural product and a low molecular weight natural product; the polymeric 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, polyglycerin, isomaltodextrin, xanthan gum, gelatin gum, tamarind seed gum, and cycloamylose; The oil-resistant agent according to any one of claims 1 to 4, wherein the low molecular weight natural product is at least one selected from the group consisting of glucose, sucrose, mannitol, sorbitol, sorbitan, maltitol, stepioxide, cyclodextrin, glycerin, menthol, xylitol, glucosamine, catechin, anthocyanin, quercetin, gluconic acid, malic acid, xylose, inositol, phytic acid, menthol, sucralose, fructose, maltose, trehalose, lactosucrose, erythritol, ascorbic acid, kojic acid, cholesterol, vanillin, lactic acid, tartaric acid, citric acid, and chlorogenic acid.

6. 6. The oil-resistant agent according to claim 1, wherein the substitution rate of hydrogen atoms of hydroxy groups with R is 3 to 100%.

7. 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, R' ３ Si group, (R'O) ３ Si group, carboxyl group, or a salt of a carboxyl group (each of R' is independently or １ ~C ４ is an alkyl group represented by the formula: The oil-resistant agent according to any one of claims 1 to 6.

8. 8. The oil-resistant agent according to claim 1, wherein the contact angle of the oil-resistant agent with n-hexadecane is 10 degrees or more.

9. 9. The oil-resistant agent according to claim 1, wherein the modified natural product has a melting point of 40° C. or higher or does not exist.

10. The oil-resistant agent according to any one of claims 1 to 9, which has a viscosity of 5 cP or more and 100 cP or less at a solution concentration of 14.8 mg / mL.

11. The oil-proofing agent according to any one of claims 1 to 10, which is a water-dispersed composition.

12. The oil-proofing agent according to any one of claims 1 to 11, which is for paper.

13. A textile product having the oil-resistant agent according to any one of claims 1 to 12 adhered thereto.

14. Grease-resistant paper comprising the oil-resistant agent according to any one of claims 1 to 12.

15. 15. The greaseproof paper according to claim 14, which is a food packaging material or a food container.

16. A method for treating paper by externally or internally adding the oil-proofing agent according to any one of claims 1 to 12.

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