Patent Description:
Paper containers are promising as an alternative to disposable plastic containers. Paper-made food packaging materials and food containers are required to prevent oozing-out of moisture and oil content of foods and oil-resistant agents are applied to papers by internal addition or external addition. From the viewpoint of the environmental consideration, the need for biobased materials is increasing.

(<CIT> discloses a hydroxcarboxylic aid amide derivative having a polybasic hydroxycarboxylic acid as an acid component group.

<CIT> discloses a support for photographic paper in which a photographic base paper is configured to contain a reaction product of an aliphatic oxyacid with a monohydric alcohol of a C<NUM>-<NUM>-alkyl group or C<NUM>-<NUM>-alkenyl, and/or an amine having, as substituents, a C<NUM>-<NUM>-alkyl group or C<NUM>-<NUM>-alkenyl group and a C<NUM>-<NUM>-alkyl group, a C<NUM>-<NUM>-alkenyl group or hydrogen.

<CIT> discloses an oil-proof fibre container comprising a container body having a plurality of fibre layers held together with an adhesive, and an inner liner of sulfite paper impregnated with hydrogenated castor oil, said liner being secured to the inside body wall by a glue which has been dispersed in water with a sodium salt of a sulphonated dioctyl ester of a dibasic acid and with a liquid hydrocarbon.

<CIT> describes a surface treatment agent for paper, which comprises a base material of a modified ester starch that has been esterified and further appropriately hydroxyalkylated to have a viscosity of <NUM>-<NUM> Pa s at <NUM> in a paste solution of a solid content concentration of <NUM>%.

<CIT> relates to a greaseproof treated paper wherein an oil-resistant layer is provided on one or both sides of the paper substrate, the layer(s) including an undercoat film and a topcoat film having a low-viscosity decomposed starch or a hydroxylated hydrogen-substituted starch derivative capable of gelatinizing the decomposed starch as a coating film main component.

An object of the present disclosure is to provide an oil-resistant agent which can impart the sufficient oil resistance by using a modified natural product in harmony with the environment.

The present disclosure relates to a modified natural product in which a biobased compound is modified so as to have an organic modifying group. Examples of the organic modifying group are C<NUM>-<NUM>-hydrocarbon groups and optionally having a substituent, or polysiloxanes.

The modified natural product can be used as the oil-resistant agent.

The present invention provides an agent (also referred to as "the present agent" herein), which is an oil-resistant agent, comprising a modified natural product (i) having a biobased content, measured according to ASTM D6866, of ≥ <NUM>% and (ii) wherein.

Also, the present invention provides the use of the present agent for paper.

Furthermore, the present invention provides an article comprising the present agent, the article being a textile product, an oil-resistant paper, a food packaging material or a food container.

Yet further, the present invention provides a method of treating paper, comprising subjecting the paper to an external addition treatment or an internal addition treatment using the present agent.

The present agent excellent oil resistance. The present agent, which is of biobased origin, poses low load to the ecological environment.

The present agent imparts the oil resistance to a treatment target (substrate) by treating the treatment target with the present agent. The oil resistance includes e.g. a function of preventing oil stain into the treatment target, or functions of the oil repellency, or the antifouling property, but functions are not limited thereto.

Here, "oil" refers to fats and oils and organic solvents; the fats and oils include edible fats and oils (plant fatty oils, animal fatty oils, plant fats, animal fats) and industrial fats and oils; the edible fats and oils include salad oils, corn oils, sesame oils, rapeseed oils and olive oils, and industrial fats and oils include castor oils; organic solvents may be polar solvents or nonpolar solvents, and the nonpolar solvents include hexane and hexadecane, but are not limited thereto.

The treatment target may have water resistance and the water repellency. The oil-resistant agent may comprise, in addition to a modified natural product, a liquid medium (water, an organic solvent or a mixed solution thereof). The oil-resistant agent may further comprise at least one selected from surfactants, dispersants, blocked isocyanate compounds and additives.

The biobased compound is a compound having carbon of biobased origin. The biobased content is measured according to ASTM D6866. The compound having carbon of biobased origin has a biobased content of <NUM>% or higher, preferably <NUM>% or higher and most preferably <NUM>% or higher or <NUM>% or higher, for example, <NUM>%. A high biobased content means that the amount of fossil resource-based materials represented by e.g. petroleum to be used is small; and in such a viewpoint, it can be said that the higher the biobased content of the biobased compound, the better.

The biobased compound may be a compound as it is a natural product, or a compound originated from a natural product. That is, the biobased compound includes derivatives of natural products.

The modified natural product is a compound having carbon of biobased origin. The biobased content is measured according to ASTM D6866. The biobased content is <NUM>% or higher, preferably <NUM>% or higher and most preferably <NUM>% or higher or <NUM>% or higher, for example, <NUM>%. A high biobased content means that the amount of fossil resource-based materials represented by e.g. petroleum to be used is small; and in such a viewpoint, it can be said that the higher the biobased content of the modified natural product, the better.

The present disclosure provides an oil-resistant agent comprising a modified natural product (i) having a biobased content, measured according to ASTM D6866, of ≥ <NUM>% and (ii) wherein.

Examples of the substituent include hydroxyl, carboxyl, alkoxy ester, alkoxy, (Rc)<NUM>Si, (RcO)<NUM>Si, amino and amine salts (Rc each independently is H or C<NUM>-<NUM>-alkyl).

The carboxyl group of the modified natural product may have a structure of a salt. The corresponding cation is e.g. an ammonium ion, a quaternary ammonium ion, an alkali metal, or an alkaline earth metal.

The biobased compound may have functional groups other than the carboxyl group, and examples thereof include a hydroxyl group.

In the case where the biobased compound has a hydroxyl group, alternatively, hydrogen of the hydroxyl group may be replaced by -Y-R<NUM> (Rb) wherein Y is a direct bond, - C(=O)-, -C(=O)-NR<NUM>- or -C=S-, wherein R<NUM> is H or C<NUM>-<NUM>-alkyl optionally having a substituent, preferably H or methyl and more preferably H; and
R<NUM> is a C<NUM>-<NUM>-hydrocarbon group optionally having a substituent, or a polysiloxane.

Alternatively, the hydroxyl group of the modified natural product may have a structure of a salt. The corresponding cation is e.g. an ammonium ion, a quaternary ammonium ion, an alkali metal, or an alkaline earth metal.

In the modified natural product, alternatively, carboxyl groups or hydroxyl groups thereof may be crosslinked by a polyfunctional cross-linking agent.

Carboxyl groups of the modified natural product may be crosslinked by a polyfunctional cross-linking agent, and the modified natural product may have a structure in which the hydroxyl groups of carboxyl groups thereof are bonded by a bonding group Z. Z is preferably a bonding group represented by -O- or -NR<NUM>- (R<NUM> is H or alkyl having <NUM>-<NUM> or <NUM>-<NUM> carbon atoms and optionally having a substituent, preferably H or methyl and more preferably H).

Hydroxyl groups of the modified natural product may be crosslinked by a polyfunctional cross-linking agent, and the modified natural product may have a structure in which the hydroxyl groups are bonded by a group having a bonding group Z'. Z' is preferably a bonding group represented by -C(=O)- or -C(=O)-NR<NUM>- (R<NUM> is H or alkyl having <NUM>-<NUM> or <NUM>-<NUM> carbon atoms and optionally having a substituent, preferably H or methyl and more preferably H).

Examples of the polyfunctional cross-linking agent are diamines, putrescine, cadaverine, hexanemethylenediamine, phenylenediamine, ethylene glycol, propylene glycol, diethylene glycol, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, citric acid, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and hexamethylene diisocyanate (HDI).

Examples of the -X-R<NUM> group are -R<NUM>, -O-R<NUM>, -NR<NUM>-R<NUM> and - S-R<NUM>, wherein R<NUM> and R<NUM> have the same meanings as in the above. Preferable are -O-R<NUM> and -NR<NUM>-R<NUM>; more preferable is -NR<NUM>-R<NUM>; still more preferable is -NH-R<NUM> for giving a larger contact angle.

Examples of the -X-D-X'-R<NUM> group are -O-D-O-C(=O)-R<NUM>, -O-D-C(=O)-NR<NUM>R<NUM>, -O-D-NR<NUM>-C(=O)-R<NUM>, -NR<NUM>-D-O-C(=O)-R<NUM>, - NR<NUM>-D-C(=O)-NR<NUM>R<NUM> and -NR<NUM>-D-NR<NUM>-C(=O)-R<NUM>, wherein R<NUM> and R<NUM> and R<NUM> have the same meanings as in the above; R<NUM> is H or C<NUM>-<NUM>-alkyl optionally having a substituent; and D is C<NUM>-<NUM>-alkylene and preferably C<NUM>-<NUM>-alkylene. Preferable are -NR<NUM>-D-O-C(=O)-R<NUM>, -NR<NUM>-D-C(=O)-O-R<NUM>, -NR<NUM>-D-C(=O)-NR<NUM>R<NUM> and -NR<NUM>-D-NR<NUM>-C(=O)-R<NUM>; and more preferably are -NH-D-O-C(=O)-R<NUM>, -NH-D-C(=O)-O-R<NUM>, -NR<NUM>-D-C(=O)-NHR<NUM> and -NR<NUM>-D-NH-C(=O)-R<NUM>.

When the biobased compound or the modified natural product has two or more carboxyl groups, the hydroxyl groups of the two carboxyl groups may be replaced by an Rd group and bonded. The Rd group is preferably a group of the formula:.

wherein R<NUM> has the same meaning as in the above.

The number of carbon atoms of R<NUM> is <NUM>-<NUM>, and may be <NUM> or larger, <NUM> or larger, <NUM> or larger or <NUM> or larger. The number of carbon atoms of the hydrocarbon group may be <NUM> or smaller, <NUM> or smaller, <NUM> or smaller, <NUM> or smaller, <NUM> or smaller, <NUM> or smaller or <NUM> or smaller. The number is preferably <NUM> or smaller.

R<NUM> is a saturated or unsaturated C<NUM>-<NUM>-hydrocarbon group optionally having a substituent selected from OH, carboxyl, alkoxy ester, alkoxy, amino, amine salts, and (Rc)<NUM>Si and (RcO)<NUM>Si wherein Rc each independently is H or C<NUM>-<NUM>-alkyl, preferably an aliphatic hydrocarbon group optionally having a substituent and more preferably an aliphatic hydrocarbon group. The hydrocarbon group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear. R<NUM> may be, for example, a linear or branched alkyl group.

Specific examples of R<NUM> include alkyl groups such as lauryl, tridecyl, tetradecyl, pentadecyl, palmityl, heptadecyl, stearyl, behenyl, <NUM>-ethylhexyl and isostearyl; alkenyl groups such as oleyl, palmitoyl and eicosenyl; and cycloalkyl groups.

R<NUM> may be a hydrocarbon group having an A group such as an amino group or an ammonium group.

The A is preferably a group of the formula -NA<NUM>A<NUM> or -N+A<NUM>A<NUM>A<NUM>B- (A<NUM>, A<NUM> and A<NUM> are each H or C<NUM>-<NUM>-alkyl, preferably H or C<NUM>-<NUM>-alkyl and most preferably H or methyl; and B- is an ion such as a halide ion or an acetate ion).

R<NUM> and R<NUM> are each H or C<NUM>-<NUM>-alkyl optionally having a substituent, preferably H or an aliphatic C<NUM>-<NUM>-hydrocarbon, more preferably H or an aliphatic C<NUM>-<NUM>-hydrocarbon, still more preferably H or an aliphatic C<NUM>-<NUM>-hydrocarbon and most preferably H.

R<NUM> is H or C<NUM>-<NUM>-alkyl optionally having a substituent, preferably H or an aliphatic C<NUM>-<NUM>-hydrocarbon, more preferably H or an aliphatic C<NUM>-<NUM>-hydrocarbon, still more preferably H or an aliphatic C<NUM>-<NUM>-hydrocarbon and most preferably H.

The modified natural product is preferably a compound in which at least one hydroxyl group of a carboxyl group(s) of a compound of the formula:
<CHM>.

In the case where E<NUM> is alkyl, the number of carbon atoms of the alkyl group may be <NUM>-<NUM> or <NUM>-<NUM>.

m may be <NUM>-<NUM>, <NUM>-<NUM> or <NUM>-<NUM>.

Examples of the modified natural product are as follows.

wherein E<NUM> is NHE<NUM>, and E<NUM> is Boc, H or COE<NUM>; and E<NUM> and E<NUM> are each R or OH, and at least one thereof is R.

wherein E<NUM> is NHE<NUM>, COE<NUM> or OCOR<NUM>, preferably COE<NUM>; E<NUM> and E<NUM> are each H, OH or OCOR<NUM>, E<NUM> is preferably H and E<NUM> is preferably H or OAc; and E<NUM>, E<NUM> and E<NUM> are as described above.

E<NUM>-CO-CH<NUM>-C(OH)E<NUM>-CH<NUM>-COE<NUM>.

wherein E<NUM> is COE<NUM> or H; and E<NUM>, E<NUM> and E<NUM> are each R or OH and at least one thereof is R.

In the above examples, the R group is -X-R<NUM> or -X-D-X'-R<NUM>, and X, R<NUM>, D and X' are as described above.

In the above examples, Ac is acetyl, and Boc is t-butoxycarbonyl.

In the above examples, although cases of having an R group are shown, alternatively, - or the -CO-R group in every modified natural product in the above examples may be replaced by an Ra group.

In some embodiments, specific examples of the modified natural product are as follows. <CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

The biobased compound is a compound having at least one carboxyl group (carboxyl group-containing natural product).

The biobased compound may also be a low molecular one (for example, the weight-average molecular weight is lower than <NUM>,<NUM> or <NUM> or lower) and/or a polymeric one. The weight-average molecular weight of the polymer may be <NUM>,<NUM> or higher, <NUM>,<NUM> or higher, <NUM>,<NUM> or higher, <NUM>,<NUM> or higher, <NUM>,<NUM> or higher, <NUM>,<NUM> or higher, <NUM>,<NUM> or higher or <NUM>,<NUM> or higher. The weight-average molecular weight of the polymer may be <NUM>,<NUM>,<NUM> or lower, <NUM>,<NUM>,<NUM> or lower, <NUM>,<NUM>,<NUM> or lower, <NUM>,<NUM>,<NUM> or lower, <NUM>,<NUM> or lower or <NUM>,<NUM> or lower, <NUM>,<NUM> or lower, <NUM>,<NUM> or lower, <NUM>,<NUM> or less or <NUM>,<NUM> or lower. The weight-average molecular weight can be measured in terms of pullulan by gel permeation chromatography (GPC).

The biobased compound may be a polymeric natural product, a low molecular natural product, or a derivative thereof.

The biobased compound (a natural product or a compound originated from a natural product) may be, for example, glycine, citric acid, malic acid, glutaric acid, gluconic acid, alginic acid, butyric acid, lactic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, chlorogenic acid, aldonic acid, uronic acid, aldaric acid, or a derivative thereof.

The biobased compound (a natural product or a compound originated from a natural product) is preferably a compound of the formula:
<CHM>.

The modified natural product may have the biodegradability according to ASTM D5338. The biodegradability is preferably <NUM>% or higher, more preferably <NUM>% or higher, still more preferably <NUM>% or higher or <NUM>% or higher, further still more preferably <NUM>% or higher, further still more preferably <NUM>% or higher and most preferably <NUM>% or higher. The higher the degradability, the lower the environmental load, and therefore it can be said that the higher the biodegradability of the modified natural product, the better.

The modified natural product can be produced by reacting a modifying agent with a carboxyl group of the biobased compound. Examples of synthesis methods of reacting the modifying agent with the carboxyl group include a method of forming an ester bond, a method of forming an amido bond and a method of forming an oxazole ring.

The modifying agent is preferably a compound having a hydrocarbon group and especially preferably a compound having an aliphatic hydrocarbon group. Examples of the modifying agent are as follows.

wherein R<NUM> has the same meaning as in the above (a C<NUM>-<NUM>-hydrocarbon group optionally having a substituent); and R<NUM> is H or alkyl having <NUM>-<NUM> (for example, <NUM>-<NUM> or <NUM>-<NUM>) carbon atoms and optionally having a substituent.

The ratio of substitution of the carboxyl group or the hydroxyl group of the carboxyl group by the modifying agent is preferably higher than <NUM> and more preferably <NUM>% or higher, <NUM>% or higher, <NUM>% or higher or <NUM>% or higher, for example, <NUM>% or higher, <NUM>% or higher, <NUM>% or higher, <NUM>% or higher or <NUM>% or higher. The "ratio of substitution" means an average proportion (%) of the carboxyl group or the hydroxyl group of the carboxyl group present in the structure of the modified natural product substituted by the modifying agent.

The ratio of the carboxyl group unmodified (that is, the remaining ratio of the carboxyl group) is lower than <NUM>%, and may be <NUM>% or lower, <NUM>% or lower, <NUM>% or lower, <NUM>% or lower or <NUM>% or lower. The "remaining ratio" means a proportion (%) of the carboxyl group, present in the structure of the modified natural product, which has not been substituted by the modifying agent.

By using an alcohol (R<NUM>-OH), an ester bond is formed with the carboxyl group of the biobased compound.

Examples of synthesis methods of converting a carboxyl group of a natural product to an ester bond include:.

(in each method, as required, a solvent is added). In the alcohol (R<NUM>-OH), R<NUM> has the same meaning as in the above.

Specific examples of aliphatic alcohols include CH<NUM>OH, CH<NUM>CH<NUM>OH, CH<NUM>(CH<NUM>)<NUM>OH, CH<NUM>(CH<NUM>)<NUM>OH, CH<NUM>(CH<NUM>)<NUM>OH, CH<NUM>(CH<NUM>)<NUM>OH, CH<NUM>(CH<NUM>)<NUM>OH, CH<NUM>(CH<NUM>)<NUM>OH, CH<NUM>(CH<NUM>)<NUM>OH, CH<NUM>(CH<NUM>)<NUM>OH, CH<NUM>(CH<NUM>)<NUM>OH, CH<NUM>(CH<NUM>)<NUM>OH, CH<NUM>(CH<NUM>)<NUM>OH, CH<NUM>(CH<NUM>)<NUM>OH, CH<NUM>(CH<NUM>)<NUM>OH, CH<NUM>(CH<NUM>)<NUM>OH, CH<NUM>(CH<NUM>)<NUM>OH, CH<NUM>(CH<NUM>)<NUM>OH, CH<NUM>(CH<NUM>)<NUM>OH, CH<NUM>(CH<NUM>)<NUM>OH, CH<NUM>(CH<NUM>)<NUM>OH, CH<NUM>(CH<NUM>)<NUM>OH, CH<NUM>(CH<NUM>)<NUM>OH, CH<NUM>(CH<NUM>)<NUM>OH, (CH<NUM>)<NUM>CHOH, (CH<NUM>)<NUM>COH, (CH<NUM>)<NUM>CHCH<NUM>OH, (CH<NUM>)<NUM>CCH<NUM>OH, (CH<NUM>)<NUM>CH(CH<NUM>)<NUM>OH, (CH<NUM>)<NUM>C(CH<NUM>)<NUM>OH, (CH<NUM>)<NUM>CH(CH<NUM>)<NUM>OH, (CH<NUM>)<NUM>C(CH<NUM>)<NUM>OH and (CH<NUM>)<NUM>CH(CH<NUM>)<NUM>OH.

An amido bond is formed by reacting a carboxyl group of a biobased compound. The amido bond is formed by reacting the biobased compound with an amine (R<NUM>-NR<NUM>H), an isocyanate (R<NUM>-N=C=O) or an isothiocyanate (R<NUM>-N=C=S).

Synthesis methods of converting a carboxyl group of a biobased compound to an amido group include:.

Specific examples of the amine include CH<NUM>NH<NUM>, CH<NUM>CH<NUM>NH<NUM>, CH<NUM>(CH<NUM>)<NUM>NH<NUM>, CH<NUM>(CH<NUM>)<NUM>NH<NUM>, CH<NUM>(CH<NUM>)<NUM>NH<NUM>, CH<NUM>(CH<NUM>)<NUM>NH<NUM>, CH<NUM>(CH<NUM>)<NUM>NH<NUM>, CH<NUM>(CH<NUM>)<NUM>NH<NUM>, CH<NUM>(CH<NUM>)<NUM>NH<NUM>, CH<NUM>(CH<NUM>)<NUM>NH<NUM>, CH<NUM>(CH<NUM>)<NUM>NH<NUM>, CH<NUM>(CH<NUM>)<NUM>NH<NUM>, CH<NUM>(CH<NUM>)<NUM>NH<NUM>, CH<NUM>(CH<NUM>)<NUM>NH<NUM>, CH<NUM>(CH<NUM>)<NUM>NH<NUM>, CH<NUM>(CH<NUM>)<NUM>NH<NUM>, CH<NUM>(CH<NUM>)<NUM>NH<NUM>, CH<NUM>(CH<NUM>)<NUM>NH<NUM>, CH<NUM>(CH<NUM>)<NUM>NH<NUM>, CH<NUM>(CH<NUM>)<NUM>NH<NUM>, CH<NUM>(CH<NUM>)<NUM>NH<NUM>, CH<NUM>(CH<NUM>)<NUM>NH<NUM>, CH<NUM>(CH<NUM>)<NUM>NH<NUM>, CH<NUM>(CH<NUM>)<NUM>NH<NUM>, (CH<NUM>)<NUM>CHNH<NUM>, (CH<NUM>)<NUM>CNH<NUM>, (CH<NUM>)<NUM>CHCH<NUM>NH<NUM>, (CH<NUM>)<NUM>CCH<NUM>NH<NUM>, (CH<NUM>)<NUM>CH(CH<NUM>)<NUM>NH<NUM>, (CH<NUM>)<NUM>C(CH<NUM>)<NUM>NH<NUM>, (CH<NUM>)<NUM>CH(CH<NUM>)<NUM>NH<NUM>, (CH<NUM>)<NUM>C(CH<NUM>)<NUM>NH<NUM> and (CH<NUM>)<NUM>CH(CH<NUM>)<NUM>NH<NUM>.

Specific examples of the isocyanate include CH<NUM>NCO, CH<NUM>CH<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>0NCO, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCO, (CH<NUM>)<NUM>CHNCO, (CH<NUM>)<NUM>CNCO, (CH<NUM>)<NUM>CHCH<NUM>NCO, (CH<NUM>)<NUM>CCH<NUM>NCO, (CH<NUM>)<NUM>CH(CH<NUM>)<NUM>NCO, (CH<NUM>)<NUM>C(CH<NUM>)<NUM>NCO, (CH<NUM>)<NUM>CH(CH<NUM>)<NUM>NCO, (CH<NUM>)<NUM>C(CH<NUM>)<NUM>NCO and (CH<NUM>)<NUM>CH(CH<NUM>)<NUM>NCO.

Specific examples of the isothioisocyanate include CH<NUM>NCS, CH<NUM>CH<NUM>NCS, CH<NUM>(CH<NUM>)<NUM>NCS, CH<NUM>(CH<NUM>)<NUM>NCS, CH<NUM>(CH<NUM>)<NUM>NCS, CH<NUM>(CH<NUM>)<NUM>NCS, CH<NUM>(CH<NUM>)<NUM>NCS, CH<NUM>(CH<NUM>)<NUM>NCS, CH<NUM>(CH<NUM>)<NUM>NCS, CH<NUM>(CH<NUM>)<NUM>NCS, CH<NUM>(CH<NUM>)<NUM>NCS, CH<NUM>(CH<NUM>)<NUM>NCS, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCO, CH<NUM>(CH<NUM>)<NUM>NCS, CH<NUM>(CH<NUM>)<NUM>NCS, CH<NUM>(CH<NUM>)<NUM>NCS, CH<NUM>(CH<NUM>)<NUM>NCS, CH<NUM>(CH<NUM>)<NUM>NCS, CH<NUM>(CH<NUM>)<NUM>NCS, CH<NUM>(CH<NUM>)<NUM>NCS, CH<NUM>(CH<NUM>)<NUM>NCS, (CH<NUM>)<NUM>CHNCS, (CH<NUM>)<NUM>CNCS, (CH<NUM>)<NUM>CHCH<NUM>NCS, (CH<NUM>)<NUM>CCH<NUM>NCS, (CH<NUM>)<NUM>CH(CH<NUM>)<NUM>NCS, (CH<NUM>)<NUM>C(CH<NUM>)<NUM>NCS, (CH<NUM>)<NUM>CH(CH<NUM>)<NUM>NCS, (CH<NUM>)<NUM>C(CH<NUM>)<NUM>NCS and (CH<NUM>)<NUM>CH(CH<NUM>)<NUM>NCS.

R<NUM> is preferably an aliphatic C<NUM>-<NUM>-hydrocarbon group optionally having a substituent. The number of carbon atoms is preferably <NUM> or larger, more preferably <NUM> or larger and still more preferably <NUM> or larger, and preferably <NUM> or smaller, more preferably <NUM> or smaller and still more preferably <NUM> or smaller.

In the present disclosure, preferable is the modified natural product modified with a primary amine.

Since the modified natural product has an oil resistance, it can be used as the "oil-resistant agent". The oil-resistant agent may be a composition configured by comprising the modified natural product, or may be composed only of the modified natural product. The oil-resistant agent may further have the water resistance, the water repellency and the oil repellency. The oil-resistant agent may contain, in addition to the modified natural product, a liquid medium (water, an organic solvent or a mixed solution thereof). The oil-resistant agent may further contain at least one selected from surfactants, dispersants, cross-linking agents such as blocked isocyanate compounds, and additives.

The amount of the modified natural product may be, with respect to the oil-resistant agent, <NUM> wt. % or larger, <NUM> wt. % or larger, <NUM> wt. % or larger, <NUM> wt. % or larger, <NUM> wt. % or larger or <NUM> wt. % or larger. The amount of the modified natural product may be, with respect to the oil-resistant agent, <NUM> wt. % or smaller, <NUM> wt. % or smaller, <NUM> wt. % or smaller or <NUM> wt. % or smaller.

The oil-resistant agent may contain a liquid medium. The liquid medium is singly water, singly an organic solvent, or a mixed solution of water and an organic solvent, and is preferably singly water.

The amount of the liquid medium may be, with respect to the oil-resistant agent, <NUM> wt. % or larger, <NUM> wt. % or larger or <NUM> wt. % or larger, and the amount of the liquid medium may be smaller than <NUM> wt. %, <NUM> wt. % or smaller, <NUM> wt. % or smaller, <NUM> wt. % or smaller or <NUM> wt. % or smaller.

The oil-resistant agent does not necessarily contain a surfactant (emulsifier) or a dispersant, or may contain.

During the reaction time or after the reaction, a small amount (for example, with respect to <NUM> parts by mass (pbm) of the modified natural product, <NUM>-<NUM> pbm or <NUM>-<NUM> pbm, for example, <NUM>-<NUM> pbm) of the surfactant or the dispersant may be added. When a surfactant or a dispersant is added, the stability of a water dispersion is usually improved.

It is preferable that the surfactant contain one or more kinds of surfactants selected from cationic surfactants, nonionic surfactants, anionic surfactants and amphoteric surfactants; and it is more preferable to use a nonionic surfactant, a cationic surfactant or a combination of a nonionic surfactant and a cationic surfactant.

The surfactant may be a combination of each one kind or each two or more kinds of nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants.

The surfactant or the dispersant may be added in an amount of, with respect to <NUM> pbm of the modified natural product, <NUM> wt. % or larger, <NUM> wt. % or larger, <NUM> wt. % or larger, <NUM> wt. % or larger, <NUM> wt. % or larger, <NUM> wt. % or larger or <NUM> wt. % or larger, and then, <NUM> wt. % or smaller, <NUM> wt. % or smaller, <NUM> wt. % or smaller or <NUM> wt. % or smaller. The addition of the surfactant or the dispersant usually improves the stability of a water dispersion.

Examples of the nonionic surfactant (emulsifier) or dispersant include glycerol fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycols, fatty acid polyethylene glycols, fatty acid polyoxyethylene sorbitan, fatty acid alkanolamides and polyethyleneimine ethoxylates.

Examples of the cationic surfactant (emulsifier) or dispersant include alkylamine salts and quaternary ammonium salts; the alkylamine salts include monoalkylamine salts, dialkylamine salts and trialkylamine salts, and the quaternary ammonium salts include a trimethylammonium chloride salt, dialkyldimethylammonium chloride salts and alkyl benzalkonium chloride salts.

Examples of the anionic surfactant (emulsifier) or dispersant include carboxylate salts, sulfonate salts, sulfate ester salts and phosphate ester salts; and examples of the carboxylate salts include aliphatic monocarboxylate salts and alkyl ether carboxylate salts; examples of the sulfonate salts include dialkylsulfosuccinate salts, alkanesulfonate salts, alkylbenzenesulfonate salts and alkylnaphthalenesulfonate salts; examples of the sulfate ester salts include alkylsulfate salts and fat-and-oil sulfate ester salts; and examples of the phosphate ester salts include alkylphosphate salts and polyoxyethylene alkyl ether phosphate salts.

Examples of the amphoteric surfactant (emulsifier) or dispersant include alkyl betaines, fatty acid amide propyl betaines, <NUM>-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium salts, alkyl diethylene triaminoacetatic acids, dialkyl diethylene triaminoacetatic acids and alkylamine oxides.

When the surfactant (emulsifier) or the dispersant is added during or after the reaction of the modified natural product, heating may be carried out. After the dispersant is added to the modified natural product, they may be heated and melted and then dispersed; or they may be dispersed or dissolved by adding a solution (preferably, water) under further heating. The heating temperature may be <NUM> or higher, <NUM> or higher or <NUM> or higher.

The oil-resistant agent does not necessarily contain a blocked isocyanate compound, or may contain. The blocked isocyanate compound may be added before the substitution reaction of the carboxyl group, or may be added after the reaction (for example, before a curing process).

Preferable blocked isocyanate compounds are blocked isocyanates such as oxime blocked toluene diisocyanate, blocked hexamethylene diisocyanate and blocked diphenylmethane diisocyanate.

The amount of the blocked isocyanate compound may be, with respect to <NUM> pbw of the modified natural product, <NUM> pbw or smaller, <NUM> pbw or smaller, <NUM> pbw or smaller, <NUM> pbw or smaller or <NUM> pbw or smaller.

The oil-resistant agent may contain additives. Examples of the additives are binder resins, dispersants, water-resistant agents, oil-resistant agents, water repellents, oil repellents, drying rate adjusters, cross-linking agents, film forming assistants, compatibilizers, antifreezing agents, viscosity adjusters, ultraviolet absorbents, antioxidants, pH adjusters, antifoaming agents, texture modifiers, slippage modifiers, antistatic agents, hydrophilizing agents, antibacterial agents, antiseptic agents, insect repellents, fragrant agents, flame retarders, retention aids, sizing agents, paper strength additives and fillers.

Examples of the retention aids include aluminum sulfate, acrylic polymers, starch, modified starch, cellulose, modified cellulose and silica.

Examples of the sizing agents include rosin-based sizing agents, alkyl ketene dimers (AKD), alkenyl succinic anhydrides (ASA), polyvinyl alcohols (PVA), modified starch, styrene·acrylic copolymers and styrene·methacrylic copolymers.

Examples of the pH adjusters include lactic acid, carbon dioxide, succinic acid, gluconic acid, citric acid, trisodium citrate, phosphoric acid, potassium carbonate and sodium hydrogencarbonate.

Examples of the fillers include talc, kaolin, calcium carbonate, titanium oxide and barium sulfate.

Examples of the paper strength additives include urea formaldehyde resins, melamine formaldehyde resins, polyamide polyamine epichlorohydrins (PAE), polyvinylamines (PVAm), modified starch, polyacrylamides and polyvinyl alcohols.

The amount of the additives is, with respect to <NUM> pbw of the modified natural product, larger than <NUM> and preferably <NUM> pbw or larger and more preferably <NUM> pbw or larger, and <NUM> pbw or smaller, more preferably <NUM> pbw or smaller and still more preferably <NUM> pbw or smaller.

The melting point of functional groups (side chains) of the modified natural product, preferably, is <NUM> or higher or exhibits no melting point, and is preferably <NUM> or higher, <NUM> or higher or <NUM> or higher. Then, the melting point of the functional groups (side chains) is preferably <NUM> or lower, <NUM> or lower or <NUM> or lower. With the melting point of the functional groups (side chains) in the above range, the resistance to temperature is improved and in particular, from the viewpoint of high-temperature oil resistance, the melting point being in the above range is preferable. Here, the functional groups (side chains) in the modified natural product are intended to be the R groups, particularly C<NUM>-<NUM>-hydrocarbon groups, of the modified natural product. The melting point of the functional groups (side chains) in the modified natural product is a temperature at which when a solid of the modified natural product is heated from a low temperature, the arrangement of the R groups of the modified natural product is distorted, and may be the glass transition temperature of the modified natural product.

The contact angle of n-hexadecane against the oil-resistant agent (on a glass substrate) may be <NUM>° or larger, <NUM>° or larger or <NUM>° or larger, preferably <NUM>° or larger or <NUM>° or larger, more preferably <NUM>° or larger and most preferably <NUM>° or larger or <NUM>° or larger. With the contact angle of n-hexadecane in the above range, the oil-resistant agent is excellent in the liquid repellency, and in particular, from the viewpoint of the oil resistance, the contact angle being in the above range is preferable.

The melting point of the modified natural product is preferably <NUM> or higher, more preferably <NUM> or higher, still more preferably <NUM> or higher and most preferably <NUM> or higher. Then, the melting point of the oil-resistant agent is preferably <NUM> or lower, <NUM> or lower or <NUM> or lower.

With the melting point of the oil-resistant agent in the above range, the coatability when the oil-resistant agent is applied to a texture product, and the resistance to temperature are improved and in particular, from the viewpoint of the high-temperature oil resistance, the melting point being in the above range is preferable.

The glass transition temperature of the modified natural product, preferably, is <NUM> or higher or exhibits no glass transition temperature, more preferably, is <NUM> or higher or exhibits no glass transition temperature, still more preferably, is <NUM> or higher or exhibits no glass transition temperature, and most preferably, is <NUM> or higher or exhibits no glass transition temperature. Then, the glass transition temperature of the oil-resistant agent is preferably <NUM> or lower, <NUM> or lower or <NUM>°° or lower. With the glass transition temperature of the oil-resistant agent in the above range, the coatability when the oil-resistant agent is applied to a texture product, and the resistance to temperature are improved and in particular, from the viewpoint of the oil resistance, the glass transition temperature being in the above range is preferable.

The viscosity of the oil-resistant agent (solution or dispersion) in a concentration of the modified natural product of <NUM>/mL is preferably <NUM> cP or higher, <NUM> cP or higher, <NUM> cP or higher or <NUM> cP or higher. Then, the viscosity of the oil-resistant agent (a solution or a dispersion) in a concentration of the modified natural product of <NUM>/mL is preferably <NUM>,000cP or lower, <NUM> cP or lower or <NUM> cP or lower. With the viscosity of the solution (dispersion) in the above range, the coatability when the oil-resistant agent is applied to a texture product is improved and in particular, from the viewpoint of the oil resistance, the viscosity being in the above range is preferable.

The air permeability of a treated paper, which is fabricated by three times carrying out an operation in which the oil-resistant agent (a solution or a dispersion) in a concentration of the modified natural product of <NUM>/mL is coated by a Baker applicator set at <NUM> mil on a base paper of a paper of <NUM>/cm3 in paper density and <NUM>/m2 in basis weight, and dried, and annealing the resultant at a temperature of <NUM> to <NUM> for <NUM>, is preferably <NUM>,<NUM>/<NUM> cc or lower, more preferably <NUM>,<NUM>/<NUM> cc or lower, still more preferably <NUM>,<NUM>/<NUM> cc or lower and most preferably <NUM>,<NUM>/<NUM> cc or lower.

A preferable range (hexadecane contact angle × melting point) of combinations of the contact angle of hexadecane against the oil-resistant agent and the melting point of the oil-resistant agent may be <NUM>° or larger × <NUM> or higher, <NUM>° or larger × <NUM> or higher, <NUM>° or larger × <NUM> or higher or <NUM>° or larger × <NUM> or higher.

The oil-resistant agent can be used as various types of agents, such as a water-resistant agent, a water repellent, an oil repellent, a soil resistant agent, a soil release agent, a release agent and a mold release agent, and also as a component of these.

The oil-resistant agent can be used as a treatment agent such as an external treatment agent (surface-treating agent) or an internal treatment agent, or as a component thereof.

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

The surface coating structure can be formed by applying the oil-resistant agent to a treatment target (substrate) by a conventionally well-known method to adhere the oil-resistant agent on the substrate surface. A method is usually adopted in which the modified natural product is dispersed in and diluted with an organic solvent or water, and the resultant is made to adhere on the surface of the treatment target by a well-known method such as dip coating, spray coating or foam coating, and dried. Then, as required, the modified natural product may be applied together with a suitable cross-linking agent (for example, a blocked isocyanate compound) and then cured. Further, it is also possible to add and concurrently use an insect repellent, a softening agent, an antibacterial agent, a flame retarder, an antistatic agent, a coating material fixing agent, a wrinkle-resistant agent, a sizing agent, and a paper strength additive.

Treatment targets to be treated with the oil-resistant agent include textile products, stone, filters (for example, electrostatic filters), dust-free masks, parts (for example, gas diffusion electrodes and gas diffusion supports) of fuel cells, glass, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces and plaster.

As the textile products, various types thereof can be cited, but examples thereof include fabric products and paper products.

Examples of the fabric 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, semisynthetic fibers such as rayon and acetate fibers, inorganic fibers such as glass fibers, carbon fibers and asbestos fibers, and mixed fibers thereof. The fabric products include woven fabrics, knitted fabrics and nonwoven fabrics, and fabrics in clothing forms and carpets; and some treatment may be carried out on fibers, threads and intermediate textile products (for example, slivers or slubbings) in the state before being made into the fabrics.

Examples of the paper products include papers composed of bleached or unbleached chemical pulps, such as kraft pulp and sulfite pulp, bleached or unbleached high yield pulps, such as groundwood pulp, mechanical pulp and thermomechanical pulp, and papers composed of waste paper pulps such as news, magazine waste papers, corrugated fiberboard waste pulps or deinked waste papers, containers composed of papers, and formed articles composed of papers. Specific examples of the paper products are wrapping papers for food, gypsum liner boards, base coated papers, mechanical papers, general use liners and corrugating media, neutral pure white machine glazed papers, neutral liners, rust-preventive liners and metal-laminated papers, kraft papers, neutral printing writing papers, neutral base coated papers, neutral PPC papers, neutral thermosensitive papers, neutral pressure sensitive papers, neutral inkjet papers and neutral specialty papers for communication, and mold papers (mold containers). The modified natural product of the present disclosure is excellent in the oil resistance (for example, high-temperature oil resistance), and hence is suitably used in applications requiring the oil resistance, particularly for food packaging materials and food containers.

The oil-resistant agent can be applied to fibrous substrates (for example, textile products, and textile raw materials such as pulps) by any of methods known for treating textile products with a liquid. The fibrous substrate means both of a textile product and a textile raw material. When the textile product is a fabric, the fabric may be dipped in a solution (or a dispersion), or a solution (or a dispersion) may be adhered or sprayed on the fabric. The treatment may be an external addition treatment or an internal addition treatment. When the textile product is a paper, a solution (or a dispersion) may be coated on the paper, or a solution (or a dispersion) may be adhered or sprayed on the paper, or alternatively, a solution (or a dispersion) may be mixed with a pulp slurry before papermaking for the treatment. The treatment may be an external addition treatment or an internal addition treatment.

The oil-resistant agent may be applied to textile products (particularly, papers and fabrics) previously formed, or may also be applied at various stages of papermaking, for example, during the paper drying period.

For example, the fibrous substrate may be a leather. In order to render the leather hydrophobic and oleophobic, the oil-resistant agent may be applied as an aqueous solution or an aqueous emulsion to the leather at various stages in the leather processing period, for example, during a wet processing of the leather, or during the leather finishing period.

The oil-resistant agent can be used also be as an external mold release agent. For example, the surface of a substrate can easily be peeled off from another surface (the other surface of the substrate, or the surface of another substrate).

The "treatment" means applying the oil-resistant agent to a treatment target by e.g. dipping, spraying, or coating. By the treatment, the modified natural product being an active component of the oil-resistant agent penetrates into the inside of the treatment target and/or adheres on the surface of the treatment target.

In order to develop the oil resistance, the treatment target (substrate) treated is dried, preferably heated, for example, at a temperature of not lower than the glass transition temperature (Tg) of the modified natural product, for example, <NUM> or higher, <NUM> or higher or <NUM> or higher, or at a temperature of <NUM> or lower or <NUM> or lower. By the treatment at a temperature of not lower than Tg of the modified natural product, the arrangement of side chains is induced in some cases. The treatment temperature is more preferably a temperature of the melting point (Tm) or higher. By the treatment at a temperature of not lower than Tm of the modified natural product, the substrate surface is coated with the modified natural product. Thereby, a surface coating structure excellent in hydrophobicity can be formed.

In the case of the treatment with the oil-resistant agent in a liquid state, in order to enhance the desolventizing (dehydrating) property or the adhesion between the modified natural product and the substrate, the fibrous substrate treated may be pressurized, and the treatment is carried out at a pressure of <NUM> MPa or higher, preferably <NUM> MPa or higher and more preferably <NUM> MPa or higher.

The oil-resistant agent can suitably be used particularly for an additive for paper. The additive for paper containing the oil-resistant agent can be used, in addition to an oil-resistant agent, as a water-resistant agent, a water repellent, and/or an oil repellent. It is preferable that the additive for paper be in a form of solution, emulsion or aerosol. The additive for paper may contain the modified natural product and a medium (for example, a liquid medium such as an organic medium or water), and is preferably a water dispersion of the modified natural product. In the additive for paper, the concentration of the modified natural product may be, for example, <NUM>-<NUM> wt. The additive for paper may not contain a surfactant.

The removal of the solution (organic solvent, water) contained in the additive for paper can be carried out by heating the modified natural product solution (dispersion) at a temperature of <NUM> or higher, <NUM> or higher or <NUM> or higher, and a temperature of <NUM> or lower or <NUM> or lower.

The additive for paper can be used to treat (for example, surface treatment) a paper base. The additive for paper can be applied to a treatment target by a conventionally well-known method. Usually, a method (surface treatment) is adopted in which the additive for paper is dispersed in and diluted with an organic solvent or water, and adhered on the surface of a treatment target by a well-known method such as dip coating, spray coating or foam coating, and dried. Paper bases of the treatment target include papers, containers composed of a paper, formed articles composed of a paper (for example, pulp mold). The modified natural product of the present disclosure adheres well on paper bases. Here, "adhere" refers to the formation of a physical bond or a chemical bond. By making the modified natural product to adhere on paper bases, oil-resistant papers are obtained.

Hitherto, embodiments have been described, but it is to be understood that modes and details may be modified and changed variously without departing from the gist and the scope of the claims.

Then, the present disclosure will be described specifically by way of Examples. However, the present disclosure is not any more limited to these descriptions. Hereinafter, parts, % and ratio denote, unless otherwise specified, parts by weight (pbw), wt. % and weight ratio.

Test methods used in the below were as follows.

A pulp slurry was prepared which, as a wood pulp, had weight ratios of LBKP (broad-leaved tree bleached kraft pulp) and NBKP (needle-leaved tree bleached kraft pulp) of <NUM> wt. % and <NUM> wt. %, and a freeness of <NUM> of the pulp (Canadian Standard Freeness); a wet paper strength agent and a sizing agent were added to the pulp slurry and a paper of <NUM>/cm<NUM> in paper density and <NUM>/m<NUM> in basis weight was fabricated by a Fourdrinier paper machine; and the paper was used as a base paper for external addition treatment (size press treatment). The oil resistance (KIT value) of the base paper was <NUM>; and the water resistance (Cobb value) was <NUM>/m<NUM>.

As an emulsifier and a dispersant, used was a polyoxyethylene alkyl ether, a polyoxyethylene polyoxypropylene alkyl ether, a polyoxyethylene polyoxybutylene alkyl ether, a polyoxyethylene polyoxypropylene glycol, an alkylamine salt, a quaternary ammonium salt, a carboxylate salt, a polyethyleneimine ethoxylate or an analogous compound thereof.

In the case of fabricating a modified natural product solution (or dispersion) by using an organic solvent, an operation was three times repeated in which the modified natural product solution (or dispersion) (used chloroform, toluene or acetone as its solvent) of <NUM>/cm<NUM> was coated on the base paper by a Baker applicator set at a gap of <NUM> mil, and dried, and then, the resultant was annealed at <NUM> for <NUM>, to fabricate a treated paper.

In the case of fabricating a modified natural product solution (or dispersion) by using water, an operation was three times repeated in which the modified natural product solution (or dispersion) of <NUM> wt. % was coated on the base paper by a Baker applicator set at a gap of <NUM> mil, and dried, and then, the resultant was annealed at <NUM> for <NUM>, to fabricate a treated paper.

The oil resistance was measured by a <NUM> Kit Test (TAPPI T-<NUM>-<NUM>). The <NUM> Kit Test method involved placing a test oil containing castor oil, toluene and heptane blended therein on a surface of the treated paper, and after <NUM>, wiping out the test oil and then, evaluating the oil resistance by checking the presence/absence of oil stain into the treated paper. The test was carried out by using test oils of kit Nos. <NUM> to <NUM>, and the maximum kit number of the oil exhibited no staining was used as an evaluation result of the oil resistance.

Evaluation of the corn oil resistance (oil resistance)
a corn oil was placed on a surface of the treated paper, and after <NUM>, wiped out and then, the oil resistance was evaluated by checking the presence/absence of oil stain into the treated paper. The case where no stain was observed was taken as "Good"; and the case where stain was observed was taken as "Poor".

The liquid repellency was evaluated by spin coating a solution (or dispersion) of <NUM>% in solid content concentration of the modified natural product on a glass substrate having a cellophane film pasted thereon, and measuring the static contact angle. The static contact angle was obtained by dropping <NUM>µL of hexadecane (HD) on the resultant coating film, and measuring the contact angle at <NUM> after the liquid dropping.

The air permeability (air resistance) of the treated paper was measured by using an automatic Gurley densometer (product No. <NUM>-AUTO, vent diameter: <NUM> ±<NUM>), manufactured by Yasuda Seiki Seisakusho, Ltd. , according to JIS P8117 (<NUM>).

The melting point was measured by using a differential scanning calorimeter. A temperature exhibiting the highest endothermic peak was taken as a melting point of the modified natural product; and a temperature exhibiting the second highest endothermic peak was taken as a melting point of functional groups (side chains) in the modified natural product.

A mold was molded by using an automatic mold molding machine. In the lower section, a metal-made pulp mold forming mold provided with a large number of suction holes and having a network body disposed thereon was arranged; and in the upper section, a metal-made tank was arranged; and a pulp slurry was put in the upper-section metal tank. The pulp-containing aqueous composition was suctioned and dehydrated from the opposite side to the side of the pulp mold forming mold where the network body was disposed through the pulp mold forming mold and the network body, at <NUM>-<NUM> MPa by a vacuum pump, to cause a solid content (e.g. pulp) contained in the pulp-containing aqueous composition to deposit on the network body to obtain a pulp mold intermediate. Then, the obtained pulp mold intermediate was dried under a pressure of <NUM>-<NUM> MPa from the upside and downside in metal-made female and male molds heated at <NUM>-<NUM>. Thereby, a pulp mold product formed into a container shape was produced.

<NUM> of a corn oil at <NUM> was poured in the mold, and allowed to stand at room temperature for <NUM>; and thereafter, the degree of oil stain on the mold was evaluated. According to the degree of penetration, the evaluation numerical values were set as follows.

<NUM> of water at <NUM> was poured in the mold, and allowed to stand at room temperature for <NUM>; and thereafter, the degree of stain on the mold was evaluated. According to the degree of penetration, the evaluation numerical values were set as follows.

In a reaction container equipped with a reflux condenser and a Dean-Stark trap, a stirring bar, <NUM> of citric acid and <NUM> of octadecylamine were added, and heated to <NUM>; and <NUM> of toluene was added. The resultant was heated and stirred at <NUM> for <NUM> hours. The reaction container was cooled to room temperature; <NUM> of toluene was further added; and the resultant was cleaned with acetone and ethanol in order to obtain a modified natural product. The biobased content of the obtained modified natural product was <NUM>%. Then, the melting point of the obtained modified natural product was evaluated; and a <NUM>/cm<NUM> chloroform solution of the obtained modified natural product was fabricated, and the KIT test, the corn oil resistance, the liquid repellency and the air permeability were evaluated; and the evaluation results of these are shown in Table <NUM>.

In a reaction container equipped with a reflux condenser and a dean-stark trap, a stirring bar, <NUM> of citric acid, <NUM> of stearyl alcohol and <NUM> of toluene were added, and <NUM> of sulfuric acid was dropwise charged under stirring. The resultant was slowly heated to <NUM> and heated and stirred at <NUM> for <NUM> hours. The resultant was cooled to room temperature, and thereafter, <NUM> of chloroform was added, and heated and dissolved; thereafter, the resultant was cleaned with ethanol to obtain a modified natural product. The biobased content of the obtained modified natural product was <NUM>%. Then, the melting point of the obtained modified natural product was evaluated; and a <NUM>/cm<NUM> chloroform solution of the obtained modified natural product was fabricated, and the KIT test, the corn oil resistance, the liquid repellency and the air permeability were evaluated; and the evaluation results of these are shown in Table <NUM>.

By using a cellulose (<NUM>, powder) as the oil-resistant agent, the KIT test, the corn oil resistance, the liquid repellency and the air permeability were evaluated. The results are shown in Table <NUM>.

<NUM> of the modified natural product obtained in Example <NUM>, <NUM> of sodium oleate and <NUM> of water were added and heated at <NUM>; thereafter, hot water was added so that the concentration of the modified natural product became <NUM> wt. %, and the resultant was dispersed under heating at <NUM> by an ultrasonic homogenizer to fabricate a dispersion. By using this dispersion, the KIT test, the corn oil resistance and the air permeability were evaluated. The results are shown in Table <NUM>.

<NUM> of the modified natural product obtained in Example <NUM> and <NUM> of an emulsifier (polyoxyethylene oleyl ether) were added and heated at <NUM>; thereafter, hot water was added so that the concentration of the modified natural product became <NUM> wt. %, and the resultant was dispersed under heating at <NUM> by a mechanical shearing homogenizer to obtain a dispersion.

The same operation as in the method described in Example <NUM> was carried out, except for altering the emulsifier to sodium oleate to obtain a dispersion.

In each Example thereof, to <NUM> of a <NUM> wt. % water dispersion of a mixture of <NUM> parts of a broad-leaved tree bleached kraft pulp and <NUM> parts of a needle-leaved tree bleached kraft pulp, which had been beaten to a freeness of <NUM> cc (Canadian freeness), <NUM>,<NUM> of water was added. The water dispersion of the modified natural product obtained in Example <NUM> or <NUM> was added, under stirring, in a solid content concentration of the modified natural product per pulp weight as described in Table <NUM>, to prepare a pulp slurry.

Each pulp slurry of Examples <NUM> to <NUM> was charged in an automatic mold tester, and pressed at a pressure of <NUM> MPa, at a temperature of <NUM> for <NUM>, and thereafter pressed at a pressure of <NUM> MPa, at a temperature of <NUM> for <NUM> to fabricate a pulp mold of about <NUM> in weight. The obtained pulp mold was subjected to the practical oil resistance test and the practical water resistance test. The results are shown in Table <NUM>.

To <NUM> of a <NUM> wt. % water dispersion of a mixture of <NUM> parts of a broad-leaved tree bleached kraft pulp and <NUM> parts of a needle-leaved tree bleached kraft pulp, which had been beaten to a freeness of <NUM> cc (Canadian freeness), <NUM>,<NUM> of water was added to prepare a pulp slurry; the pulp slurry was charged in an automatic mold tester, and pressed at a pressure of <NUM> MPa, at a temperature of <NUM> for <NUM>, and thereafter pressed at a pressure of <NUM> MPa, at a temperature of <NUM> for <NUM> to fabricate a pulp mold of about <NUM> in weight. The obtained pulp mold was subjected to the practical oil resistance test and the practical water resistance test. The results are shown in Table <NUM>.

<NUM> of the modified natural product obtained in Example <NUM>, <NUM> of a polyoxyethylene trimethylnonyl ether and <NUM> of isopropyl alcohol were added, and heated at <NUM>, and the modified natural product was thereby dissolved. Hot water was added thereto so that the concentration of the modified natural product became <NUM> wt. %, and thereafter, the resultant was three times crushed at <NUM> MPa by a Star Burst Mini (model No. HJP-<NUM>), manufactured by Sugino Machine Ltd. , to obtain a dispersion.

The same operation as in the method described in Example <NUM> was carried out, except for altering the polyoxyethylene trimethylnonyl ether to an emulsifier or dispersant described in Table <NUM>, to obtain a dispersion.

The same operation as in the method described in Examples <NUM> to <NUM> was carried out, except for altering the concentration of the modified natural product to <NUM> wt. %, the number of times of the crushing to one time and the emulsifier or dispersant to one described in Table <NUM>, to obtain a dispersion. The dispersibility was improved compared to the cases wherein the concentration of the modified natural product is <NUM> wt%.

In each Example thereof, to <NUM> of a <NUM> wt. % water dispersion of a mixture of <NUM> parts of a broad-leaved tree bleached kraft pulp and <NUM> parts of a needle-leaved tree bleached kraft pulp, which had been beaten to a freeness of <NUM> cc (Canadian freeness), <NUM>,<NUM> of water was added. The corresponding water dispersion of the modified natural product obtained in Examples <NUM> to <NUM> was added, under stirring, so that the solid content concentration per pulp weight of the modified natural product became <NUM>%, to prepare a pulp slurry. The pulp slurry was charged in an automatic mold tester, and pressed at a pressure of <NUM> MPa, at a temperature of <NUM> for <NUM>, and thereafter pressed at a pressure of <NUM> MPa, at a temperature of <NUM> for <NUM> to fabricate a pulp mold of about <NUM> in weight. The obtained pulp mold was subjected to the practical oil resistance test. The results are shown in Table <NUM>.

An emulsifier aqueous solution (dispersion) was prepared by adding <NUM> of water to <NUM> of an emulsifier A (a polyoxyethylene polyoxypropylene alkyl ether), and thereafter <NUM> of the modified natural product obtained in Example <NUM> was added and stirred, and three times crushed at <NUM> MPa by the STAR Burst Mini to obtain a dispersion.

An emulsifier aqueous solution (dispersion) was prepared by adding <NUM> of water to <NUM> of the emulsifier A (a polyoxyethylene polyoxypropylene alkyl ether) and <NUM> of an emulsifier B (a hydroxyethylalkylmethylammonium chloride), and thereafter <NUM> of the modified natural product obtained in Example <NUM> was added and stirred, and three times crushed at <NUM> MPa by the STAR Burst Mini to obtain a dispersion.

In each Example thereof, the same operation as in the method described in Example <NUM> was carried out, except for altering the emulsifier B and the additive to those described in Table <NUM>, to obtain a dispersion.

To <NUM> of a <NUM> wt. % water dispersion of a mixture of <NUM> parts of a broad-leaved tree bleached kraft pulp and <NUM> parts of a needle-leaved tree bleached kraft pulp, which had been beaten to a freeness of <NUM> cc (Canadian freeness), <NUM>,<NUM> of water was added. The water dispersion of the modified natural product obtained in Examples <NUM> to <NUM> was added, under stirring, so that the solid content concentration per pulp weight of the modified natural product became <NUM>%, to prepare a pulp slurry. The pulp slurry was charged in an automatic mold tester, and pressed at a pressure of <NUM> MPa, at a temperature of <NUM> for <NUM>, and thereafter pressed at a pressure of <NUM> MPa, at a temperature of <NUM> for <NUM> to fabricate a pulp mold of about <NUM> in weight. The obtained pulp mold was subjected to the practical oil resistance test. The results are shown in Table <NUM>.

<NUM> of dimethyl <NUM>-hydroxyglutarate was dissolved in <NUM> of dehydrated toluene, and thereafter, <NUM> of stearylamine was added, and stirred over night at an oil bath temperature of <NUM>. The next day, the resultant was cooled to room temperature, and <NUM> of methanol was added, and the reaction solution was filtered. An obtained solid was dried to obtain <NUM> of a compound A. <CHM>
<NUM>H NMR (CDCl<NUM>, <NUM>) δ: <NUM> (t, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM>,<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (br s, <NUM>).

A <NUM>/cm<NUM> chloroform solution of the compound A was fabricated, and the KIT test and the corn oil resistance were evaluated. The results are shown in Table <NUM>.

<NUM> of D,L-malic acid was dissolved in <NUM> of acetyl chloride, and thereafter stirred at an oil bath temperature of <NUM> for <NUM> hours. After <NUM> hours, the resultant was concentrated to dryness to obtain <NUM> of an intermediate compound.

<CHM>
<NUM>H NMR (CDCl<NUM>, <NUM>) δ: <NUM> (s, <NUM>), <NUM> (dd, <NUM>), <NUM> (dd, <NUM>), <NUM> (dd, <NUM>).

<NUM> of the intermediate compound was dissolved in <NUM> of dehydrated dichloromethane, and thereafter, <NUM> of stearylamine was added, and stirred over night at an oil bath temperature of <NUM>. The next day, the resultant was concentrated to dryness, thereafter suspended in <NUM> of dichloromethane, and thereafter filtered and dried to obtain <NUM> of a compound B. <CHM>
wherein Ac is an acetyl group.

<NUM>H NMR (CDCl<NUM>, <NUM>) δ: <NUM> (t, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (t, <NUM>), <NUM> (br s, <NUM>).

<NUM> of the compound B was dissolved in <NUM> of dehydrated chloroform, and thereafter stirred for <NUM> in an ice bath, and thereafter, <NUM> of stearylamine, <NUM> of <NUM>,<NUM>-dimethylaminopyridine and <NUM> of a <NUM>-ethyl-<NUM>-(<NUM>-dimethylaminopropyl)carbodiimide hydrochloric acid salt were added in order. The reaction solution was stirred overnight, and thereafter concentrated to dryness. Then, the residue was cleaned with <NUM> of water and <NUM> of methanol in order, and thereafter filtered and dried to obtain <NUM> of a compound C. <CHM>
wherein Ac is an acetyl group.

<NUM>H NMR (CDCl<NUM>, <NUM>) δ: <NUM> (t, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (br s, <NUM>).

A <NUM>/cm<NUM> chloroform solution of the compound C was fabricated, and the KIT test and the corn oil resistance were evaluated. The results are shown in Table <NUM>.

<CHM>
wherein Boc is a t-butoxycarbonyl group.

A <NUM>/cm<NUM> chloroform solution of the compound D was fabricated, and the KIT test and the corn oil resistance were evaluated. The results are shown in Table <NUM>.

Claim 1:
An agent, which is an oil-resistant agent, comprising a modified natural product (i) having a biobased content, measured according to ASTM D6866, of ≥ <NUM>% and (ii) wherein
- a hydroxyl group of a carboxyl group of a biobased compound having at least one carboxyl group is replaced by -X-R<NUM> or -X-D-X'-R<NUM>, or
- a carboxyl group of the biobased compound is replaced by
<CHM>
wherein
X is a direct bond, -O-, -NR<NUM>- or -S-;
R<NUM> is a C<NUM>-<NUM>-hydrocarbon group optionally having a substituent selected from OH, carboxyl, alkoxy ester, alkoxy, amino, amine salts, and (Rc)<NUM>Si and (RcO)<NUM>Si wherein Rc each independently is H or C<NUM>-<NUM>-alkyl;
D is C<NUM>-<NUM>-alkylene; and
X' is -C(=O)-O-, -O-C(=O)-, -C(=O)-NR<NUM>- or -NR<NUM>-C(=O)-, wherein R<NUM> and R<NUM> are each H or C<NUM>-<NUM>-alkyl optionally having a substituent.