Oil-resistant agent

Abstract

This invention provides an oil-resistant agent comprising a modified natural product containing a bio-based compound having at least one carboxyl group, wherein the hydroxyl group of the carboxyl group is replaced by an R group, or the carboxyl group is replaced by an Ra group. This oil-resistant agent is environmentally friendly and imparts sufficient oil resistance. R group: -X-R 1 Or -X-D-X′-R 1 Ra group: the following groups. [Where X is a valence bond, -O-, -NR] 11 - or -S-, R 1 It is a hydrocarbon group with 1 to 40 carbon atoms, or a polysiloxane, where D is an alkylene group with 1 to 10 carbon atoms, and X′ is -C(=O)-O-, -O-C(=O)-, or -C(=O)-NR. 12 - or - NR 12 -C(=O)-(where, R) 11 and R 12 It is either hydrogen or an alkyl group having 1 to 40 carbon atoms.

Description

Technical Field

[0001] This invention relates to oil-resistant agents for modified natural products obtained by modifying bio-based compounds. Background Technology

[0002] Paper containers are highly anticipated as an alternative to single-use plastic containers. Paper food packaging materials and containers need to prevent the leakage of moisture and oil from food, thus requiring the application of oil-resistant agents, either internally or externally. Furthermore, from an environmental perspective, the demand for bio-based materials is also increasing.

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

[0004] Patent document 2 (Japanese Patent Application Publication No. 7-120876) discloses a support for photographic paper, wherein the base paper contains an aliphatic oxyacid, a monohydric alcohol with alkyl or alkenyl groups having 8 to 24 carbon atoms, and / or a reaction product of an alkyl or alkenyl group having 4 to 24 carbon atoms and an amine substituented with an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 3 to 24 carbon atoms, or hydrogen.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 9-286768

[0008] Patent Document 2: Japanese Patent Application Publication No. 7-120876 Summary of the Invention

[0009] The technical problem that the invention aims to solve

[0010] The purpose of this invention is to provide an oil-resistant agent that is environmentally friendly and can be given sufficient oil resistance by using modified natural substances.

[0011] Technical means for solving technical problems

[0012] This invention relates to modified natural products obtained by modifying bio-based compounds with organic modifying groups. Examples of organic modifying groups include hydrocarbon groups having 1 to 40 carbon atoms and having substituents, or polysiloxanes.

[0013] Modified natural substances can be used as oil-resistant agents.

[0014] The preferred embodiment of the present invention is as follows.

[0015] Method 1:

[0016] An oil-resistant agent comprising a modified natural product of a bio-based compound having at least one carboxyl group in which the hydroxyl group of the carboxyl group is replaced by an R group, or a modified natural product in which the carboxyl group is replaced by an Ra group, wherein the R group is: -X-R 1 Or -X-D-X′-R 1

[0017] Ra-base:

[0018]

[0019] [In the formula, X represents valence bond, -O-, -NR] 11 - or -S-,

[0020] R 1 It can be a hydrocarbon group with 1 to 40 carbon atoms that can have substituents, or a polysiloxane.

[0021] D is an alkylene group having 1 to 10 carbon atoms.

[0022] X′ is -C(=O)-O-, -O-C(=O)-, -C(=O)-NR 12 - or - NR 12 -C(=O)-. (Where R is...) 11 and R 12 It is hydrogen, or an alkyl group having 1 to 40 carbon atoms that may have substituents.

[0023] Method 2:

[0024] The oil-resistant agent as described in Method 1, wherein the carboxyl group of the modified natural product has a salt structure.

[0025] Method 3:

[0026] The oil-resistant agent as described in any one of methods 1 to 2, wherein the bio-based compound has hydroxyl groups.

[0027] Method 4:

[0028] The oil-resistant agent as described in any one of methods 1 to 3, wherein the hydrogen of the hydroxyl group of the bio-based compound is replaced by an Rb group.

[0029] Rb base: -Y-R 21

[0030] [In the formula, Y represents the valence bond, -C(=O)-, -C(=O)-NR] 22 - or C = S - (R) 22 (It can be hydrogen or a hydrocarbon group with 1 to 4 carbon atoms that may have substituents),

[0031] R 21 It can be a hydrocarbon group with 1 to 40 carbon atoms that may have substituents, or a polysiloxane.

[0032] Method 5:

[0033] The oil-resistant agent as described in any one of methods 1 to 4, wherein the carboxyl or hydroxyl group is cross-linked by a multifunctional cross-linking agent.

[0034] Method 6:

[0035] The oil-resistant agent as described in any one of methods 1 to 5, wherein the bio-based compound is a compound of the natural product itself or a compound derived from the natural product.

[0036] Method 7:

[0037] The oil-resistant agent according to any one of methods 1 to 6, wherein the bio-based compound is selected from at least one of citric acid, malic acid, gluconic acid, alginic acid, butyric acid, lactic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, chlorogenic acid, aldonic acid, uronic acid, aldonic acid and its derivatives.

[0038] Method 8:

[0039] The oil-resistant agent as described in any one of methods 1 to 7, wherein the bio-based compound is a compound represented by the following formula.

[0040]

[0041] [In the formula, each E] 1 Whether they are the same or different, they are hydrogen or -COOH.

[0042] Each E 2 The same or different, either hydrogen or -OH,

[0043] E 3 -COOE 4 (where E) 4 (either hydrogen or an alkyl group having 1 to 22 carbon atoms), -CH3, -NH2, or -OH.

[0044] m is a number between 0 and 10.

[0045] Method 9:

[0046] The oil-resistant agent as described in any one of methods 1 to 8, wherein the bio-based compound has two or more carboxyl groups.

[0047] Method 10:

[0048] The oil-resistant agent as described in any one of methods 1 to 9, wherein R 1 It can be an aliphatic hydrocarbon group with 1 to 40 carbon atoms that can have substituents.

[0049] Method 11:

[0050] The oil-resistant agent as described in any one of methods 1 to 10, wherein the carboxyl group of the modified natural product is cross-linked by a multifunctional cross-linking agent, and the hydroxyl group having the carboxyl group is cross-linked by a binding group Z (Z is -O-, -NR). 31 -(R) 31 It is a structure in which hydrogen or alkyl groups having 1 to 8 carbon atoms can be bonded together.

[0051] Method 12:

[0052] The oil-resistant agent as described in any one of methods 1 to 11, wherein the hydroxyl groups of the modified natural product are cross-linked by a multifunctional cross-linking agent, and the hydrogen having the hydroxyl group is cross-linked by a binding group Z′ (Z′ is -C(=O)− or -C(=O)−NR). 41 -(R) 41 It is a structure in which hydrogen or alkyl groups having 1 to 4 carbon atoms are bonded together.

[0053] Method 13:

[0054] The oil-resistant agent according to any one of methods 1 to 12, wherein the bio-based content is 30% or more.

[0055] Method 14:

[0056] The oil-resistant agent as described in any one of methods 1 to 13, wherein the biodegradability is 5% or more.

[0057] Method 15:

[0058] The oil-resistant agent as described in any one of methods 1 to 14 is a water-dispersible composition.

[0059] Method 16:

[0060] The oil-resistant agent as described in any one of methods 1 to 15 contains an emulsifier or a dispersant.

[0061] Method 17:

[0062] The oil-resistant agent according to any one of methods 1 to 16 contains an emulsifier or dispersant, wherein the emulsifier or dispersant is a cationic, nonionic, and / or anionic emulsifier or dispersant.

[0063] Method 18:

[0064] The oil-resistant agent as described in any one of methods 1 to 17 contains at least one selected from a self-retention agent, a sizing agent, a pH adjuster, a filler, and a paper strength enhancer.

[0065] Method 19:

[0066] The oil-resistant agent according to any one of methods 1 to 18 contains a retention aid, which comprises at least one selected from aluminum sulfate, acrylic polymer, starch, modified starch, cellulose, modified cellulose and silica.

[0067] Method 20:

[0068] The oil-resistant agent according to any one of methods 1 to 19 contains a sizing agent comprising at least one selected from rosin-based sizing agents, alkyl ketene dimers (AKD), alkenyl succinic anhydride (ASA), polyvinyl alcohol (PVA), modified starch, styrene / acrylic acid copolymers, and styrene / methacrylic acid copolymers.

[0069] Method 21:

[0070] The oil-resistant agent according to any one of methods 1 to 20 contains a paper strength enhancer, which comprises at least one selected from urea-formaldehyde resin, melamine-formaldehyde resin, polyamide-polyamine-epoxychloropropane (PAE), polyethyleneamine (PVAm), dry-modified starch, polyacrylamide, and polyvinyl alcohol.

[0071] Method 22:

[0072] The oil-resistant agent as described in any one of methods 1 to 21, wherein the melting point is above 25°C.

[0073] Method 23:

[0074] The oil-resistant agent as described in any one of methods 1 to 22, wherein the HD contact angle is 10° or more.

[0075] Method 24:

[0076] The oil-resistant agent as described in any one of methods 1 to 23 is an oil-resistant agent.

[0077] Method 25:

[0078] A fiber product comprising any one of the methods 1 to 24.

[0079] Method 26:

[0080] An oil-resistant paper containing any one of the methods 1 to 24.

[0081] Method 27:

[0082] A food packaging material or food container comprising any one of the methods 1 to 24.

[0083] Method 28:

[0084] A treatment method wherein the oil-resistant agent described in any one of methods 1 to 24 is used to perform external or internal treatment on paper.

[0085] Method 29:

[0086] A method for treating fibers, wherein a fibrous substrate containing an oil-resistant agent as described in any one of methods 1 to 24 is molded or desolventized under a pressure higher than 0.1 MPa.

[0087] Method 30:

[0088] A method for treating fibers, wherein a fibrous substrate containing an oil-resistant agent as described in any one of methods 1 to 24 is heated, shaped, or dried at a temperature of 25°C or higher.

[0089] Method 31:

[0090] A compound shown in the following formula.

[0091]

[0092] [In the formula, each R″ may be the same or different, and can be -OH or -NH-R.] 1 (R 1 (These can be hydrocarbon groups with 1 to 40 carbon atoms that can have substituents).

[0093] R′ is either hydrogen or acetyl.

[0094] Invention Effects

[0095] The oil-resistant agent of this invention exhibits excellent oil resistance. Furthermore, the oil-resistant agent of this invention is bio-based, thus having a low environmental impact. Detailed Implementation

[0096] Oil-resistant agents impart oil resistance by treating the substrate. Oil resistance can include functions such as preventing oil from penetrating the substrate, oil repellency, or stain resistance, but is not limited to these.

[0097] Here, "oil" refers to fats or organic solvents. Examples of fats include edible oils (vegetable fats, animal fats, vegetable fats, animal fats) and industrial oils. Examples of edible oils include salad oil, corn oil, sesame oil, rapeseed oil, and olive oil. Examples of industrial oils include castor oil. Organic solvents can be polar or non-polar. Examples of non-polar solvents include hexane and hexadecane, but are not limited to these.

[0098] In addition, the treated material can possess water resistance and water repellency. Besides containing modified natural substances, oil-resistant agents may also contain liquid media (water, organic solvents, or mixtures thereof). Oil-resistant agents may also contain at least one selected from surfactants, dispersants, terminated isocyanate compounds, and additives.

[0099] Bio-based compounds are preferably compounds containing carbon derived from bio-based sources. The bio-based content is determined according to ASTM D6866. The bio-based content of compounds containing carbon derived from bio-based sources is not 0%. The bio-based content is preferably 10% or more, more preferably 30% or more, further preferably 50% or more, and most preferably 80% or 90% or more, for example, 100%. A high bio-based content means less use of fossil resources such as petroleum; from this perspective, it can be said that the higher the bio-based content of the bio-based compound, the better.

[0100] Bio-based compounds can be compounds derived from natural substances or those that are themselves natural substances. That is, bio-based compounds also include derivatives of natural substances.

[0101] The modified natural material is preferably a compound containing carbon derived from bio-based sources. The bio-based content is determined according to ASTM D6866. The bio-based content is not 0%. Preferably, the bio-based content is 10% or more, more preferably 30% or more, further preferably 50% or more, and most preferably 80% or 90% or more, for example, 100%. A high bio-based content means less use of fossil resources such as petroleum; from this perspective, it can be said that the higher the bio-based content of the modified natural material, the better.

[0102] The present invention provides an oil-resistant agent comprising a modified natural product containing at least one R-group substituted hydroxyl group of a bio-based compound having at least one carboxyl group, or a modified natural product containing at least one R-group substituted hydroxyl group of a carboxyl group, preferably a modified natural product containing at least one R-group substituted hydroxyl group of a carboxyl group.

[0103] The R-basis is given by:

[0104] -X-R 1

[0105] [In the formula, X represents valence bond, -O-, -NR] 11 -(R) 11 It is hydrogen, or an alkyl group having 1 to 40 carbon atoms (e.g., 1 to 10 or 1 to 4) that may have substituents, or -S-.

[0106] R 1 [A hydrocarbon group having 1 to 40 carbon atoms that can have substituents, or a polysiloxane], or the formula: -X-D-X′-R 1

[0107] [In the formula, X′ is -C(=O)-O-, -O-C(=O-, -C(=O-NR)] 12 - or - NR 12 -C(=O)-(R) 12 It can be hydrogen or an alkyl group having 1 to 40 carbon atoms (e.g., 1 to 10 or 1 to 4) that may have substituents.

[0108] D is an alkylene group having 1 to 10 carbon atoms.

[0109] X and R 1 The meaning is the same as the group shown above.

[0110] The Ra group is a group represented by the following formula.

[0111]

[0112] [In the formula, R] 1 It can be a hydrocarbon group with 1 to 40 carbon atoms that may have substituents, or a polysiloxane.

[0113] Examples of substituents include hydroxyl, carboxyl, alkoxy ester, alkoxy, (Rc)3Si, (RcO)3Si, amino, and amine salts (each Rc may be the same or different, and may be a hydrogen atom or an alkyl group with C1 to C4 carbon atoms).

[0114] Modifying the carboxyl group of natural substances can give them a salt structure. Corresponding cations include ammonium ions, quaternary ammonium ions, alkali metals, and alkaline earth metals.

[0115] Bio-based compounds can also have functional groups other than carboxyl groups; examples of other functional groups include hydroxyl groups.

[0116] In bio-based compounds with hydroxyl groups, the hydrogen atoms of the hydroxyl group can be replaced by Rb groups.

[0117] Rb base: -Y-R 21

[0118] [In the formula, Y represents the valence bond, -C(=O)-, -C(=O)-NR] 22 - or C = S - (R) 22 It is hydrogen, or an alkyl group having 1 to 40 carbon atoms that may have substituents, preferably hydrogen or methyl, more preferably hydrogen.

[0119] R 21 It can be a hydrocarbon group with 1 to 40 carbon atoms that may have substituents, or a polysiloxane.

[0120] Modifying the hydroxyl groups of natural substances can give them a salt structure. Corresponding cations include ammonium ions, quaternary ammonium ions, alkali metals, and alkaline earth metals.

[0121] The carboxyl or hydroxyl groups of modified natural products can be cross-linked by multifunctional cross-linking agents.

[0122] The carboxyl group of the modified natural product can be cross-linked by a multifunctional cross-linking agent, resulting in a structure where the hydroxyl group of the carboxyl group is bonded through a binding group Z. Z is preferably -O- or -NR. 31 -(R) 31 The group is hydrogen, or an alkyl group having 1 to 9 or 1 to 4 carbon atoms that may have a substituent, preferably hydrogen or methyl, and more preferably hydrogen.

[0123] The hydroxyl groups of the modified natural product can be cross-linked by a multifunctional cross-linking agent, allowing for a structure where the hydrogen atoms of the hydroxyl group are bonded through groups having a binding group Z′. Z′ is preferably -C(=O)− or -C(=O)−NR. 41 -(R) 41 The group is hydrogen, or an alkyl group having 1 to 9 or 1 to 4 carbon atoms that may have a substituent, preferably hydrogen or methyl, and more preferably hydrogen.

[0124] Multifunctional crosslinking agents include, for example, diamine, putrescine, cadaverine, hexamethylenediamine, 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, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and hexamethylene diisocyanate (HDI).

[0125] -X-R 1 Examples of bases include -R 1 -O-R 1 、-NR 11 -R 1 -S-R 1 (where R is in the formula) 1 and R 11 (The meaning is the same as above). Preferably, it is -O-R. 1 、-NR 11 -R 1 More preferably -NR 11 -R 1 It is further preferred as -NH-R because it can provide a higher contact angle. 1 .

[0126] -X-D-X′-R 1 Examples of bases include -O-D-O-C (=O)-R 1 -O-D-C(=O)-NR 11 R 1 -O-D-NR 12 -C(=O)-R 1 、-NR 13-D-O-C(=O)-R 1 、-NR 13 -D-C(=O)-NR 11 R 1 、-NR 13 -D-NR 12 -C(=O)-R 1 (where R is in the formula) 1 R 11 and R 12 The meaning is the same as above, R 13 It is hydrogen, or an alkyl group having 1 to 40 carbon atoms that may have substituents. D is a C1 to 10 alkylene group, preferably a C1 to 4 alkylene group. Preferably -NR 13 -D-O-C(=O)-R 1 、-NR 13 -D-C(=O)-O-R 1 、-NR 13 -D-C(=O)-NR 11 R 1 、-NR 13 -D-NR 12 -C(=O)-R 1 More preferably, it is -NH-D-O-C(=O)-R 1 ,-NH-D-C(=O)-O-R 1 、-NR 13 -D-C(=O)-NHR 1 、-NR 13 -D-NH-C(=O)-R 1 .

[0127] When a bio-based compound or modified natural product has two or more carboxyl groups, the hydroxyl groups of the two carboxyl groups can be replaced by Rd ​​groups for bonding. The Rd group is preferably a group shown in the following formula:

[0128] -NR 1 -.

[0129] [In the formula, R] 1 The meaning is the same as above.

[0130] R 1 The number of carbon atoms is 1 to 40, and can be 2 or more, 4 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, or 20 or more, preferably 8 or more or 12 or more. The number of carbon atoms in the hydrocarbon group can be 40 or less, 35 or less, 30 or less, 25 or less, 22 or less, 20 or less, or 18 or less. Preferably 30 or less. For example, R 1 The number of carbon atoms can be 4–35, 6–30, 8–25, or 10–22.

[0131] R 1 The hydrocarbon group can be saturated or unsaturated and may have substituents, preferably an aliphatic hydrocarbon group, and more preferably an aliphatic hydrocarbon group. The hydrocarbon group can be straight-chain, branched, or cyclic, preferably straight-chain or branched, and more preferably straight-chain. For example, R 1 It can be a straight-chain or branched alkyl group.

[0132] R 1 The bio-based group may have substituents containing carbon derived from bio-based materials. Preferably, the bio-based content, as measured using ASTM D6866, is not 0%, or is 10% or more, more preferably 30% or more, further preferably 50% or more, and most preferably 80% or more. The upper limit for the bio-based content may be 100%, 95%, 90%, or 85%.

[0133] As R 1 Specific examples include: n-propyl, isopropyl, n-butyl, tert-butyl, neopentyl, octyl, isooctyl, nonyl, decyl, undecyl, lauryl, tridecyl, tetradecyl, pentadecyl, palmityl, heptadecanyl, stearyl, benzyl, 2-ethylhexyl, isostearyl, etc.; alkenyl groups such as oleyl, palmylene, eicosene, etc.; and cyclohexyl groups such as cyclohexyl.

[0134] R 1 It can be a hydrocarbon group containing an A group, such as an amino group or an ammonium group.

[0135] A is the preferred formula: -NA 1 A 2 or -N + A 1 A 2 A 3 B － (A 1 A 2 and A 3 It is hydrogen or an alkyl group having 1 to 10 carbon atoms, preferably hydrogen or an alkyl group having 1 to 3 carbon atoms, and most preferably hydrogen or methyl. － The group is represented by ions such as halide ions and acetate ions.

[0136] R 11 and R 12 It is hydrogen or an alkyl group having 1 to 40 carbon atoms that may have substituents, preferably hydrogen or an aliphatic hydrocarbon having 1 to 40 carbon atoms, more preferably hydrogen or an aliphatic hydrocarbon having 1 to 25 carbon atoms, even more preferably hydrogen or an aliphatic hydrocarbon having 1 to 10 carbon atoms, and most preferably hydrogen.

[0137] R 13It is hydrogen or an alkyl group having 1 to 40 carbon atoms that may have substituents, preferably hydrogen or an aliphatic hydrocarbon having 1 to 40 carbon atoms, more preferably hydrogen or an aliphatic hydrocarbon having 1 to 25 carbon atoms, even more preferably hydrogen or an aliphatic hydrocarbon having 1 to 10 carbon atoms, and most preferably hydrogen.

[0138] The modified natural compound is preferably a compound in which at least one of the hydroxyl groups of the carboxyl group is replaced by an R group, or a compound in which the carboxyl group is replaced by an Ra group.

[0139]

[0140] [In the formula, each E] 1 Whether they are the same or different, they are hydrogen or -COOH.

[0141] Each E 2 The same or different, either hydrogen or -OH,

[0142] E 3 -COOE 4 (where E) 4 (either hydrogen or an alkyl group having 1 to 22 carbon atoms), -CH3, -NH2, or -OH.

[0143] m is a number between 0 and 10.

[0144] In E 4 When the alkyl group is an alkyl group, the number of carbon atoms in the alkyl group can be 1 to 4 or 1 to 10.

[0145] m can be 1–8, 2–6, or 3–5.

[0146] Examples of modifications to natural substances are as follows.

[0147] E5-CH2-COE 11

[0148] [In the formula, E5 is NHE6, and E6 is Boc, H and COE] 12 Any one of them, E 11 and E 12 They are either R or OH, and at least one is R.

[0149] E7-CHE8-CHE9-COE 11

[0150] [In the formula, E7 represents NHE6 and COE] 12 OCOR 1 Any one of them, preferably COE 12 E8 and E9 are H, OH, or OCOR, respectively. 1 E8 is preferably H, E9 is preferably H or OAc, E6, E 11 and E12 As above.

[0151] E 12 -CO-CH2-C(OH)E 10 -CH2-COE 11

[0152] [In the formula, E] 10 For COE 13 Or H, E 11 E 12 E 13 They are either R or OH, and at least one is R.

[0153] In the above example, the R basis is -X-R. 1 Or -X-D-X′-R 1 X, R 1 D and X′ are as above.

[0154] In the above examples, Ac represents acetyl and Boc represents tert-butoxycarbonyl.

[0155] The above examples illustrate the presence of an R group, but one or more -CO-R groups in each of the modified natural products in the above examples can also be replaced with a Ra group.

[0156] Among several methods, specific examples of modifying natural substances are as follows.

[0157]

[0158] [In the formula, Ac is an acetyl group]

[0159] Boc is a tert-butoxycarbonyl group.

[0160] R 1 It can be a polysiloxane. A polysiloxane is, for example, a group represented by the following formula:

[0161] -R 51 -[Si(R) 52 (R) 53 )] a -[Si(R) 54 (R) 55 )] b -Si(R) 56 (R) 57 (R) 58 ).

[0162] [In the formula, R] 51 R is an O (oxygen atom) or a hydrocarbon group with 1 to 10 carbon atoms. 52 R 53 R 54 R 55R 56 R 57 R 58 These are hydrogen, hydroxyl, alkoxy group (1-40 carbon atoms), and hydrocarbon group (1-40 carbon atoms), which may be the same or different. 'a' represents an integer greater than or equal to 0, 'b' represents an integer greater than or equal to 1, and (a+b) ranges from 3 to 200.

[0163] R 51 It is an O or a hydrocarbon group having 1 to 10 carbon atoms, preferably an O or an alkylene group having 1 to 5 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms.

[0164] R 52 R 53 R 54 R 55 R 56 R 57 R 58 The groups are hydrogen, hydroxyl, alkoxy group with 1 to 40 carbon atoms, and hydrocarbon group with 1 to 40 carbon atoms, which may be the same or different. Preferably, the groups are hydrogen, hydroxyl, alkoxy group with 1 to 10 carbon atoms, saturated hydrocarbon group with 1 to 40 carbon atoms, and aryl group with 6 to 20 carbon atoms. More preferably, the groups are hydrogen, hydroxyl, alkoxy group with 1 to 3 carbon atoms, and saturated hydrocarbon group with 1 to 30 carbon atoms. Even more preferably, the groups are hydrogen, hydroxyl, methyl, methoxy, ethylene, propyl, and saturated hydrocarbon group with 10 to 24 carbon atoms.

[0165] In R 52 R 53 R 54 R 55 R 56 R 57 R 58 In this compound, alkyl groups with 1 to 40 carbon atoms and aryl groups with 6 to 20 carbon atoms can be unsubstituted or substituted.

[0166] R 52 R 53 R 54 R 55 R 56 R 57 R 58 Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, tolyl, naphthyl, etc.

[0167] In R 52 R 53 R 54 R 55 R 56 R 57R 58 In this context, alkoxy groups with 1 to 10 carbon atoms can be either straight-chain or branched. Examples include methoxy, ethoxy, propoxy, and butoxy.

[0168] From the perspective of ease of industrial manufacturing and availability, R 52 R 53 R 54 R 55 R 56 R 57 R 58 Preferably, it contains hydrogen atoms or methyl groups, more preferably methyl groups.

[0169] The sum of a and b is 3 to 200 or 5 to 200. From the perspective of ease of industrial manufacture, availability, and operation, the sum of a and b is preferably 10 to 100, more preferably 40 to 60. a can be 0 to 150, for example 1 to 100. The lower limit of b can be 1, 2, or 3, and the upper limit of b can be 150, 10, or 5.

[0170] Bio-based compounds are compounds having at least one carboxyl group (natural compounds containing carboxyl groups).

[0171] Bio-based compounds can be low molecular weight (e.g., weight-average molecular weight less than 1000, or less than 500) and / or high molecular weight. High molecular weights can have a weight-average molecular weight of 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more. High molecular weights can also have a weight-average molecular weight of less than 7,500,000, less than 5,000,000, less than 3,000,000, less than 1,000,000, less than 750,000, less than 500,000, less than 300,000, less than 100,000, less than 75,000, or less than 50,000. Weight-average molecular weight can be determined using gel permeation chromatography (GPC) via pullulan conversion.

[0172] Bio-based compounds can be high-molecular-weight natural products, low-molecular-weight natural products, or their derivatives.

[0173] Bio-based compounds (natural substances or compounds derived from natural substances) may include, for example, glycine, citric acid, malic acid, glutaric acid, gluconic acid, alginic acid, butyric acid, lactic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, chlorogenic acid, aldonic acid, uronic acid, aldonic acid, or derivatives thereof.

[0174] Bio-based compounds (natural or derived from natural substances) are preferably compounds represented by the following formula:

[0175]

[0176] [In the formula, each E] 1 Whether they are the same or different, they are hydrogen or -COOH.

[0177] Each E 2 The same or different, either hydrogen or -OH,

[0178] E 3 -COOE 4 (where E) 4 (either hydrogen or an alkyl group having 1 to 22 carbon atoms), -CH3, -NH2, or -OH.

[0179] m is a number between 0 and 10.

[0180] In E 4 When the alkyl group is an alkyl group, the number of carbon atoms in the alkyl group can be 1 to 4 or 1 to 10.

[0181] m can be 1–8, 2–6, or 3–5.

[0182] Modified natural materials can possess the biodegradability specified in ASTM D5338. Preferably, the content is 5% or more, more preferably 10% or more, more preferably 20% or more, 30% or more, more preferably 50% or more, further preferably 80% or more, and most preferably 90% or more. Higher biodegradability results in a lower environmental burden; therefore, it can be said that the higher the biodegradability of the modified natural materials, the better.

[0183] Modified natural compounds can be produced by reacting a modifier with the carboxyl group of a bio-based compound. Examples of synthetic methods involving the reaction of a modifier with a carboxyl group include methods for forming ester bonds, amide bonds, and oxazole rings.

[0184] Modifiers are preferably compounds with hydrocarbon groups, especially those with aliphatic hydrocarbon groups. Examples of modifiers are as follows.

[0185] alcohol (R) 1 -OH),

[0186] Amine (R) 1 -NR 2 H)

[0187] Isocyanate (R) 1 -N=C=O),

[0188] Isothiocyanate (R) 1 -N=C=S)

[0189] [In the formula,

[0190] R 1The meaning is the same as above (it can be a hydrocarbon group with 1 to 40 carbon atoms having substituents, or a polysiloxane).

[0191] R 2 It is hydrogen, or an alkyl group having 1 to 40 carbon atoms (e.g., 1 to 10 or 1 to 4) that may have substituents.

[0192] Regarding the substitution rate of the carboxyl group or the hydroxyl group of the carboxyl group achieved by the modifying agent, the substitution rate is greater than 0, and more preferably 1% or more, 3% or more, 5% or more, or 10% or more, for example, 15% or more, 20% or more, 30% or more, 80% or more, 90% or more, or 95% or more. "Substitution rate" refers to the average percentage (%) of the carboxyl group or the hydroxyl group of the carboxyl group present in the structure of the modified natural product being replaced by the modifying agent.

[0193] The percentage of unmodified carboxyl groups (i.e., the residual carboxyl group content) is less than 100%, which can be below 95%, below 90%, below 60%, below 40%, or below 20%. "Residual carboxyl group content" refers to the percentage (%) of carboxyl groups present in the structure of the modified natural product that have not been replaced by the modifying agent.

[0194] <Methods for forming ester bonds>

[0195] Use alcohol (R) 1 -OH) forms an ester bond with the carboxyl group of bio-based compounds.

[0196] Synthetic methods that convert the carboxyl groups of natural substances into ester groups include the following (solvents may be added as needed):

[0197] (a) Use of bio-based compounds, alcohols (R 1 Methods for forming ester bonds using acid catalysts (e.g., -OH) and acid catalysts;

[0198] (b) Use of bio-based compounds, alcohols (R 1 Methods for forming ester bonds using condensing agents (-OH) and condensing agents;

[0199] (c) After converting a bio-based compound into an acyl compound, using an alcohol (R 1 Methods for forming ester bonds with -OH).

[0200] In alcohol (R) 1 In -OH), R 1 The meaning is the same as above.

[0201] Specific examples of aliphatic alcohols include CH3OH, CH3CH2OH, CH3(CH2)2OH, CH3(CH2)3OH, CH3(CH2)4OH, CH3(CH2)5OH, CH3(CH2)6OH, CH3(CH2)7OH, CH3(CH2)8OH, CH3(CH2)9OH, and CH3(CH2)2OH. 10 OH, CH3(CH2) 11 OH, CH3(CH2) 12 OH, CH3(CH2) 13 OH, CH3(CH2) 14 OH, CH3(CH2) 15 OH, CH3(CH2) 16 OH, CH3(CH2) 17 OH, CH3(CH2) 18 OH, CH3(CH2) 19 OH, CH3(CH2) 20 OH, CH3(CH2) 21 OH, CH3(CH2) 22 OH, CH3(CH2) 23 OH, (CH3)2CHOH, (CH3)3COH, (CH3)2CHCH2OH, (CH3)3CCH2OH, (CH3)2CH(CH2)2OH, (CH3)3C(CH2) 14 OH, (CH3)2CH(CH2) 15 OH, (CH3)3C(CH2) 18 OH, (CH3)2CH(CH2) 18 OH.

[0202] <Methods for forming amide bonds>

[0203] This allows the carboxyl group of a bio-based compound to react and form an amide bond. The amide bond then allows the bio-based compound to react with an amine (R... 1 -NR 2 H), isocyanate (R) 1 -N=C=O) or isothiocyanate (R 1 It is formed by the reaction of -N=C=S.

[0204] Synthetic methods that convert the carboxyl group of a bio-based compound into an amide group include, for example, the following:

[0205] (a) Bio-based compounds, with amines (R 1 -NR 2 H), isocyanate (R) 1 -N=C=O) or isothiocyanate (R1 A method for forming amide bonds by mixing any of the following: -N=C=S;

[0206] (b) Use of bio-based compounds, and amines (R 1 -NR 2 H), isocyanate (R) 1 -N=C=O) or isothiocyanate (R 1 A method for forming amide bonds using any type of condensing agent in (N=C=S);

[0207] (c) Use of bio-based compounds, and amines (R 1 -NR 2 H), isocyanate (R) 1 -N=C=O) or isothiocyanate (R 1 Methods for forming amide bonds using any of the following metal catalysts (e.g., tin catalysts): -N=C=S;

[0208] (d) After converting the bio-based compound into an acyl compound, add an amine (R 1 -NR 2 H), isocyanate (R) 1 -N=C=O) or isothiocyanate (R 1 Any of the following methods for forming amide bonds (N=C=S)

[0209] In amine (R) 1 -NR 2 H), isocyanate isocyanate (R) 1 -N=C=O) and isothiocyanates (R 1 In (-N=C=S), R 1 The meaning is the same as above.

[0210] Specific examples of amines include CH3NH2, CH3CH2NH2, CH3(CH2)2NH2, CH3(CH2)3NH2, CH3(CH2)4NH2, CH3(CH2)5NH2, CH3(CH2)6NH2, CH3(CH2)7NH2, CH3(CH2)8NH2, CH3(CH2)9NH2, and CH3(CH2) 10 NH2, CH3(CH2) 11 NH2, CH3(CH2) 12 NH2, CH3(CH2) 13 NH2, CH3(CH2) 14 NH2, CH3(CH2) 15 NH2, CH3(CH2) 16 NH2, CH3(CH2) 17 NH2, CH3(CH2)18 NH2, CH3(CH2) 19 NH2, CH3(CH2) 20 NH2, CH3(CH2) 21 NH2, CH3(CH2) 22 NH2, CH3(CH2) 23 NH2, (CH3)2CHNH2, (CH3)3CNH2, (CH3)2CHCH2NH2, (CH3)3CCH2NH2, (CH3)2CH(CH2)2NH2, (CH3)3C(CH2) 14 NH2, (CH3)2CH(CH2) 15 NH2, (CH3)3C(CH2) 18 NH2, (CH3)2CH(CH2) 18 NH2.

[0211] Specific examples of isocyanates include CH3NCO, CH3CH2NCO, CH3(CH2)2NCO, CH3(CH2)3NCO, CH3(CH2)4NCO, CH3(CH2)5NCO, CH3(CH2)6NCO, CH3(CH2)7NCO, CH3(CH2)8NCO, CH3(CH2)9NCO, and CH3(CH2) 10 NCO, CH3(CH2) 11 NCO, CH3(CH2) 12 NCO, CH3(CH2) 13 NCO, CH3(CH2) 14 NCO, CH3(CH2) 15 NCO, CH3(CH2) 16 NCO, CH3(CH2) 17 NCO, CH3(CH2) 18 NCO, CH3(CH2) 19 NCO, CH3(CH2) 20 NCO, CH3(CH2) 21 NCO, CH3(CH2) 22 NCO, CH3(CH2) 23 NCO, (CH3)2CHNCO, (CH3)3CNCO, (CH3)2CHCH2NCO, (CH3)3CCH2NCO, (CH3)2CH(CH2)2NCO, (CH3)3C(CH2) 14 NCO, (CH3)2CH(CH2) 15 NCO, (CH3)3C(CH2) 18NCO, (CH3)2CH(CH2) 18 NCO.

[0212] Specific examples of isothiocyanates include CH3NCS, CH3CH2NCS, CH3(CH2)2NCS, CH3(CH2)3NCS, CH3(CH2)4NCS, CH3(CH2)5NCS, CH3(CH2)6NCS, CH3(CH2)7NCS, CH3(CH2)8NCS, CH3(CH2)9NCS, and CH3(CH2)2NCS. 10 NCS, CH3(CH2) 11 NCS, CH3(CH2) 12 NCO, CH3(CH2) 13 NCO, CH3(CH2) 14 NCO, CH3(CH2) 15 NCO, CH3(CH2) 16 NCS, CH3(CH2) 17 NCS, CH3(CH2) 18 NCS, CH3(CH2) 19 NCS, CH3(CH2) 20 NCS, CH3(CH2) 21 NCS, CH3(CH2) 22 NCS, CH3(CH2) 23 NCS, (CH3)2CHNCS, (CH3)3CNCS, (CH3)2CHCH2NCS, (CH3)3CCH2NCS, (CH3)2CH(CH2)2NCS, (CH3)3C(CH2) 14 NCS, (CH3)2CH(CH2) 15 NCS, (CH3)3C(CH2) 18 NCS, (CH3)2CH(CH2) 18 NCS.

[0213] R 21 Preferably, the substituent is an aliphatic hydrocarbon group having 1 to 40 carbon atoms. The number of carbon atoms is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more; preferably 35 or less, more preferably 30 or less, and even more preferably 25 or less.

[0214] In this invention, modified natural products modified with primary amines are preferred.

[0215] This invention provides a malic acid compound or a glutaric acid compound as a novel compound.

[0216] Malic acid compounds or glutaric acid compounds are compounds represented by the following formula:

[0217]

[0218] [In the formula, each R″ may be the same or different, and can be -OH or -NH-R.] 1 (R 1 (These can be hydrocarbon groups with 1 to 40 carbon atoms that can have substituents).

[0219] R′ is either hydrogen or acetyl.

[0220] It is possible to have only one R″ as -NH-R 1 However, it is preferable that both R″ are simultaneously -NH-R. 1 .

[0221] R 1 Preferably, it is a hydrocarbon group with 12 to 22 carbon atoms, and particularly preferably an alkyl group.

[0222] R′ is preferably an acetyl group.

[0223] Specific examples of malic acid compounds or glutaric acid compounds are as follows.

[0224]

[0225] <Oil-resistant agent>

[0226] Modified natural compounds, due to their oil resistance, can be used as "oil-resistant agents." Oil-resistant agents can be compositions containing modified natural compounds, or they can consist solely of modified natural compounds. Oil-resistant agents can further possess water resistance, water-repellent, and oil-repellent properties. In addition to containing modified natural compounds, oil-resistant agents may also contain a liquid medium (water, organic solvents, or mixtures thereof). Oil-resistant agents may also contain at least one crosslinking agent and additive selected from surfactants, dispersants, terminated isocyanate compounds, and other crosslinking agents.

[0227] The amount of modified natural substances relative to the oil-resistant agent can be 0.01% by weight or more, 0.1% by weight or more, 1% by weight or more, 10% by weight or more, 20% by weight or more, or 30% by weight or more. The amount of modified natural substances relative to the oil-resistant agent can be less than 100% by weight, less than 95% by weight, less than 90% by weight, or less than 80% by weight.

[0228] Oil-resistant agents may contain a liquid medium. The liquid medium may be water alone, an organic solvent alone, or a mixture of water and an organic solvent, preferably water alone.

[0229] Compared to oil-resistant agents, the amount of liquid medium can be 60% or more, 80% or more, or 90% or more, and the amount of liquid medium can be less than 100% by weight, specifically 99% or less, 95% or less, 90% or less, or 80% or less.

[0230] <Surfactant or dispersant>

[0231] Oil-resistant agents may or may not contain surfactants (emulsifiers) or dispersants.

[0232] Surfactants or dispersants can be added in small amounts (e.g., 0.01 to 100 parts by weight or 0.01 to 50 parts by weight relative to 100 parts by weight of the modified natural product, for example, 0.1 to 30 parts by weight) during or after the reaction. Generally, the stability of the aqueous dispersion is improved upon the addition of a surfactant or dispersant.

[0233] The surfactant preferably contains one or more surfactants selected from cationic surfactants, nonionic surfactants, anionic surfactants and amphoteric surfactants, and more preferably uses nonionic surfactants, cationic surfactants, or a combination of nonionic surfactants and cationic surfactants.

[0234] Nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants can each be one or a combination of two or more.

[0235] The amount of surfactant or dispersant added relative to 100 parts by weight of the modified natural product can be 0.01% by weight or more, 0.1% by weight or more, 1% by weight or more, 5% by weight or more, 10% by weight or more, 30% by weight or more, or 50% by weight or more, and can be less than 100% by weight, less than 95% by weight, less than 90% by weight, or less than 70% by weight. Generally, the stability of the aqueous dispersion is improved when surfactants or dispersants are added.

[0236] Examples of nonionic surfactants (emulsifiers) or dispersants include glycerol fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycol, fatty acid polyethylene glycol esters, polyoxyethylene sorbitan fatty acid esters, fatty acid alkanolamides, and polyethyleneimine ethoxylates.

[0237] Examples of cationic surfactants (emulsifiers) or dispersants include alkylamine salts and quaternary ammonium salts. Alkylamine salts include monoalkylamine salts, dialkylamine salts, and trialkylamine salts. Quaternary ammonium salts can be listed as trimethylammonium chloride, dialkyldimethylammonium chloride, and alkylbenzal-ammonium chloride.

[0238] Anionic surfactants (emulsifiers) or dispersants include carboxylates, sulfonates, sulfates, and phosphates. For example, aliphatic monocarboxylic acids and alkyl ether carboxylates can be listed as carboxylates; dialkyl sulfosuccinates, alkane sulfonates, alkylbenzene sulfonates, and alkylnaphthalene sulfonates can be listed as sulfonates; alkyl sulfates and oil sulfates can be listed as sulfates; and alkyl phosphates and polyoxyethylene alkyl ether phosphates can be listed as phosphates.

[0239] Examples of amphoteric surfactants (emulsifiers) or dispersants include alkyl betaine, fatty acid amyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazoline onion salt, alkyl diethylenetriaminoacetic acid, dialkyl diethylenetriaminoacetic acid, and alkylamine oxides.

[0240] Heating can be performed when adding surfactants (emulsifiers) or dispersants during or after the reaction of modifying natural substances. After adding the modified natural substance and dispersant, heating can be used to dissolve and disperse them, or a solution (preferably water) can be added while heating to disperse or dissolve them. The heating temperature can be above 40°C, above 60°C, or above 80°C.

[0241] Oil-resistant agents may or may not contain end-capped isocyanate compounds. End-capped isocyanate compounds can be added before the carboxyl group substitution reaction or after the reaction (e.g., before the curing process).

[0242] As the end-capped isocyanate compound, preferred end-capped isocyanates include oxime-terminated toluene diisocyanate, end-capped hexamethylene diisocyanate, and end-capped diphenylmethane diisocyanate.

[0243] The amount of the capped isocyanate compound relative to 100 parts by weight of the modified natural product can be less than 15 parts by weight, less than 10 parts by weight, less than 7.5 parts by weight, less than 5 parts by weight, or less than 2.5 parts by weight.

[0244] Oil-resistant agents may contain additives. Examples of additives include adhesive resins, dispersants, water-resistant agents, oil-resistant agents, water-repellent agents, oil-repellent agents, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, defoamers, hand feel modifiers, slip properties modifiers, antistatic agents, hydrophilic agents, antibacterial agents, preservatives, insect repellents, fragrances, flame retardants, retention aids, sizing agents, paper strength enhancers, and fillers.

[0245] Examples of retention aids include aluminum sulfate, acrylic polymers, starch, modified starch, cellulose, modified cellulose, and silica.

[0246] Examples of sizing agents include rosin-based sizing agents, alkyl ketone dimers (AKD), alkenyl succinic anhydride (ASA), polyvinyl alcohol (PVA), modified starch, styrene / acrylic acid copolymers, and styrene / methacrylic acid copolymers.

[0247] Examples of pH adjusters include lactic acid, carbon dioxide, succinic acid, gluconic acid, citric acid, trisodium citrate, phosphoric acid, potassium carbonate, and sodium bicarbonate.

[0248] Examples of fillers include talc, kaolin, calcium carbonate, titanium dioxide, and barium sulfate.

[0249] Examples of paper strength enhancers include urea-formaldehyde resin, melamine-formaldehyde resin, polyamide-polyamine-epoxychloropropane (PAE), polyvinylamine (PVAm), modified starch and polyacrylamide, polyvinyl alcohol, etc.

[0250] The amount of additive is greater than 0 relative to 100 parts by weight of the modified natural substance, preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, and less than 100 parts by weight, more preferably 80 parts by weight or less, and more preferably 50 parts by weight or less.

[0251] <Properties of oil-resistant and modified natural products>

[0252] The melting point of the functional group (side chain) in the modified natural product is preferably above 0°C or has no melting point, and more preferably above 20°C, 40°C, or 60°C. Furthermore, the melting point of the functional group (side chain) is preferably below 180°C, 140°C, or 120°C. A melting point within the above range improves temperature resistance, and is particularly preferred from the viewpoint of high-temperature oil resistance. The functional group (side chain) in the modified natural product refers to the R-group of the modified natural product, particularly a hydrocarbon group with 1 to 40 carbon atoms. The melting point of the functional group (side chain) in the modified natural product is the temperature at which the arrangement of the R-groups of the modified natural product disintegrates when the solid of the modified natural product is heated from a low temperature; it can be considered the glass transition temperature of the modified natural product.

[0253] Regarding the oil-resistant agent, the contact angle (on the glass substrate) of n-hexadecane can be 5° or more, 10° or more, or 15° or more, preferably 20° or more, 25° or more, more preferably 30° or more, and most preferably 35° or more, or 40° or more. With the contact angle of n-hexadecane within the above range, the oil-resistant agent exhibits excellent liquid-repellent properties, which is particularly preferred from the viewpoint of oil resistance.

[0254] The melting point of the modified natural substance is preferably above 20°C, more preferably above 40°C, further preferably above 60°C, and most preferably above 80°C. Furthermore, the melting point of the oil-resistant agent is preferably below 200°C, below 180°C, or below 160°C.

[0255] By ensuring that the melting point of the oil-resistant agent is within the aforementioned range, the coverage and temperature resistance of the fiber product are improved when it is treated, which is particularly preferred from the viewpoint of high-temperature oil resistance.

[0256] The glass transition temperature of the modified natural material is preferably 0°C or higher or has no glass transition temperature, more preferably 20°C or higher or has no glass transition temperature, further preferably 40°C or higher or has no glass transition temperature, and most preferably 60°C or higher or has no glass transition temperature. Furthermore, the glass transition temperature of the oil-resistant agent is preferably 180°C or lower, 140°C or lower, or 120°C or lower. Having the glass transition temperature of the oil-resistant agent within the above range improves the coverage and temperature resistance of the fiber product during treatment, which is particularly preferable from the viewpoint of oil resistance.

[0257] The viscosity of the oil-resistant agent (solution or dispersion) with a natural product concentration of 14.8 mg / mL is preferably 3 cP or more, 5 cP or more, 7 cP or more, or 10 cP or more. Furthermore, the viscosity of the oil-resistant agent (solution or dispersion) with a natural product concentration of 14.8 mg / mL is preferably 1000 cP or less, 500 cP or less, or 100 cP or less. Having the viscosity of the solution (or dispersion) within the above range improves the coverage of the fiber product during treatment, which is particularly preferable from the viewpoint of oil resistance.

[0258] Using a Baker-type coating machine set to 0 mil, an oil-resistant agent (solution or dispersion) with a natural product concentration of 14.8 mg / mL was applied to paper with a density of 0.58 g / cm³. 3 The unit area weight is 45g / m² 2 The paper is repeatedly dried on the base paper, and this operation is repeated three times. Then, it is annealed at a temperature of 70°C to 100°C for 10 minutes. The air permeability of the resulting treated paper is preferably below 10000s / 100cc, more preferably below 5000s / 100cc, even more preferably below 3000s / 100cc, and most preferably below 1000s / 100cc.

[0259] The preferred range of combinations of contact angle and melting point of hexadecane in oil-resistant agents (hexadecane contact angle × melting point) can be 5° or more × 0° or more, 10° or more × 20° or more, 20° or more × 40° or more, or 30° or more × 60° or more.

[0260] <Applications of Oil-Resistant Agents>

[0261] Oil-resistant agents can also be used as water-resistant agents, water-repellent agents, oil-repellent agents, anti-fouling agents, stain removers, release agents, or mold release agents, etc., in various formulations or as components thereof.

[0262] Oil-resistant agents can be used as external treatment agents (surface treatment agents) or internal treatment agents, or as components thereof.

[0263] By treating the substrate with an oil-resistant agent, the modified natural material can form a surface coating structure on the substrate surface.

[0264] Surface coating structures are formed by applying oil-resistant agents to the substrate using known methods, allowing them to adhere to the substrate surface. Common methods include: dispersing the modified natural agent in an organic solvent or water for dilution, applying it to the surface of the substrate using known methods such as dip coating, spraying, or foam coating, and then drying. It can also be applied and cured together with a suitable crosslinking agent (e.g., a capped isocyanate compound), as needed. Additionally, insect repellents, softeners, antibacterial agents, flame retardants, antistatic agents, paint fixatives, wrinkle-resistant agents, sizing agents, paper strength enhancers, etc., can be added and used in combination with the modified natural agent.

[0265] Examples of materials that can be treated with oil-resistant agents include fiber products, stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, coated surfaces, and gypsum.

[0266] As a fiber product, various examples can be listed, such as cloth products or paper products.

[0267] Examples of textile products include natural plant and animal fibers such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber; or blends thereof. Textile products include woven fabrics, knitted fabrics, and nonwoven fabrics, as well as clothing fabrics and carpets. However, they can also be made from fibers, yarns, and intermediate fiber products (such as cotton slivers or rovings) in their state before being made into fabric.

[0268] Examples of paper products include paper made from bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp, high-yield pulps such as wood pulp, mechanical pulp or thermomechanical pulp, old newspapers, old magazines, old corrugated paper or deinked old paper, containers made of paper, and molded bodies made of paper. Specific examples of paper products include food packaging paper, gypsum board base paper, coated base paper, medium-quality paper, ordinary liner paper and core paper, neutral pure white roll paper, neutral liner paper, rust-proof liner paper and metal composite 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, and molded paper (molded containers). The modified natural materials of this invention have excellent oil resistance (e.g., high-temperature oil resistance), making them suitable for applications requiring oil resistance, and particularly suitable for food packaging materials and food containers.

[0269] Oil-resistant agents can be applied to fibrous substrates (e.g., fibrous products, pulp, and other fibrous raw materials) using any known method for treating fibrous products with liquids. A fibrous substrate refers to both the fibrous product and the fibrous raw material. When the fibrous product is cloth, the cloth can be immersed in the solution (or dispersion), or the solution (or dispersion) can be adhered to or sprayed onto the cloth. The treatment can be either external or internal. When the fibrous product is paper, the agent can be coated onto the paper, or the solution (or dispersion) can be adhered to or sprayed onto the paper, or it can be mixed with pulp before papermaking. The treatment can also be either external or internal.

[0270] Oil-resistant agents can be applied to pre-formed fibrous products (especially paper, cloth, etc.), or they can be applied at various stages of papermaking, such as during the paper drying process.

[0271] Alternatively, the fibrous substrate can also be leather. To make the leather hydrophobic and oleophobic, an oil-resistant agent can be applied to the leather using an aqueous solution or an aqueous emulsion at various stages of leather processing, such as during the wetting process or during the finishing process.

[0272] Oil-resistant agents can also be used as external release agents. For example, they can easily peel the surface of a substrate from other surfaces (other surfaces of the substrate, or the surface of other substrates).

[0273] <Processing>

[0274] "Treatment" refers to the application of an oil-resistant agent (treatment agent) to a workpiece through methods such as impregnation, spraying, or coating. Through treatment, the modifying natural substances, which are the active ingredients of the oil-resistant agent, penetrate into the interior of the workpiece and / or adhere to its surface.

[0275] To exhibit oil resistance, the treated material (substrate) is preferably dried, preferably heated to a temperature above the glass transition temperature (Tg) of the modified natural material, for example, above 40°C, above 60°C, above 80°C, and below 250°C and below 200°C. Treatment at a temperature above the Tg of the modified natural material may sometimes induce the alignment of side chains. A temperature above the melting point (Tm) is further preferred. By treating at a temperature above the Tm of the modified natural material, the substrate surface is covered with the modified natural material. This allows the formation of a surface coating structure with excellent hydrophobicity.

[0276] When the oil-resistant agent is treated in a liquid state, in order to improve the desolventization (dehydration) properties or the adhesion between the modified natural material and the substrate, the treated fibrous substrate may be pressurized at a pressure greater than 0.1 MPa, preferably 0.15 MPa or more, and even more preferably 0.2 MPa or more.

[0277] <Paper Additives>

[0278] Oil-resistant agents are particularly suitable for paper additives. Paper additives containing oil-resistant agents can function not only as oil-resistant agents but also as water-resistant agents, water-repellent agents, and / or oil-repellent agents. Paper additives are preferably in the form of solutions, emulsions, or aerosols. Paper additives may contain modified natural substances and media (e.g., organic solvents and liquid media such as water), preferably aqueous dispersions of modified natural substances. The concentration of modified natural substances in paper additives can, for example, be from 0.01 to 50% by weight. Paper additives may be surfactant-free.

[0279] The removal of solutions (organic solvents, water) contained in paper additives can be achieved by heating the modified natural product solution (dispersion) at temperatures above 40°C, above 60°C, above 80°C, and below 250°C, below 200°C.

[0280] Paper additives can be used to treat paper substrates (e.g., surface treatment). Paper additives can be applied to the treated object using currently known methods. Typically, the following methods can be used: dispersing the paper additive in an organic solvent or water for dilution, then applying it to the surface of the treated object using known methods such as dip coating, spraying, or foam coating, and finally drying it (surface treatment). Examples of paper substrates that can be treated include paper, containers made of paper, and molded articles made of paper (e.g., molded pulp articles). The modified natural material of the present invention adheres well to the paper substrate. Here, adhesion refers to physical or chemical bonding. By adhering the modified natural material to the paper substrate, oil-resistant paper can be obtained.

[0281] The implementation methods have been described above, but it should be understood that various changes can be made to the implementation methods and details without departing from the spirit and scope of the claims of this invention.

[0282] Example

[0283] The present invention will now be specifically described by way of examples. However, these descriptions do not limit the present invention. Unless otherwise specified, parts, % or ratios refer to parts by weight, weight % or weight ratio.

[0284] The experimental methods used below are as follows.

[0285] Paper processing

[0286] As wood pulp, a pulp stock was prepared with LBKP (broadleaf bleached kraft pulp) and NBKP (coniferous bleached kraft pulp) at a weight ratio of 60 wt% and 40 wt% respectively, and a pulp water content of 400 ml (Canadian Standard Freeness). Wetting agent and sizing agent were added to this pulp stock, and the paper was processed using a fourdrinier paper machine to achieve a paper density of 0.58 g / cm³. 3 The unit area weight is 45g / m² 2 This paper is used as the base paper for external processing (sizing). The base paper has an oil resistance (KIT value) of 0 and a water resistance (Cobb value) of 52 g / m³. 2 .

[0287] As emulsifiers and dispersants, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycols, alkylamine salts, quaternary ammonium salts, carboxylates, polyethyleneimine ethoxylates, or similar compounds thereof are used.

[0288] When using organic solvents to prepare modified natural product solutions (or dispersions), for base paper, using a Becker coater with a gap set to 0 mil, a coating density of 14.9 mg / cm² is achieved. 3 The modified natural product solution (or dispersion) (using chloroform, toluene or acetone as solvent) is repeatedly dried, and this operation is repeated three times, followed by annealing at 70°C for 10 minutes, thereby producing treated paper.

[0289] When using water to prepare an aqueous solution (or dispersion) of the modified natural product, for the base paper, a 1 wt% aqueous solution (or dispersion) of the modified natural product is coated using a Becker coater with the gap set to 0 mil, and dried repeatedly. This operation is repeated three times, and the paper is then annealed at 100°C for 10 minutes to produce the treated paper.

[0290] KIT test (oil resistance)

[0291] The test was conducted using a 3M KIT tester (TAPPI T-559cm-02). In the 3M KIT test method, a test oil containing castor oil, toluene, and heptane was placed on the surface of the treated paper. After 15 seconds, the test oil was wiped off, and the evaluation was based on whether the oil had penetrated into the treated paper. Test oils numbered 1 to 6 were used, and the KIT number with the highest observed no penetration was taken as the evaluation result for oil resistance.

[0292] Evaluation of corn oil resistance (oil resistance)

[0293] Place corn oil on the surface of the treatment paper, wipe off the oil after 15 seconds, and evaluate whether the oil has penetrated the treatment paper. Record "○" for no penetration and "×" for observed penetration.

[0294] Liquid repellency (static contact angle)

[0295] Regarding liquid repellency, a 1.0% solids solution (or dispersion) of the modified natural ingredient was spin-coated onto a glass substrate coated with a cellulosic film, and the static contact angle was measured. The static contact angle was obtained by adding 2 μL of hexadecane (HD) to the coating and measuring the contact angle after 1 second.

[0296] Breathability

[0297] The air permeability (air resistance) of the treated paper was measured using an automatic Galley electric tester (product No. 323-AUTO, vent diameter 28.6±0.1mm) manufactured by Yasuda Seiki Co., Ltd., in accordance with JIS P8117 (2009).

[0298] Melting point

[0299] Melting points were determined using a differential scanning calorimeter. The temperature of the peak with the largest endothermic reaction was taken as the melting point of the modified natural product, and the temperature of the second largest endothermic peak was taken as the melting point of the functional groups (side chains) in the modified natural product.

[0300] Molding

[0301] An automatic molding machine is used to form molded articles. A mesh is placed on a metal pulp molding die with multiple suction holes at the bottom, and a metal trough is placed at the top. Pulp is added to the upper metal trough. From the side of the pulp molding die opposite to the side with the mesh, a vacuum pump is used to suction and dehydrate the aqueous composition containing pulp at 0.1–1 MPa through the pulp molding die and the mesh, causing the solid components (pulp, etc.) contained in the aqueous composition to accumulate on the mesh, resulting in a pulp molding intermediate. Next, using metal male and female molding dies heated to 60–200°C, the obtained pulp molding intermediate is dried from both top and bottom at a pressure of 0.1–1 MPa. This produces a pulp molding article molded into a container shape.

[0302] Practical oil resistance test

[0303] Inject 100 ml of corn oil at 65°C into the molded part. After standing at room temperature for 45 minutes, evaluate the degree of oil penetration. Based on the degree of penetration, set the evaluation values ​​as described below.

[0304] 5: No seepage on the inside.

[0305] 4: There is seepage on the inside, but no seepage on the back side.

[0306] 3: There is seepage on the inside and a small amount of seepage on the back side.

[0307] 2: There is seepage on the inside, and the seepage to the back is less than 50% of the area.

[0308] 1: There is seepage on the inside, and the seepage to the back is more than 50% but less than 100% of the area.

[0309] 0: Seep out to the entire back side.

[0310] Practical water resistance test

[0311] Pour 100ml of water at 100°C into the molded part, and after leaving it at room temperature for 30 minutes, evaluate the degree of penetration. Based on the degree of penetration, set the evaluation values ​​as described below.

[0312] 5: No seepage on the inside.

[0313] 4: There is seepage on the inside, but no seepage on the back side.

[0314] 3: There is seepage on the inside and a small amount of seepage on the back side.

[0315] 2: There is seepage on the inside, and the seepage to the back is less than 50% of the area.

[0316] 1: There is seepage on the inside, and the seepage to the back is more than 50% but less than 100% of the area.

[0317] 0: Seep out to the entire back side.

[0318] Example 1

[0319] A stir bar, 2.8 g of citric acid, and 13 g of octadecylamine were added to a reaction vessel equipped with a reflux condenser and a Dean-Stark apparatus. The mixture was heated to 70°C, and 20 ml of toluene was added. The mixture was heated and stirred at 135°C for 64 hours. The reaction vessel was cooled to room temperature, and another 20 ml of toluene was added. The mixture was washed with acetone and ethanol in that order to obtain the modified natural compound. The bio-based content of the obtained modified natural compound was 100%. Furthermore, the melting point of the modified natural compound and the preparation of a 14.9 mg / cm³ solution containing the modified natural compound were determined. 3 The results of the KIT test, corn oil resistance, liquid repellency, and air permeability evaluation of the chloroform solution are shown in Table 1.

[0320] Example 2

[0321] A stir bar, 1.9 g of citric acid, 11 g of stearyl alcohol, and 15 ml of toluene were added to a reaction vessel equipped with a reflux condenser and a Dean-Stark apparatus. While stirring, 0.2 g of sulfuric acid was added dropwise. The temperature was slowly raised to 140 °C and maintained at 140 °C with stirring for 3 hours. After cooling to room temperature, 30 ml of chloroform was added, heated to dissolve, and then washed with ethanol to obtain the modified natural product. The bio-based content of the obtained modified natural product was 100%. Furthermore, the melting point of the modified natural product and the preparation of a product containing 14.9 mg / cm³ of the modified natural product were determined. 3 The results of the KIT test, corn oil resistance, liquid repellency, and air permeability evaluation of the chloroform solution are shown in Table 1.

[0322] Comparative Example 1

[0323] As an oil-resistant agent, cellulose (20 μm powder) was used to evaluate KIT test, corn oil resistance, liquid repellency, and air permeability. The results are shown in Table 1.

[0324] Table 1

[0325] KIT (score) corn oil Static contact angle (°) Melting point (°C) Breathability (s / 100cc) Example 1 4 ○ 46.5 100 231.7 Example 2 4 ○ 41.1 60 229.3 Comparative Example 1 0 × — — 255

[0326] Example 3

[0327] Add 30 mg of the modified natural compound obtained in Example 1, 30 mg of sodium oleate, and 0.3 g of water. After heating at 100°C, add hot water to bring the modified natural compound to 1 wt%. Heat to 90°C and disperse using an ultrasonic homogenizer to prepare a dispersion. Use this dispersion to evaluate the KIT test, corn oil resistance, and air permeability. The results are shown in Table 2.

[0328] Table 2

[0329] KIT (score) corn oil Breathability (s / 100cc) Example 3 5 ○ 632.5 Comparative Example 1 0 × 255

[0330] Example 4

[0331] Add 500 mg of the modified natural product obtained in Example 1 and 500 mg of emulsifier (polyoxyethylene oleyl ether), heat at 110°C, add hot water to make the modified natural product reach 1 wt%, heat to 90°C, and disperse using a mechanical shear homogenizer to obtain a dispersion.

[0332] Example 5

[0333] Except for changing the emulsifier to sodium oleate, the same procedure as described in Example 4 was followed to obtain the dispersion.

[0334] Examples 6-9

[0335] 1300 ml of water was added to 700 g of a 1.4 wt% aqueous dispersion of a mixture of 70 parts hardwood bleached kraft pulp and 30 parts softwood bleached kraft pulp, which was pulped to a filterability of 550 cc (Canadian freeness). While stirring, the aqueous dispersion of the modified natural ingredients obtained in Examples 4 and 5 was added, so that the concentration of modified natural ingredients per unit weight of pulp, expressed as solids, was as recorded in Table 3, thus preparing the pulp stock.

[0336] Molding

[0337] The pulp materials from Examples 6-9 were placed in an automatic molding tester and pressed at a pressure of 0.3 MPa and a temperature of 80°C for 10 seconds, followed by pressing at a pressure of 0.3 MPa and a temperature of 180°C for 60 seconds, thereby producing pulp molded articles weighing approximately 10 g. Practical oil resistance and practical water resistance tests were conducted on the obtained pulp molded articles. The results are shown in Table 3.

[0338] Comparative Example 2

[0339] 1300 ml of water was added to 700 g of a 1.4 wt% aqueous dispersion of a mixture of 70 parts hardwood bleached kraft pulp and 30 parts softwood bleached kraft pulp with a filterability of 550 cc (Canadian freeness). The resulting pulp was then fed into an automatic molding tester and pressed at 0.3 MPa and 80°C for 10 seconds, followed by pressing at 0.3 MPa and 180°C for 60 seconds, thus producing a pulp molded product weighing approximately 10 g. Practical oil resistance and practical water resistance tests were conducted on the obtained pulp molded product. The results are shown in Table 3.

[0340] Table 3

[0341]

[0342] Example 10

[0343] Add 100 mg of the modified natural compound obtained in Example 1, 10 mg of polyoxyethylene trimethyl nonyl ether, and 300 mg of isopropanol. When heated to 85°C, the modified natural compound dissolves. After adding hot water to bring the modified natural compound content to 1 wt%, the mixture is pulverized three times at 245 MPa using a Star Burst Mini (model HJP-25001) manufactured by Sugino Machine Co., Ltd., to obtain a dispersion.

[0344] Examples 11-15

[0345] Except for replacing the polyoxyethylene trimethyl nonyl ether with the emulsifiers or dispersants listed in Table 4, the same procedure as described in Example 10 was followed to obtain the dispersion.

[0346] Table 4

[0347] Emulsifiers (dispersants) Example 10 Polyoxyethylene trimethyl nonyl ether Example 11 Polyoxyethylene polyoxybutylene alkyl ether Example 12 Polyoxyethylene polyoxypropylene alkyl ether Example 13 Polyoxyethylene butyl ether Example 14 Polyoxyethylene polyoxypropylene-2-ethylhexyl ether Example 15 Polyoxyethylene polyoxypropylene glycol

[0348] Examples 16-18

[0349] Except for changing the concentration of the modified natural substance to 10 wt%, changing the number of pulverizations to 1, and changing the emulsifier or dispersant as shown in Table 5, the method was operated in the same manner as described in Examples 10-15 to obtain the dispersion. The dispersibility was improved compared to the case where the concentration of the modified natural substance was 1 wt%.

[0350] Molding

[0351] 1300 ml of water was added to 700 g of a 1.4% by weight aqueous dispersion of a mixture of 70 parts of bleached hardwood kraft pulp and 30 parts of bleached softwood kraft pulp with a filterability of 550 cc (Canadian freeness). While stirring, the aqueous dispersions of modified natural materials obtained in Examples 16-18 were added to prepare a pulp stock with a modified natural material concentration of 2.5% per unit weight of pulp. This pulp stock was then placed in an automatic molding tester and pressed at 0.3 MPa and 80°C for 10 seconds, followed by pressing at 0.3 MPa and 180°C for 60 seconds, thereby producing a pulp molded product weighing approximately 10 g. A practical oil resistance test was conducted on the obtained pulp molded product. The results are shown in Table 5.

[0352] Table 5

[0353]

[0354] Example 19

[0355] Add 17.8g of water to 200mg of emulsifier A (polyoxyethylene polyoxypropylene alkyl ether) to prepare an aqueous emulsifier solution (dispersion). Then add 2g of the modified natural product obtained in Example 1 and stir. The mixture is then pulverized three times at 245MPa using a Star Burst Mini to obtain the dispersion.

[0356] Example 20

[0357] Add 17.8g of water to 10mg of emulsifier A (polyoxyethylene polyoxypropylene alkyl ether) and 53mg of emulsifier B (dihydroxyethyl alkyl methyl ammonium chloride) to prepare an aqueous emulsifier solution (dispersion). Then add 2g of the modified natural product obtained in Example 1 and stir. The mixture is then pulverized three times at 245MPa using a Star Burst Mini to obtain the dispersion.

[0358] Examples 21-28

[0359] Except for the changes to emulsifier B and additives as described in Table 6, the same operation as described in Example 20 was performed to obtain the dispersion.

[0360] Molding

[0361] 1300 ml of water was added to 700 g of a 1.4 wt% aqueous dispersion of a mixture of 70 parts of bleached hardwood kraft pulp and 30 parts of bleached softwood kraft pulp with a filterability of 550 cc (Canadian freeness). While stirring, the aqueous dispersions of modified natural materials obtained in Examples 21-28 were added to prepare a pulp stock with a natural material content of 2.5% by weight per unit pulp weight, based on solids concentration. This pulp stock was then placed in an automatic molding tester and pressed at 0.3 MPa and 80°C for 10 seconds, followed by pressing at 0.3 MPa and 180°C for 60 seconds, thereby producing a pulp molded article weighing approximately 10 g. A practical oil resistance test was conducted on the obtained pulp molded article. The results are shown in Table 6.

[0362] Table 6

[0363]

[0364] Example 29

[0365] 3.24 g of dimethyl 3-hydroxyglutarate was dissolved in 20.0 mL of dehydrated toluene, and then 2.91 g of stearylamine was added. The mixture was stirred overnight at 132 °C in an oil bath. The next day, after cooling to room temperature, 30 mL of methanol was added, and the reaction solution was filtered. The solid was dried to obtain 2.75 g of compound A.

[0366] (Compound A)

[0367]

[0368] 1 H NMR (CDCl3, 400MHz) δ: 0.87 (t, 3H), 1.10-1.50 (m, 32H), 2.30-2, 42 (m, 2H), 2 .45-2.54(m,2H),3.20-3.24(m,2H),3.73(s,3H),4.34-4.45(m,1H),5.99(br s,1H).

[0369] Prepared at 14.9 mg / cm 3 A chloroform solution containing compound A was used to evaluate the KIT test and corn oil resistance. The results are shown in Table 7.

[0370] Example 30

[0371] 0.15 g of D,L-malic acid was dissolved in 10.0 mL of acetyl chloride, and the mixture was stirred in an oil bath at 60 °C for 5 hours. After 5 hours, the mixture was concentrated and dried to obtain 0.18 g of the intermediate compound.

[0372] (Intermediate compound)

[0373]

[0374] 1 H NMR (CDCl3, 400MHz) δ: 2.21 (s, 3H), 3.39 (dd, 1H), 3.03 (dd, 1H), 5.52 (dd, 1H).

[0375] 0.18 g of the above intermediate compound was dissolved in 20.0 mL of dehydrated dichloromethane, and 0.46 g of stearylamine was added. The mixture was stirred overnight at an oil bath temperature of 40°C. The next day, after concentration and drying, the compound was suspended in 6 mL of dichloromethane, filtered, and dried to obtain 0.41 g of compound B.

[0376] (Compound B)

[0377]

[0378] [In the formula, Ac represents an acetyl group.]

[0379] 1 H NMR (CDCl3, 400MHz) δ: 0.87 (t, 3H), 1.10-1.50 (m, 32H), 2.16 (s, 3H), 2.89 - 3.03 (m, 2H), 3.20 - 3.30 (m, 2H), 5.45 (t, 1H), 6.25 (br s, 1H).

[0380] 0.41 g of compound B was dissolved in 15.0 mL of dehydrated chloroform and placed in an ice bath. After stirring for 5 minutes, stearylamine (0.334 g), 4,4-dimethylaminopyridine (11.7 mg), and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (0.22 g) were added in that order. The reaction solution was stirred overnight and then concentrated to dryness. The residue was then washed with 20 mL of water and 20 mL of methanol in that order, filtered, and dried to obtain 0.43 g of compound C.

[0381] (Compound C)

[0382]

[0383] [In the formula, Ac represents an acetyl group.]

[0384] 1 H NMR (CDCl3, 400MHz) δ: 0.87 (t, 3H), 1.10-1.50 (m, 64H), 2.13 (s, 3H), 2.70-2.83 (m, 2H), 3.10-3.27 (m, 4H), 5.42 (br s, 1H).

[0385] Prepared at 14.9 mg / cm 3 A chloroform solution containing compound C was used to evaluate the KIT test and corn oil resistance. The results are shown in Table 7.

[0386] Example 31

[0387] (Compound D)

[0388]

[0389] [In the formula, Boc represents tert-butoxycarbonyl.]

[0390] Prepared at 14.9 mg / cm 3 A chloroform solution containing compound D was used to evaluate the KIT test and corn oil resistance. The results are shown in Table 7.

[0391] Table 7

[0392] KIT (score) corn oil Example 29 4 ○ Example 30 4 ○ Example 31 4 ○

[0393] Industrial availability

[0394] The bio-based compounds of this invention, when modified with natural ingredients, can be used as oil-resistant agents, as well as water-resistant agents, water-repellent agents, oil-repellent agents, antifouling agents, detergents, release agents, or mold release agents. These modified natural ingredients are suitable for applications requiring oil resistance, and are particularly suitable for food applications such as food packaging materials and food containers.

Claims

1. An application of a modified natural product in the preparation of an oil-resistant agent, characterized in that: The modified natural product is a bio-based compound having at least one carboxyl group in which the hydroxyl group of the carboxyl group is replaced by an R group, or in which the carboxyl group is replaced by an Ra group. The bio-based content of the modified natural products is above 30%. R-base: -X-R 1 Or -X-D-X′-R 1 Ra-base: In the formula, X represents valence bond, -O-, -NR. 11 - or -S-, R 1 It can be a hydrocarbon group with 4 to 40 carbon atoms that can have substituents. R 1 The substituents that may be present are at least one selected from hydroxyl, carboxyl, alkoxy ester, alkoxy, (Rc)3Si, (RcO)3Si, amino, and amine salts, wherein each Rc may be the same or different, and is a hydrogen atom or an alkyl group having C1 to C4 carbon atoms. D is an alkylene group having 1 to 10 carbon atoms. X' is -C(=O)-O-, -O-C(=O)-, -C(=O)-NR 12 - or - NR 12 -C(=O)-, Among them, R 11 and R 12 It is hydrogen or an alkyl group having 1 to 40 carbon atoms that may have substituents.

2. The application as described in claim 1, characterized in that: The carboxyl groups of modified natural substances have a salt structure.

3. The application as described in claim 1, characterized in that: Bio-based compounds have hydroxyl groups.

4. The application as described in claim 1, characterized in that: In bio-based compounds, the hydrogen atoms of the hydroxyl groups are replaced by Rb groups. Rb group: -Y-R 21 In the formula, Y represents the valence bond, -C(=O)-, -C(=O)-NR. 22 - or C = S-, where R 22 It can be hydrogen, or a hydrocarbon group having 1 to 22 carbon atoms that may have substituents. R 21 It can be a hydrocarbon group with 1 to 40 carbon atoms that can have substituents, or a polysiloxane.

5. The application as described in claim 1, characterized in that: The bio-based compound is selected from at least one of citric acid, malic acid, gluconic acid, alginic acid, butyric acid, lactic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, chlorogenic acid, aldonic acid, uronic acid, aldonic acid and their derivatives.

6. The application as described in claim 1, characterized in that: Bio-based compounds are compounds represented by the following formula: In the formula, each E 1 Whether they are the same or different, they are hydrogen or -COOH. Each E 2 The same or different, either hydrogen or -OH, E 3 -COOE 4 -CH3, -NH2 or -OH, where E 4 It is a hydrogen or an alkyl group having 1 to 22 carbon atoms. m is a number between 0 and 10.

7. The application as described in claim 1, characterized in that: Bio-based compounds have two or more carboxyl groups.

8. The application as described in claim 1, characterized in that: R 1 It can be an aliphatic hydrocarbon group that has substituents.

9. The application as described in claim 1, characterized in that: The oil-resistant agent is a water-dispersible composition.

10. The application as described in claim 1, characterized in that: The oil-resistant agent contains an emulsifier or a dispersant.

11. The application as described in claim 1, characterized in that: The oil-resistant agent contains an emulsifier or dispersant, which is a cationic, nonionic, and / or anionic emulsifier or dispersant.

12. The application as described in claim 1, characterized in that: The oil-resistant agent contains at least one of the following: a self-retention agent, a sizing agent, a pH adjuster, a filler, and a paper strength enhancer.

13. The application as described in claim 1, characterized in that: The melting point of the oil-resistant agent is above 25°C.

14. The application as described in claim 1, characterized in that: The HD contact angle of the oil-resistant agent is greater than 10°.

15. The application as described in claim 1, characterized in that: The oil-resistant agent is a paper-grade oil-resistant agent.

16. A fiber product, characterized in that: It contains the oil-resistant agent as described in any one of claims 1 to 15.

17. An oil-resistant paper, characterized in that: It contains the oil-resistant agent as described in any one of claims 1 to 15.

18. A food packaging material or food container, characterized in that: It contains the oil-resistant agent as described in any one of claims 1 to 15.

19. A processing method, characterized in that: The paper is treated with the oil-resistant agent according to any one of claims 1 to 15, either externally or internally.

Images