Non-stick packaging material as well as preparation method and application thereof

Abstract

The invention provides a non-stick packaging material as well as a preparation method and application thereof. The palm wax modified inorganic nanoparticles used in the non-stick packaging material can be prepared by the steps of contacting inorganic nanoparticles with a dispersing agent and palm wax dissolved in an organic solvent in an organic solvent environment, and then carrying out solid-liquid separation and drying; wherein the weight ratio of the inorganic nanoparticles to the palm wax to the dispersing agent is 1: (2.5-3.8): (0.05-0.08). The non-stick packaging material is a hydrophobic film and comprises the following raw material components in parts by weight: 32-48 parts of palm wax modified inorganic nanoparticles, 50-60 parts of a modifier and 28-34 parts of bio-based organic resin, wherein the modifier comprises long-chain silane and stearic acid in a weight ratio of (10-15): (2-4). The non-stick packaging material can be used as a yoghourt packaging material, and has a good persistent non-stick yoghourt effect.

Description

Technical Field

[0001] The invention belongs to the technical field of packaging materials, and specifically relates to a non-stick packaging material suitable for yogurt packaging materials, a preparation method and application thereof, and palm wax-modified inorganic nanoparticles and a coating liquid that can be used for the non-stick packaging material. Background Art

[0002] Yogurt is one of the most common foods in life, and is widely loved by the public for its good taste and high nutritional value. However, the yogurt packaging materials currently on the market generally have the problem of yogurt sticking. There is usually a layer of yogurt stuck inside the yogurt box and on the yogurt packaging cover film. In order to avoid waste, many people have the habit of licking it, which is not only unhygienic and unsightly, but also brings troubles to consumers.

[0003] In order to solve the above problems, a layer of hydrophobic coating is often applied on the surface of yogurt packaging materials to improve the hydrophobic properties of the surface of the yogurt packaging materials and reduce the adhesion of yogurt. However, when the hydrophobic coatings commonly used in the market are used for yogurt packaging materials, the non-stick effect of the hydrophobic coatings is easily deteriorated after long-term contact with yogurt during storage, so the problem of yogurt adhesion cannot be completely solved. Summary of the invention

[0004] The object of the present invention is to provide a technical solution related to a non-stick packaging material that can enable the yogurt packaging material to have a good and lasting non-stick yogurt effect.

[0005] In order to achieve the above-mentioned purpose, the present invention provides the following technical solutions.

[0006] In a first aspect, the present invention provides palm wax modified inorganic nanoparticles, wherein the palm wax modified inorganic nanoparticles can be prepared by contacting the inorganic nanoparticles with a dispersant and palm wax in an organic solvent environment, and then undergoing steps including solid-liquid separation and drying; wherein the weight ratio of the inorganic nanoparticles, palm wax and dispersant is: 1:2.5-3.8:0.05-0.08.

[0007] According to a preferred embodiment of the first aspect, the method for preparing the palm wax modified inorganic nanomaterial comprises the following steps:

[0008] A) dissolving palm wax in an organic solvent, adding inorganic nanoparticles and cyclodextrin, and allowing the inorganic nanoparticles to contact the cyclodextrin and palm wax in an organic solvent environment to obtain a palm wax mixture;

[0009] B) cooling the palm wax mixture;

[0010] C) separating and obtaining palm wax improved inorganic nanoparticles;

[0011] Furthermore, the method for preparing the palm wax modified inorganic nanomaterial further comprises: D) drying the palm wax modified inorganic nanoparticles after step C);

[0012] Furthermore, in order to better achieve the dissolution of palm wax in an organic solvent, the palm wax is dissolved in an organic solvent at 70-90°C;

[0013] Furthermore, the dispersant is cyclodextrin; the cyclodextrin acts as a dispersant and stabilizer, so that the inorganic nanoparticles are stably dispersed in the solvent during the preparation process to avoid agglomeration and precipitation;

[0014] Further, the weight ratio of inorganic nanoparticles, palm wax and cyclodextrin is: 1:2.5-3.8:0.05-0.08; in some specific embodiments, the weight ratio of inorganic oxide nanoparticles, palm wax and cyclodextrin is 1:2.5-3.1:0.05, and / or 1:2.5-3.1:0.07, and / or 1:2.5-3.1:0.08, and / or 1:3.1-3.8:0.05, and / or 1:3.1-3.8:0.07, and / or 1:3.1-3.8:0.08, and / or 1:3.8:0.05-0.07, and / or 1:3.8:0.07-0.08, and / or or 1:3.8:0.05-0.08; for example, the weight ratio of inorganic oxide nanoparticles, palm wax and cyclodextrin is 1:2.5:0.05, and / or 1:2.5:0.07, and / or 1:2.5:0.08, and / or 1:3.1:0.05, and / or 1:3.1:0.07, and / or 1:3.1:0.08, and / or 1:3.8:0.05, and / or 1:3.8:0.07, and / or 1:3.8:0.08; experimental analysis shows that the use of long-chain silane and stearic acid in the above weight ratio as modifiers can further improve the anti-yogurt viscosity of the film, and the stability of the non-stick yogurt is relatively excellent;

[0015] Further, the organic solvent includes but is not limited to one or a combination of two or more of dimethylformamide, chloroform, toluene, ethyl acetate, tetrahydrofuran and propylene glycol methyl ether acetate;

[0016] Further, the contact temperature is the reflux temperature of the organic solvent under normal pressure; further, the contact temperature is 70-90°C;

[0017] Furthermore, the contact time is 40-60 minutes;

[0018] Furthermore, the solid-liquid separation is achieved by centrifugal separation.

[0019] According to a preferred embodiment of the first aspect, the inorganic nanoparticles in the palm wax modified inorganic nanoparticles are inorganic oxide nanoparticles;

[0020] Furthermore, the inorganic nanoparticles in the palm wax modified inorganic nanoparticles include but are not limited to one or a combination of two or more of silicon dioxide, zinc oxide, titanium dioxide, and ferrosoferric oxide.

[0021] Through experimental analysis, it is known that in the process of preparing palm wax modified inorganic nanoparticles, by screening the weight ratio of inorganic nanoparticles, palm wax and cyclodextrin to be 1:2.5-3.8:0.05-0.08 and screening the types of inorganic nanoparticles at the same time, the anti-yogurt viscosity and stability of the hydrophobic film can be further improved.

[0022] According to a preferred embodiment of the first aspect, the particle size of the inorganic nanoparticles in the palm wax modified inorganic nanoparticles is 200-800 nm.

[0023] In a second aspect, the present invention provides use of the palm wax modified inorganic nanoparticles provided in the first aspect in preparing a hydrophobic film or a hydrophobic coating.

[0024] In a third aspect, the present invention provides a non-stick packaging material, wherein the non-stick packaging material is a hydrophobic film, wherein the raw material components of the hydrophobic film include:

[0025] 32-48 parts by weight of palm wax modified inorganic nanoparticles, 50-60 parts by weight of a modifier, and 28-34 parts by weight of a bio-based organic resin;

[0026] Wherein, the modifier comprises long-chain silane and stearic acid in a weight ratio of 10-15:2-4;

[0027] Wherein, the chemical formula of the long-chain silane is X is an alkoxy group, and R is an alkyl group having not less than 10 carbon atoms.

[0028] The present invention uses palm wax modified inorganic nanoparticles as hydrophobic nanoparticles, long-chain silane and stearic acid in a weight ratio of 10-15:2-4 as modifiers, and bio-based organic resins as adhesive film-forming agents, and controls the amount of each raw material component to form a hydrophobic film with excellent non-stick yogurt effect, that is, the non-stick packaging material provided by the third aspect of the present invention. The hydrophobic film is a non-stick yogurt film, which can significantly improve the anti-yogurt adhesion of the surface of the yogurt packaging material, reduce the combination between the film and yogurt, improve the non-stick yogurt effect, and still have a high non-stick yogurt property after long-term contact with yogurt during the yogurt storage process.

[0029] The hydrophobic film in the technical solution of the third aspect of the present invention uses palm wax modified inorganic nanoparticles obtained by modifying inorganic nanoparticles with palm wax. The palm wax modified inorganic nanoparticles can form synapses on the surface of the bio-based organic resin film layer, reduce the tension on the surface of the film, and effectively prevent yogurt from accumulating on the surface of the film; at the same time, the hydrophobic film in the present invention uses long-chain silane and stearic acid as modifiers to further improve the super-hydrophobicity of the bio-based organic resin film, thereby improving the effect of the film not sticking to yogurt. Under the coordinated action of palm wax modified inorganic nanoparticles, long-chain silane and stearic acid, the bio-based organic resin hydrophobic film has a good and lasting non-stick yogurt effect.

[0030] The non-stick packaging material provided by the present invention can usually be prepared by coating and drying the coating liquid (ie, coating and curing). The non-stick packaging material may contain residual solvents that are not completely removed during the drying process.

[0031] According to a preferred embodiment of the third aspect, in some specific embodiments, the addition amount of the palm wax modified inorganic nanoparticles is 40-48 parts by weight; in other specific embodiments, the addition amount of the palm wax modified inorganic nanoparticles is 32-40 parts; for example, the addition amount of the palm wax modified inorganic nanoparticles is 32 parts, and / or 40 parts, and / or 48 parts.

[0032] According to a preferred embodiment of the third aspect, in some specific embodiments, the amount of the modifier added is 53-57 parts; in other specific embodiments, the amount of the modifier added is 50-53 parts, and / or 50-55 parts, and / or 50-57 parts, and / or 53-55 parts, and / or 53-60 parts, and / or 55-57 parts, and / or 55-60 parts, and / or 57-60 parts; for example, the amount of the modifier added is 50 parts, and / or 53 parts, and / or 55 parts, and / or 57 parts, and / or 60 parts.

[0033] Through experimental analysis, it is known that when the addition amount of palm wax modified inorganic nanoparticles and modifiers is controlled within the above range, the film's anti-yogurt stickiness can be effectively improved and has higher stability.

[0034] According to a preferred embodiment of the third aspect, in some specific embodiments, the weight ratio of long-chain silane to stearic acid in the modifier is 10-12:2, and / or 10-12:3, and / or 10-12:4, and / or 12-15:2, and / or 12-15:3, and / or 12-15:4, and / or 15:2-3, and / or 15:3-4, and / or 15:2-4; for example, the weight ratio of long-chain silane to stearic acid in the modifier is 10:2, and / or 10:3, and / or 10:4, and / or 12:2, and / or 12:3, and / or 12:4, and / or 15:2, and / or 15:3, and / or 15:4.

[0035] The experimental analysis shows that using the long-chain silane and stearic acid in the above weight ratio as modifiers can effectively improve the film's anti-yogurt stickiness and has higher stability.

[0036] According to a preferred embodiment of the third aspect, the palm wax modified inorganic nanoparticles can be prepared by contacting the inorganic nanoparticles with a dispersant and palm wax in an organic solvent environment, followed by steps including solid-liquid separation and drying;

[0037] Furthermore, the palm wax modified inorganic nanoparticles can be prepared specifically by the following method:

[0038] A) dissolving palm wax in an organic solvent, adding inorganic nanoparticles and cyclodextrin, and allowing the inorganic nanoparticles to contact the cyclodextrin and palm wax in an organic solvent environment to obtain a palm wax mixture;

[0039] B) cooling the palm wax mixture;

[0040] C) separating and obtaining palm wax improved inorganic nanoparticles;

[0041] Furthermore, the method for preparing the palm wax modified inorganic nanomaterial further comprises: D) drying the palm wax modified inorganic nanoparticles after step C);

[0042] Furthermore, in order to better achieve the dissolution of palm wax in an organic solvent, the palm wax is dissolved in an organic solvent at 70-90°C;

[0043] Furthermore, the dispersant is cyclodextrin; the cyclodextrin acts as a dispersant and stabilizer, so that the inorganic nanoparticles are stably dispersed in the solvent during the preparation process to avoid agglomeration and precipitation;

[0044] Further, the weight ratio of inorganic nanoparticles, palm wax and cyclodextrin is: 1:2.5-3.8:0.05-0.08; in some specific embodiments, the weight ratio of inorganic oxide nanoparticles, palm wax and cyclodextrin is 1:2.5-3.1:0.05, and / or 1:2.5-3.1:0.07, and / or 1:2.5-3.1:0.08, and / or 1:3.1-3.8:0.05, and / or 1:3.1-3.8:0.07, and / or 1:3.1-3.8:0.08, and / or 1:3.8:0.05-0.07, and / or 1:3.8:0.07-0.08, and / or or 1:3.8:0.05-0.08; for example, the weight ratio of inorganic oxide nanoparticles, palm wax and cyclodextrin is 1:2.5:0.05, and / or 1:2.5:0.07, and / or 1:2.5:0.08, and / or 1:3.1:0.05, and / or 1:3.1:0.07, and / or 1:3.1:0.08, and / or 1:3.8:0.05, and / or 1:3.8:0.07, and / or 1:3.8:0.08; experimental analysis shows that the use of long-chain silane and stearic acid in the above weight ratio as modifiers can further improve the anti-yogurt viscosity of the film, and the stability of the non-stick yogurt is relatively excellent;

[0045] Further, the organic solvent includes but is not limited to one or a combination of two or more of dimethylformamide, chloroform, toluene, ethyl acetate, tetrahydrofuran and propylene glycol methyl ether acetate;

[0046] Further, the contact temperature is the reflux temperature of the organic solvent under normal pressure; further, the contact temperature is 70-90°C;

[0047] Furthermore, the contact time is 40-60 minutes;

[0048] Furthermore, the solid-liquid separation is achieved by centrifugal separation.

[0049] According to a preferred embodiment of the third aspect, the inorganic nanoparticles in the palm wax modified inorganic nanoparticles are inorganic oxide nanoparticles;

[0050] Furthermore, the inorganic nanoparticles in the palm wax modified inorganic nanoparticles include but are not limited to one or a combination of two or more of silicon dioxide, zinc oxide, titanium dioxide, and ferrosoferric oxide.

[0051] Through experimental analysis, it is known that in the process of preparing palm wax modified inorganic nanoparticles, by screening the weight ratio of inorganic nanoparticles, palm wax and cyclodextrin to be 1:2.5-3.8:0.05-0.08 and screening the types of inorganic nanoparticles at the same time, the anti-yogurt viscosity and stability of the hydrophobic film can be further improved.

[0052] According to a preferred embodiment of the third aspect, the particle size of the inorganic nanoparticles in the palm wax modified inorganic nanoparticles is 200-800 nm.

[0053] According to a preferred embodiment of the third aspect, in the chemical formula of the long-chain silane, R is an alkyl group with a carbon number of 10-18, and the carbon numbers of the A and B groups are both less than the carbon number of R; generally, the A and B groups can be alkyl, alkenyl (e.g., vinyl), alkoxy (e.g., ethoxy), carboxyl (e.g., methacrylic), amino, mercapto, etc.;

[0054] Furthermore, the long-chain silane includes but is not limited to one or a combination of two or more of octadecyltrimethoxysilane, octadecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, octadecylmethyldimethoxysilane, octadecylethyldimethoxysilane, octadecylmethyldiethoxysilane and octadecylethyldiethoxysilane.

[0055] Through experimental analysis, it can be seen that if short-chain silane and stearic acid are used in combination as modifiers, the prepared film has poor non-stick effect on yogurt; while using the above-mentioned long-chain silane and stearic acid as modifiers, a film with excellent anti-yogurt stickiness effect can be obtained.

[0056] According to a preferred embodiment of the third aspect, the bio-based organic resin can be selected from the bio-based organic resins listed in the "GB 9685-2016 National Food Safety Standard for the Use of Additives for Food Contact Materials and Articles" that meet the use standards for additives for food contact materials and articles, including but not limited to one or a combination of two or more of chlorinated polypropylene resin cpp521, organic polysilazane resin 1500RC and modified ethylene-vinyl acetate copolymer resin heat-sealing resin 53021.

[0057] According to a preferred embodiment of the third aspect, the thickness of the hydrophobic membrane is 0.5-15 microns.

[0058] In a fourth aspect, the present invention provides a coating liquid, which can be used to prepare the non-stick packaging material provided in the third aspect, wherein the raw material components of the coating liquid include:

[0059] 32-48 parts by weight of palm wax modified inorganic nanoparticles, 50-60 parts by weight of a modifier, 28-34 parts by weight of a bio-based organic resin and a solvent;

[0060] Wherein, the modifier comprises long-chain silane and stearic acid in a weight ratio of 10-15:2-4;

[0061] Wherein, the ratio of the total weight of the palm wax modified inorganic nanoparticles, the modifier and the bio-based organic resin to the weight of the solvent is 1:1-25.

[0062] The coating liquid provided in the fourth aspect of the present invention uses the components of the hydrophobic film in the third aspect of the present invention as a dispersant and a solvent as a dispersant. The non-stick packaging material provided in the third aspect of the present invention can be obtained by coating and drying the coating liquid provided in the fourth aspect of the present invention (i.e., the hydrophobic film in the third aspect of the present invention, i.e., the non-stick packaging material, can be obtained by coating and drying the coating liquid provided in the fourth aspect of the present invention).

[0063] According to a preferred embodiment of the fourth aspect, in some specific embodiments, the addition amount of the palm wax modified inorganic nanoparticles is 40-48 parts by weight; in other specific embodiments, the addition amount of the palm wax modified inorganic nanoparticles is 32-40 parts; for example, the addition amount of the palm wax modified inorganic nanoparticles is 32 parts, and / or 40 parts, and / or 48 parts.

[0064] According to a preferred embodiment of the fourth aspect, in some specific embodiments, the amount of the modifier added is 53-57 parts; in other specific embodiments, the amount of the modifier added is 50-53 parts, and / or 50-55 parts, and / or 50-57 parts, and / or 53-55 parts, and / or 53-60 parts, and / or 55-57 parts, and / or 55-60 parts, and / or 57-60 parts; for example, the amount of the modifier added is 50 parts, and / or 53 parts, and / or 55 parts, and / or 57 parts, and / or 60 parts.

[0065] According to a preferred embodiment of the fourth aspect, in some specific embodiments, the weight ratio of long-chain silane to stearic acid in the modifier is 10-12:2, and / or 10-12:3, and / or 10-12:4, and / or 12-15:2, and / or 12-15:3, and / or 12-15:4, and / or 15:2-3, and / or 15:3-4, and / or 15:2-4; for example, the weight ratio of long-chain silane to stearic acid in the modifier is 10:2, and / or 10:3, and / or 10:4, and / or 12:2, and / or 12:3, and / or 12:4, and / or 15:2, and / or 15:3, and / or 15:4.

[0066] According to a preferred embodiment of the fourth aspect,

[0067] The palm wax modified inorganic nanoparticles can be prepared by contacting the inorganic nanoparticles with a dispersant and palm wax in an organic solvent environment, followed by steps including solid-liquid separation and drying.

[0068] Furthermore, the palm wax modified inorganic nanoparticles can be prepared specifically by the following method:

[0069] A) dissolving palm wax in an organic solvent, adding inorganic nanoparticles and cyclodextrin, and allowing the inorganic nanoparticles to contact the cyclodextrin and palm wax in an organic solvent environment to obtain a palm wax mixture;

[0070] B) cooling the palm wax mixture;

[0071] C) Separating and obtaining palm wax improved inorganic nanoparticles;

[0072] Furthermore, the method for preparing the palm wax modified inorganic nanomaterial further comprises: D) drying the palm wax modified inorganic nanoparticles after step C);

[0073] Furthermore, in order to better achieve the dissolution of palm wax in an organic solvent, the palm wax is dissolved in an organic solvent at 70-90°C;

[0074] Furthermore, the dispersant is cyclodextrin; the cyclodextrin acts as a dispersant and stabilizer, so that the inorganic nanoparticles are stably dispersed in the solvent during the preparation process to avoid agglomeration and precipitation;

[0075] Further, the weight ratio of inorganic nanoparticles, palm wax and cyclodextrin is: 1:2.5-3.8:0.05-0.08; in some specific embodiments, the weight ratio of inorganic oxide nanoparticles, palm wax and cyclodextrin is 1:2.5-3.1:0.05, and / or 1:2.5-3.1:0.07, and / or 1:2.5-3.1:0.08, and / or 1:3.1-3.8:0.05, and / or 1:3.1-3.8:0.07, and / or 1:3.1-3.8:0.08, and / or 1:3.8:0 .05-0.07, and / or 1:3.8:0.07-0.08, and / or 1:3.8:0.05-0.08; for example, the weight ratio of inorganic oxide nanoparticles, palm wax and cyclodextrin is 1:2.5:0.05, and / or 1:2.5:0.07, and / or 1:2.5:0.08, and / or 1:3.1:0.05, and / or 1:3.1:0.07, and / or 1:3.1:0.08, and / or 1:3.8:0.05, and / or 1:3.8:0.07, and / or 1:3.8:0.08;

[0076] Further, the organic solvent includes but is not limited to one or a combination of two or more of dimethylformamide, chloroform, toluene, ethyl acetate, tetrahydrofuran and propylene glycol methyl ether acetate;

[0077] Further, the contact temperature is the reflux temperature of the organic solvent under normal pressure; further, the contact temperature is 70-90°C;

[0078] Furthermore, the contact time is 40-60 minutes;

[0079] Furthermore, the solid-liquid separation is achieved by centrifugal separation.

[0080] According to a preferred embodiment of the fourth aspect, the inorganic nanoparticles in the palm wax modified inorganic nanoparticles are inorganic oxide nanoparticles;

[0081] Furthermore, the inorganic nanoparticles in the palm wax modified inorganic nanoparticles include but are not limited to one or a combination of two or more of silicon dioxide, zinc oxide, titanium dioxide, and ferrosoferric oxide.

[0082] According to a preferred embodiment of the fourth aspect, the particle size of the inorganic nanoparticles in the palm wax modified inorganic nanoparticles is 200-800 nm.

[0083] According to a preferred embodiment of the fourth aspect, the long-chain silane includes but is not limited to one or a combination of two or more of hexadecyltrimethoxysilane and dodecyltrimethoxysilane.

[0084] According to a preferred embodiment of the fourth aspect, the bio-based organic resin includes but is not limited to one or a combination of two or more of chlorinated polypropylene resin cpp521, organic polysilazane resin 1500RC and heat-sealing resin 53021 of modified ethylene-vinyl acetate copolymer resin.

[0085] According to a preferred embodiment of the fourth aspect, the raw material component solvent of the coating liquid can be selected from the solvents listed in the "GB9685-2016 National Food Safety Standard for the Use of Additives in Food Contact Materials and Articles" that meet the use standards for additives in food contact materials and articles, including but not limited to one or a combination of more than two of ethanol, ethyl acetate, acetone and butanol.

[0086] According to a preferred embodiment of the fourth aspect, the coating liquid can be prepared by the following method:

[0087] dispersing the palm wax modified inorganic nanoparticles in a solvent to obtain a suspension;

[0088] The modifying agent and the bio-based organic resin are added to the suspension to obtain the coating solution.

[0089] In a fifth aspect, the present invention provides a method for preparing the non-stick packaging material in the third aspect, wherein the method comprises:

[0090] The coating liquid provided in the fourth aspect is coated on the surface of the substrate and dried to obtain the hydrophobic film, namely the non-stick packaging material.

[0091] The non-stick packaging material provided by the invention has simple preparation process, convenient operation, low cost and broad application prospect.

[0092] According to a preferred embodiment of the fifth aspect, the preparation method comprises:

[0093] Dispersing the palm wax modified inorganic nanoparticles in a solvent (see the solvent component included in the coating solution provided in the fourth aspect) to obtain a suspension;

[0094] Adding the modifier and the bio-based organic resin to the suspension to obtain a coating solution (i.e., the coating solution provided in the fourth aspect);

[0095] The coating liquid is evenly coated on the surface of the substrate and dried to obtain the hydrophobic film, namely the non-stick packaging material.

[0096] According to a preferred embodiment of the fifth aspect, the specific conditions for coating are: the wire roller coating speed is 35-60 m / min, the coating amount is 0.8-1.5 g / m 2 .

[0097] According to a preferred embodiment of the fifth aspect, the drying temperature is 55-100°C.

[0098] In a sixth aspect, the present invention provides use of the non-stick packaging material in the third aspect in food packaging materials.

[0099] According to a preferred embodiment of the sixth aspect, the food comprises liquid milk and / or sauce;

[0100] Furthermore, the liquid milk includes one or a combination of two or more of fermented milk, milk beverage and fresh milk.

[0101] According to a preferred embodiment of the sixth aspect, the non-stick packaging material is coated on the surface of the food packaging material.

[0102] The non-stick packaging material provided by the present invention can effectively prevent yogurt from sticking to the inner layer of the cover film, thereby preventing yogurt from being wasted, while also improving the sensory effect of consumers and enhancing the drinking experience.

[0103] In summary, compared with the prior art, the technical solution provided by the present invention has the following effects:

[0104] The technical solution provided by the present invention utilizes palm wax modified inorganic nanoparticles as hydrophobic nanoparticles, long-chain silane and stearic acid as modifiers, and bio-based organic resins as adhesive film-forming agents, and screens the amount of each raw material, so that the obtained non-stick packaging material (hydrophobic film) has a good and lasting non-stick yogurt effect. In the existing bottled yogurt and cup yogurt, the yogurt will stick to the packaging and cannot be poured out completely, resulting in a certain degree of waste. The above problem can be solved by arranging the non-stick packaging material of the present invention on the inner wall of the yogurt packaging bottle or the inner wall of the sealing film of the common cup yogurt. When the yogurt is packaged in this packaging bottle or cup, after a long period of storage, even after experiencing a large bump during transportation, the yogurt will still not stick to the surface of the non-stick packaging material, so that it can flow out basically completely or completely, reducing or completely avoiding waste. DETAILED DESCRIPTION

[0105] In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments. It should be understood by those skilled in the art that the content specifically described below is illustrative and non-restrictive, and protection scope of the present invention should not be limited by this. Efforts have been made to ensure the accuracy of numbers (such as amounts, temperatures, etc.), but some errors and deviations should be taken into account.

[0106] A specific embodiment of the present invention provides a palm wax modified inorganic nanoparticle, wherein the palm wax modified inorganic nanoparticle is prepared by the following method:

[0107] Dissolve palm wax in an organic solvent at 70-90° C., add inorganic nanoparticles and cyclodextrin, reflux for 40-60 minutes at a constant temperature, cool, separate solid and liquid, and dry to obtain palm wax modified inorganic nanoparticles; wherein the weight ratio of inorganic nanoparticles, palm wax and cyclodextrin is 1:2.5-3.8:0.05-0.08;

[0108] The inorganic nanoparticles are selected from inorganic oxide nanoparticles; specifically, the inorganic nanoparticles are selected from one or a combination of two or more of silicon dioxide, zinc oxide, titanium dioxide and ferrosoferric oxide;

[0109] Wherein, the particle size of the inorganic nanoparticles is 200-800nm;

[0110] The organic solvent is selected from one or a combination of two or more of dimethylformamide, chloroform, toluene, ethyl acetate, tetrahydrofuran and propylene glycol methyl ether acetate.

[0111] A specific embodiment of the present invention provides a non-stick packaging material, wherein the non-stick packaging material is a hydrophobic film, and the raw material components of the hydrophobic film include:

[0112] 32-48 parts by weight of palm wax modified inorganic nanoparticles, 50-60 parts by weight of a modifier, and 28-34 parts by weight of a bio-based organic resin; the modifier comprises long-chain silane and stearic acid in a weight ratio of 10-15:2-4.

[0113] The palm wax modified inorganic nanoparticles are prepared by the following method:

[0114] Dissolve palm wax in an organic solvent at 70-90° C., add inorganic nanoparticles and cyclodextrin, reflux for 40-60 minutes at a constant temperature, cool, separate solid and liquid, and dry to obtain palm wax modified inorganic nanoparticles; wherein the weight ratio of inorganic nanoparticles, palm wax and cyclodextrin is 1:2.5-3.8:0.05-0.08;

[0115] The inorganic nanoparticles are selected from inorganic oxide nanoparticles; specifically, the inorganic nanoparticles are selected from one or a combination of two or more of silicon dioxide, zinc oxide, titanium dioxide and ferrosoferric oxide;

[0116] Wherein, the particle size of the inorganic nanoparticles is 200-800nm;

[0117] The organic solvent is selected from one or a combination of two or more of dimethylformamide, chloroform, toluene, ethyl acetate, tetrahydrofuran and propylene glycol methyl ether acetate.

[0118] Wherein, the long-chain silane is selected from hexadecyltrimethoxysilane and / or dodecyltrimethoxysilane.

[0119] The bio-based organic resin is selected from one or a combination of two or more of chlorinated polypropylene resin cpp521, organic polysilazane resin 1500RC and heat-sealing resin 53021 of modified ethylene-vinyl acetate copolymer resin.

[0120] The thickness of the hydrophobic membrane is 0.5-15 microns.

[0121] Another specific embodiment of the present invention provides a coating solution, the raw material components of which include:

[0122] The raw material components and solvents of the hydrophobic membrane in the above specific embodiments;

[0123] The coating liquid uses the raw material components of the hydrophobic film in the above specific embodiment as a dispersant and a solvent as a dispersant.

[0124] Another specific embodiment of the present invention provides a method for preparing the non-stick packaging material provided in the above specific embodiment, which specifically comprises the following steps:

[0125] Under normal temperature conditions, the palm wax modified inorganic nanoparticles are dispersed in a solvent (the solvent included in the coating solution provided in the above specific embodiment is selected) to obtain a suspension;

[0126] Adding a modifier and a bio-based organic resin to the suspension to obtain a coating solution (and the coating solution provided in the above specific embodiment);

[0127] The coating liquid is evenly coated on the surface of the substrate and dried to obtain a hydrophobic film, namely the non-stick packaging material.

[0128] The specific coating conditions are: the wire roller coating speed is 35-60m / min, the coating amount is 0.8-1.5g / m 2 .

[0129] Wherein, the drying temperature is 55-100°C.

[0130] Another specific embodiment of the present invention provides the use of the non-stick packaging material provided in the above specific embodiment in yogurt packaging material.

[0131] Wherein, the non-stick packaging material is coated on the surface of the yogurt packaging material.

[0132] The technical solution provided by the present invention is further described in detail below in conjunction with embodiments, comparative examples and performance testing experiments. These embodiments should not be construed as limiting the scope of protection claimed in this application.

[0133] Materials used in the embodiments of the present invention:

[0134] Palm wax: brand 84, purchased from Dongguang Taixin Wax Products Factory.

[0135] Cyclodextrin: food grade, purchased from Zhengzhou Yuhe Food Additive Co., Ltd.;

[0136] The remaining raw materials were purchased from commercial sources.

[0137] Preparation Example

[0138] Preparation Example 1

[0139] This preparation example provides a palm wax modified inorganic nanoparticle. It is prepared by the following method:

[0140] First, palm wax was dissolved in 1000 mL of ethyl acetate at 85°C, and then zinc oxide with a particle size of 500±50 nm was added as inorganic nanoparticles and cyclodextrin, and refluxed for 50 minutes at a constant temperature; then the reaction solution was cooled to room temperature, centrifuged at 6000 r / min for 10 minutes, and dried in an oven at 80°C to obtain palm wax modified inorganic nanoparticles. The amounts of inorganic nanoparticles, palm wax, and cyclodextrin are shown in Table 1.

[0141] Preparation Example 2

[0142] This preparation example provides a palm wax modified inorganic nanoparticle. The difference between this preparation example and preparation example 1 is that the amounts of inorganic nanoparticles, palm wax, and cyclodextrin are different, see Table 1 for details.

[0143] Preparation Example 3

[0144] This preparation example provides a palm wax modified inorganic nanoparticle. The difference between this preparation example and preparation example 1 is that the amounts of inorganic nanoparticles, palm wax, and cyclodextrin are different, see Table 1 for details.

[0145] Preparation Example 4

[0146] This preparation example provides a palm wax modified inorganic nanoparticle. The difference between this preparation example and preparation example 1 is that the amounts of inorganic nanoparticles, palm wax, and cyclodextrin are different, see Table 1 for details.

[0147] Preparation Example 5

[0148] This preparation example provides a palm wax modified inorganic nanoparticle. The difference between this preparation example and preparation example 1 is that the amounts of inorganic nanoparticles, palm wax, and cyclodextrin are different, see Table 1 for details.

[0149] Preparation Example 6

[0150] This preparation example provides a palm wax modified inorganic nanoparticle. The difference between this preparation example and preparation example 3 is that the types of inorganic nanoparticles are different, see Table 1 for details.

[0151] Preparation Example 7

[0152] This preparation example provides a palm wax modified inorganic nanoparticle. The difference between this preparation example and preparation example 3 is that the types of inorganic nanoparticles are different, see Table 1 for details.

[0153] Preparation Example 8

[0154] This preparation example provides a palm wax modified inorganic nanoparticle. The difference between this preparation example and preparation example 3 is that the types of inorganic nanoparticles are different, see Table 1 for details.

[0155] Table 1

[0156]

[0157] Example

[0158] Example 1

[0159] This embodiment provides a non-stick packaging material, which is a hydrophobic film and is prepared by the following method:

[0160] Under normal temperature conditions, the palm wax modified inorganic nanoparticles provided in Preparation Example 3 were dispersed in 200 mL of ethyl acetate solvent to obtain a suspension;

[0161] Adding hexadecyltrimethoxysilane and stearic acid in a weight ratio of 12:3 as a modifier and chlorinated polypropylene resin cpp521 as a bio-based organic resin to the suspension to obtain a coating solution for later use;

[0162] The coating liquid was evenly coated on the surface of the aluminum foil substrate. The coating conditions were: the wire roller coating speed was 40m / min, the coating amount was 1.1g / m 2 After drying in an oven at 60°C, a hydrophobic film is obtained, wherein the thickness of the hydrophobic film layer is 10±1 μm.

[0163] The amounts of palm wax-modified inorganic nanoparticles, modifiers, and bio-based organic resins are shown in Table 2.

[0164] Example 2

[0165] This embodiment provides a non-stick packaging material, which is a hydrophobic film. The difference between this embodiment and embodiment 1 is that the amount of palm wax modified inorganic nanoparticles, modifier, and bio-based organic resin is different, see Table 2 for details.

[0166] Example 3

[0167] This embodiment provides a non-stick packaging material, which is a hydrophobic film. The difference between this embodiment and embodiment 1 is that the amount of palm wax modified inorganic nanoparticles, modifier, and bio-based organic resin is different, see Table 2 for details.

[0168] Example 4

[0169] This embodiment provides a non-stick packaging material, which is a hydrophobic film. The difference between this embodiment and embodiment 1 is that the amount of palm wax modified inorganic nanoparticles, modifier, and bio-based organic resin is different, see Table 2 for details.

[0170] Example 5

[0171] This embodiment provides a non-stick packaging material, which is a hydrophobic film. The difference between this embodiment and embodiment 1 is that the amount of palm wax modified inorganic nanoparticles, modifier, and bio-based organic resin is different, see Table 2 for details.

[0172] Example 6

[0173] This embodiment provides a non-stick packaging material, which is a hydrophobic film. The difference between this embodiment and embodiment 1 is that the types of palm wax-modified inorganic nanoparticles are different, see Table 2 for details.

[0174] Example 7

[0175] This embodiment provides a non-stick packaging material, which is a hydrophobic film. The difference between this embodiment and embodiment 1 is that the types of palm wax-modified inorganic nanoparticles are different, see Table 2 for details.

[0176] Example 8

[0177] This embodiment provides a non-stick packaging material, which is a hydrophobic film. The difference between this embodiment and embodiment 1 is that the types of palm wax-modified inorganic nanoparticles are different, see Table 2 for details.

[0178] Example 9

[0179] This embodiment provides a non-stick packaging material, which is a hydrophobic film. The difference between this embodiment and embodiment 1 is that the types of palm wax-modified inorganic nanoparticles are different, see Table 2 for details.

[0180] Example 10

[0181] This embodiment provides a non-stick packaging material, which is a hydrophobic film. The difference between this embodiment and embodiment 1 is that the types of palm wax-modified inorganic nanoparticles are different, see Table 2 for details.

[0182] Embodiment 11

[0183] This embodiment provides a non-stick packaging material, which is a hydrophobic film. The difference between this embodiment and embodiment 1 is that the types of palm wax-modified inorganic nanoparticles are different, see Table 2 for details.

[0184] Example 12

[0185] This embodiment provides a non-stick packaging material, which is a hydrophobic film. The difference between this embodiment and embodiment 1 is that the types of palm wax-modified inorganic nanoparticles are different, see Table 2 for details.

[0186] Embodiment 13

[0187] This embodiment provides a non-stick packaging material, which is a hydrophobic film. The difference between this embodiment and embodiment 1 is that the type of the modifier is different, see Table 2 for details.

[0188] Embodiment 14

[0189] This embodiment provides a non-stick packaging material, which is a hydrophobic film. The difference between this embodiment and embodiment 1 is that the type of the modifier is different, see Table 2 for details.

[0190] Embodiment 15

[0191] This embodiment provides a non-stick packaging material, which is a hydrophobic film. The difference between this embodiment and embodiment 1 is that the type of the modifier is different, see Table 2 for details.

[0192] Table 2

[0193]

[0194]

[0195] Comparative Example

[0196] Comparative Example 1

[0197] This comparative example provides a non-stick packaging material, which is a hydrophobic film. The difference between this comparative example and Example 1 is that the amount of palm wax modified inorganic nanoparticles added is 25 g.

[0198] Comparative Example 2

[0199] This comparative example provides a non-stick packaging material, which is a hydrophobic film. The difference between this comparative example and Example 1 is that the amount of palm wax modified inorganic nanoparticles added is 55 g.

[0200] Comparative Example 3

[0201] This comparative example provides a non-stick packaging material, which is a hydrophobic film. The difference between this comparative example and Example 1 is that unmodified zinc oxide (particle size of 500±50 nm) is used instead of palm wax modified inorganic nanoparticles.

[0202] Comparative Example 4

[0203] This comparative example provides a non-stick packaging material, which is a hydrophobic film. The difference between this comparative example and Example 1 is that the type of the modifier is different, and the modifier is vinyl trichlorosilane and stearic acid in a ratio of 12:3.

[0204] Comparative Example 5

[0205] This comparative example provides a non-stick packaging material, which is a hydrophobic film. The difference between this comparative example and Example 1 is that the type of the modifier is different, and the modifier is hexadecyltrimethoxysilane and stearic acid in a ratio of 16:2.

[0206] Comparative Example 6

[0207] This comparative example provides a non-stick packaging material, which is a hydrophobic film. The difference between this comparative example and Example 1 is that the type of the modifier is different, and the modifier is hexadecyltrimethoxysilane and stearic acid in a ratio of 9:4.

[0208] Performance testing

[0209] The yogurts used in the performance test were all commercially available Yili Anmuxi Greek-flavored yogurt with batch number 20230219A12, and the production date was within 2 months.

[0210] (1) Test on the anti-yogurt adhesion of hydrophobic membranes

[0211] The non-stick effect of the hydrophobic film is evaluated by testing the yogurt contact angle and yogurt rolling angle of the hydrophobic film. The specific method is as follows:

[0212] Yogurt contact angle: The yogurt contact angle was tested using a contact angle tester; the test temperature was 25°C ± 2°C;

[0213] Yogurt rolling angle: first, the aluminum foil substrate coated with a hydrophobic film in each embodiment and each comparative example is fixed on a flat plate, a drop of yogurt (about 0.2 mL) is dripped on the surface of the hydrophobic film, and then the flat plate is slowly tilted until the yogurt rolls off. The measured inclination angle of the flat plate when the yogurt rolls off is the yogurt rolling angle; wherein, the test temperature is 25°C ± 2°C.

[0214] (2) Stability test of hydrophobic membrane

[0215] The stability of the hydrophobic film was evaluated by testing the amount of yogurt attached under different conditions. The specific method is as follows:

[0216] A. Heat-seal the aluminum foil substrate coated with a hydrophobic film on the surface of each embodiment and each comparative example on a cup product filled with yogurt to form a yogurt cover film; the heat-seal temperature is 200° C., the pressure is 0.5 MPa, and the time is 2 seconds;

[0217] B. Use a Japanese IDEX BF-25H simple vibration tester to conduct a vibration test; the vibration conditions are: 30Hz, 2.2mm vertical amplitude, acceleration of about 1G, and time of 5min;

[0218] C. Then open the yogurt cover film with your fingers, and weigh the weight of the yogurt cover film attached to the yogurt using a 1 / 10,000 balance, then rinse off the yogurt with clean water and weigh the weight of the yogurt cover film after air drying, and then calculate the weight of the yogurt attached to the yogurt cover film; perform parallel measurements 3 times and take the average value;

[0219] D. At the same time, take two more portions of heat-sealed yogurt and store them at room temperature and 4°C for 21 days respectively, and then test them according to the above step C.

[0220] The test results are shown in Table 3.

[0221] Table 3

[0222]

[0223]

[0224] Combined with Table 3, by comparing the test results of Example 1-Example 15 with Comparative Example 1-Comparative Example 6, it can be seen that the present invention uses palm wax modified inorganic nanoparticles as hydrophobic nanoparticles, long-chain silane and stearic acid with a weight ratio of 10-15:2-4 as modifiers and bio-based organic resins as adhesive film-forming agents, and controls the amount of each raw material component, and the yogurt contact angle of the obtained hydrophobic film is greater than 141°, and the yogurt rolling angle is less than 23°. When the film is used as a packaging material for yogurt, the yogurt adhesion amount measured by the vibration test is less than 0.14g / cup; after the yogurt is stored at room temperature for 21 days, the yogurt adhesion amount is less than 0.24g / cup; after the yogurt is refrigerated at 4°C for 21 days, the yogurt adhesion amount is less than 0.28g / cup. The above test results show that the non-stick packaging material (hydrophobic film) provided by the present invention can significantly improve the anti-yogurt stickiness performance of the surface of the yogurt packaging material, reduce the possibility of bonding between the film and the yogurt, and thus improve the non-stick effect; at the same time, the non-stick packaging material (hydrophobic film) provided by the present invention has high non-stick stability.

[0225] By comparing the test results of Example 1 and Comparative Example 3, when unmodified zinc oxide is added to the hydrophobic film, the contact angle of yogurt is only 96°, the rolling angle of yogurt is 28°, and the adhesion amount of yogurt is greater than 0.759 g / cup; while the present invention uses palm wax to modify inorganic nanoparticles as hydrophobic nanoparticles, which can significantly improve the non-stick effect and stability of the hydrophobic film.

[0226] By comparing the test results of Examples 1 to 5 with Comparative Examples 1 to 2, when the addition amount of the palm wax-modified inorganic nanoparticles is controlled to be 32-48 parts, the non-stick effect and stability of the hydrophobic film can be further improved.

[0227] At the same time, by comparing the test results of Example 1 with those of Example 6-Example 12, in the process of palm wax modification of inorganic nanoparticles, when zinc oxide is selected as the inorganic nanoparticles and the weight ratio of the inorganic nanoparticles, palm wax and cyclodextrin is controlled to be 1:2.5-3.8:0.05-0.08, the non-stick effect and stability of the hydrophobic film can be further improved.

[0228] By comparing the test results of Example 1, Example 13-Example 15 and Comparative Examples 5-Comparative Examples 6, when short-chain silane (vinyl trichlorosilane) and fatty acid are selected as modifiers, the contact angle of yogurt is only 105°, the yogurt rolling angle is 27°, and the yogurt adhesion amount is greater than 0.623 g / cup; while the present invention selects long-chain silane and fatty acid as modifiers, which can effectively improve the non-stick effect and stability of the hydrophobic film. Further, the present invention controls the weight ratio of long-chain silane to fatty acid to 10-15:2-4.

[0229] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.

Claims

1. A palm wax modified inorganic nanoparticle, wherein: The palm wax modified inorganic nanoparticles can be prepared by contacting the inorganic nanoparticles with a dispersant and palm wax in an organic solvent environment, followed by solid-liquid separation and drying. The weight ratio of the inorganic nanoparticles, palm wax and dispersant is 1:2.5-3.8:0.05-0.

08. Preferably, the method for preparing the palm wax modified inorganic nanomaterial comprises the following steps: A) dissolving palm wax in an organic solvent, adding inorganic nanoparticles and cyclodextrin, and allowing the inorganic nanoparticles to contact the cyclodextrin and palm wax in an organic solvent environment to obtain a palm wax mixture; B) cooling the palm wax mixture; C) separating and obtaining palm wax improved inorganic nanoparticles; More preferably, the method for preparing the palm wax modified inorganic nanomaterial further comprises: D) drying the palm wax modified inorganic nanoparticles after step C); Preferably, the organic solvent comprises one or a combination of two or more of dimethylformamide, chloroform, toluene, ethyl acetate, tetrahydrofuran and propylene glycol methyl ether acetate; Preferably, the dispersant is cyclodextrin; Preferably, the contact temperature is the reflux temperature of the organic solvent under normal pressure; more preferably, the contact temperature is 70-90°C; Preferably, the contact time is 40-60 min.

2. The palm wax modified inorganic nanoparticles according to claim 1, wherein: The inorganic nanoparticles in the palm wax modified inorganic nanoparticles are inorganic oxide nanoparticles; preferably, the inorganic nanoparticles in the palm wax modified inorganic nanoparticles include one or a combination of two or more of silicon dioxide, zinc oxide, titanium dioxide and ferrosoferric oxide; and / or The particle size of the inorganic nanoparticles in the palm wax modified inorganic nanoparticles is 200-800 nm.

3. Use of the palm wax modified inorganic nanoparticles according to claim 1 or 2 in the preparation of hydrophobic films or hydrophobic coatings.

4. A non-stick packaging material, the non-stick packaging material is a hydrophobic film, wherein: The raw material components of the hydrophobic membrane include: 32-48 parts by weight of the palm wax modified inorganic nanoparticles according to claim 1 or 2, 50-60 parts by weight of a modifier, and 28-34 parts by weight of a bio-based organic resin; Wherein, the modifier comprises long-chain silane and stearic acid in a weight ratio of 10-15:2-4; Wherein, the chemical formula of the long-chain silane is X is an alkoxy group, and R is an alkyl group having not less than 10 carbon atoms.

5. The non-stick packaging material according to claim 4, wherein: In the chemical formula of the long-chain silane, R is an alkyl group with a carbon number of 10-18, and the carbon numbers of the A and B groups are both smaller than the carbon number of R; Preferably, the long-chain silane includes one or a combination of two or more of octadecyltrimethoxysilane, octadecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, octadecylmethyldimethoxysilane, octadecylethyldimethoxysilane, octadecylmethyldiethoxysilane and octadecylethyldiethoxysilane.

6. The non-stick packaging material according to claim 4, wherein: The bio-based organic resin includes one or a combination of two or more of chlorinated polypropylene resin cpp521, organic polysilazane resin 1500RC and heat-sealing resin 53021 of modified ethylene-vinyl acetate copolymer resin.

7. A coating liquid for preparing the non-stick packaging material according to any one of claims 4 to 6, wherein: The raw material components of the coating solution include: The palm wax modified inorganic nanoparticles, the modifier, the bio-based organic resin and a solvent; Wherein, the ratio of the total weight of the palm wax modified inorganic nanoparticles, the modifier and the bio-based organic resin to the weight of the solvent is: 1:1-25; Preferably, the raw material component solvent of the coating solution includes one or a combination of two or more of ethanol, ethyl acetate, acetone and butanol.

8. The method for preparing the non-stick packaging material according to any one of claims 4 to 6, wherein: The method includes: The coating liquid according to claim 7 is applied to the surface of a substrate and dried to obtain the hydrophobic film, namely the non-stick packaging material.

9. The preparation method according to claim 8, wherein The specific conditions of the coating are: the wire roller coating speed is 35-45m / min, the coating amount is 0.8-1.2g / m 2 .

10. Use of the non-stick packaging material according to any one of claims 4 to 6 in food packaging materials; Preferably, the food comprises liquid milk and / or sauce; more preferably, the liquid milk comprises one or a combination of two or more of fermented milk, milk beverage and fresh milk.

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