A composite film, a preparation method thereof, and an application thereof

Abstract

The present invention discloses a composite film, a preparation method thereof, and an application. The composite film comprises an A layer, a B layer, and a C layer stacked in sequence; the A layer is a super matte PP synthetic paper layer; the B layer is a PU layer; the C layer is a TPU layer or a PVC layer. The composite film prepared by the present invention has a good matte effect, a smoother surface, does not turn white, and can simultaneously have various performance effects such as scratch resistance, environmental protection, not easily embrittling, and low temperature resistance. The composite film has broad application prospects.

Description

Technical Field

[0001] The present invention specifically relates to a composite film, a preparation method thereof, and an application thereof. Background Art

[0002] With the ever-changing development of the clothing industry, different consumers have different requirements for clothing. Among them, waterproof zippers, as a new type of zipper, are widely popular among consumers. The main use of waterproof zippers is to provide a waterproof function when encountering rain. Waterproof zippers are widely used and are suitable for: cold-proof clothes, ski clothes, down jackets, sailing clothes, diving suits, tents, vehicle and ship covers, raincoats, motorcycle raincoats, waterproof shoes, fire-fighting suits, luggage, assault jackets, fishing clothes, and other waterproof-related series of products.

[0003] The composite film that can be used for the above products is generally made of polyvinyl chloride (PVC) or thermoplastic polyurethane elastomer rubber (TPU). Among them, because TPU overcomes many defects of PVC such as poor fluidity, low shrinkage rate, and easy release of toxic gases during the molding process, the above products containing TPU materials have many characteristics such as non-whitening, non-brittle, low-temperature resistance, environmental protection, softness, and good waterproofness, and are superior to products containing PVC materials in terms of performance. However, due to its production process, the surface gloss of the above products containing TPU materials is relatively bright, which is contrary to the consumer's demand for a matte and high-class feeling.

[0004] Chinese Patent Document: CN00108268.X discloses a waterproof zipper film and a manufacturing method thereof. The obtained composite film has a single function and only has a waterproof effect.

[0005] Therefore, those skilled in the art urgently need to develop a composite film with a good matte effect and diverse functions. Summary of the Invention

[0006] The technical problem solved by the present invention is to overcome the defect of poor matte effect of TPU films in the prior art, and to provide a composite film, a preparation method thereof, and an application thereof. The composite film prepared by the present invention has a good matte effect, a smoother surface, non-whitening, and can simultaneously have multiple performance effects such as scratch resistance, environmental protection, not easy to brittle, and low-temperature resistance (can withstand a low-temperature environment of more than minus 50 degrees Celsius, and the embrittlement temperature is low). The application prospect of this composite film is broad.

[0007] The present invention provides the following technical solutions to solve the above technical problems.

[0008] The present invention provides a type I composite film, which includes an A layer, a B layer, and a C layer stacked in sequence;

[0009] The A layer is a super-matte PP synthetic paper layer;

[0010] The B layer is a PU layer;

[0011] The C layer is a TPU layer or a PVC layer.

[0012] In the present invention, the super matte PP synthetic paper layer is preferably a super matte PP synthetic paper with the model number HYL-020 and the manufacturer being Suzhou Libiao Packaging Company.

[0013] In the present invention, the size of the super matte PP synthetic paper layer can be a conventional size in the art. For example, in the present invention, the width of the super matte PP synthetic paper layer can be 1200 - 1800 mm, preferably 1600 mm.

[0014] In the present invention, the roll length of the super matte PP synthetic paper layer can be 100 - 1000 m, preferably 1000 m.

[0015] In the present invention, the thickness of the super matte PP synthetic paper layer can be 0.1 - 0.5 mm, preferably 0.2 - 0.5 mm.

[0016] In the present invention, the thickness of the PU layer can be 0.01 - 0.05 mm, preferably 0.03 - 0.05 mm.

[0017] In the present invention, the C layer is preferably a TPU layer.

[0018] In the present invention, when the C layer is a TPU layer, the thickness of the TPU layer can be 0.05 - 0.5 mm, preferably 0.1 - 0.5 mm.

[0019] In the present invention, when the C layer is a PVC layer, the thickness of the PVC layer can be 0.05 - 0.5 mm, preferably 0.1 - 0.5 mm.

[0020] In the present invention, the preparation steps of the PU layer include: coating the PU slurry on the super matte PP synthetic paper layer and drying it.

[0021] Among them, the PU slurry can include PU and a solvent.

[0022] The PU can be a conventional type of PU in the art, such as polyester-type PU, polyether-type PU, or aliphatic PU. Preferably, it is polyester-type PU, such as polyurethane resin.

[0023] When the weight fraction of the PU slurry is 150 - 200 parts, such as 179.3 parts, the weight fraction of the PU can be 100 - 200 parts, preferably 100 parts. The weight fraction refers to the weight fraction of the PU in the total weight of the PU slurry.

[0024] Preferably, the PU paste further includes additives, which may be one or more of a diluent, a colorant, a matting agent, and a leveling agent, preferably a matting agent, a leveling agent, a diluent, and a colorant. The types of the additives can be selected according to actual needs. The content of the additives can be adjusted conventionally according to actual needs.

[0025] When the additive includes a diluent, the diluent can be a conventional diluent in the art, preferably 2-butanone (MEK).

[0026] When the weight parts of PU in the PU paste are 100-200 parts, such as 100 parts, the content of the diluent can be 20-100 weight parts, preferably 45-80 weight parts, and the weight parts refer to the weight parts of the diluent in the total weight of the PU paste.

[0027] When the additive includes a colorant, the colorant can be a conventional colorant in the art, preferably a color powder. The color powder can be one or more of ferric sulfate, cobalt aluminate, lead chromate, iron zincate, and high pigment carbon black, preferably high pigment carbon black.

[0028] When the weight parts of PU in the PU paste are 100-200 parts, such as 100 parts, the content of the colorant can be 1-20 weight parts, preferably 4-10 weight parts, and the weight parts refer to the weight parts of the colorant in the total weight of the PU paste.

[0029] When the additive includes a leveling agent, the leveling agent can be a conventional leveling agent in the art, preferably one or more of polyacrylic acids, carboxymethyl cellulose, polymethylphenylsiloxane, and polydimethylsiloxane, more preferably polydimethylsiloxane.

[0030] When the weight parts of PU in the PU paste are 100-200 parts, such as 100 parts, the content of the leveling agent can be 0.1-10 weight parts, preferably 0.3-5 weight parts, and the weight parts refer to the weight parts of the leveling agent in the total weight of the PU paste.

[0031] When the additive includes a matting agent, the matting agent can be a conventional matting agent in the art, preferably one or more of silica gel method silica, diatomaceous earth, titanium dioxide, and calcium carbonate, more preferably silica gel method silica.

[0032] When the weight parts of PU in the PU paste are 100-200 parts, such as 100 parts, the content of the matting agent can be 1-20 weight parts, preferably 5-10 weight parts, and the weight parts refer to the weight parts of the matting agent in the total weight of the PU paste.

[0033] Among them, the solvent can be a conventional solvent in the art, such as N,N-dimethylformamide (DMF) and / or isobutanol (IBA), preferably N,N-dimethylformamide (DMF) and isobutanol (IBA).

[0034] The amount of the solvent used can be a conventional amount in the art, generally just enough to disperse the PU. For example, when the weight parts of PU in the PU slurry are 100 - 200 parts, such as 100 parts, the amount of the solvent used can be 10 - 80 parts, preferably 15 - 60 parts. The weight parts refer to the weight parts of the solvent in the total weight of the PU slurry.

[0035] Among them, the drying method and conditions can be conventional methods and conditions in the art, such as drying by baking.

[0036] In the present invention, when the C layer is a TPU layer, the TPU in the TPU layer can be a conventional type of TPU in the art, such as polyester-based TPU, polyether-based TPU, or aliphatic TPU, preferably polyester-based TPU.

[0037] In the present invention, when the C layer is a TPU layer, the TPU layer can be prepared from TPU in particle form. The hardness of the TPU in particle form can be 80 - 95 Shore A, preferably 80 - 85 Shore A, such as 85 Shore A. The amount of the TPU used can be 50 - 100%, preferably 100%. The percentage refers to the percentage of the TPU in the total mass of the TPU layer.

[0038] In the present invention, when the C layer is a PVC layer, the PVC in the PVC layer can be a conventional type of PVC in the art, such as polyvinyl chloride copolymer or polyvinyl chloride resin. The amount of the PVC used can be 50 - 100%, preferably 100%. The percentage refers to the percentage of the PVC in the total mass of the TPU layer.

[0039] The present invention also provides a type II composite film, which comprises a B layer and a C layer stacked in sequence;

[0040] The B layer is a PU layer;

[0041] The preparation steps of the PU layer include: coating the PU slurry on the super matte PP synthetic paper layer, drying, and removing the super matte PP synthetic paper layer.

[0042] The C layer is a TPU layer or a PVC layer.

[0043] In the present invention, the thickness of the PU layer is as described above.

[0044] In the present invention, the C layer is preferably a TPU layer.

[0045] In the present invention, when the C layer is a TPU layer, the thickness of the TPU layer is as described above.

[0046] In the present invention, when the C layer is a PVC layer, the thickness of the PVC layer is as described above.

[0047] In the present invention, the type of the super matte PP synthetic paper is as described above.

[0048] In the present invention, the size of the super matte PP synthetic paper is as described above.

[0049] In the present invention, the thickness of the super matte PP synthetic paper is as described above.

[0050] In the present invention, the PU slurry is as described above.

[0051] In the present invention, the drying method and conditions are as described above.

[0052] In the present invention, the method and conditions for removing the super matte PP synthetic paper layer can be conventional methods and conditions in the art. For example, the super matte PP synthetic paper can be torn off.

[0053] In the present invention, when the C layer is a TPU layer, the type of TPU in the TPU layer is as described above.

[0054] In the present invention, when the C layer is a TPU layer, the dosage of TPU in the TPU layer is as described above.

[0055] In the present invention, when the C layer is a PVC layer, the type of PVC in the PVC layer is as described above.

[0056] In the present invention, when the C layer is a PVC layer, the dosage of PVC in the PVC layer is as described above.

[0057] The present invention also provides a method for preparing the type I composite film as described above, which comprises the following steps:

[0058] S1. Prepare a PU film: Coating the PU slurry on the super matte PP synthetic paper and drying;

[0059] S2. Prepare a TPU film or a PVC film: Subjecting TPU or PVC to film-forming treatment;

[0060] S3. Prepare a composite film: Combining the side of the PU film that is not coated with the PU slurry with the TPU film or the PVC film.

[0061] In step S1 of the present invention, the super matte PP synthetic paper is preferably the super matte PP synthetic paper with the model number HYL-020 and the manufacturer being Suzhou Libiao Packaging Company.

[0062] In step S1 of the present invention, the size of the super matte PP synthetic paper can be a conventional size in the art. For example, the width of the super matte PP synthetic paper can be 1200 - 1800 mm, preferably 1600 mm.

[0063] In step S1 of the present invention, the roll length of the super matte PP synthetic paper can be 100 - 1000 m, preferably 1000 m.

[0064] In step S1 of the present invention, the PU slurry can be prepared by a conventional method in the art. For example, it includes the following preparation steps: Mix the solution containing PU evenly.

[0065] Among them, the PU can be a conventional type of PU in the art, such as polyester type PU, polyether type PU or aliphatic PU, preferably polyester type PU, such as polyurethane resin.

[0066] When the weight parts of the PU slurry are 150 - 200 parts, such as 179.3 parts, the weight parts of the PU can be 100 - 200 parts, preferably 100 parts. The weight parts refer to the weight parts of the PU accounting for the total weight of the raw materials of the PU slurry.

[0067] Among them, the solvent of the solution containing PU can be a conventional solvent in the art, such as N,N - dimethylformamide (DMF) and / or isobutanol (IBA), preferably N,N - dimethylformamide (DMF) and isobutanol (IBA).

[0068] Among them, the dosage of the solvent of the solution containing PU can be a conventional dosage in the art, generally just enabling the PU to be dispersed. For example, when the weight parts of the PU in the solution containing PU are 100 - 200 parts, such as 100 parts, the weight parts of the solvent can be 10 - 80 parts, preferably 15 - 60 parts. The weight parts refer to the weight parts of the solvent accounting for the total weight of the solution containing PU.

[0069] In step S1 of the present invention, the solution containing PU generally further includes additives. The additives can be one or more of a diluent, a colorant, a matting agent, a toner and a leveling agent, preferably a matting agent, a leveling agent, a diluent and a toner.

[0070] When the additives include a diluent, the diluent can be a conventional diluent in the art, preferably 2 - butanone and / or N,N - dimethylformamide, more preferably 2 - butanone.

[0071] When the weight part of PU in the solution containing PU is 100 - 200 parts, for example 100 parts, the weight part of the diluent can be 20 - 100 parts, preferably 45 - 80 parts. The weight part refers to the weight part of the diluent in the total weight of the raw materials of the PU slurry.

[0072] When the auxiliary agent includes a colorant, the colorant can be a conventional colorant in the art, preferably a color powder. The color powder can be one or more of ferric sulfate, cobalt aluminate, lead chromate, iron zincate, and high - pigment carbon black, preferably high - pigment carbon black.

[0073] When the weight part of PU in the solution containing PU is 100 - 200 parts, for example 100 parts, the weight part of the colorant can be 1 - 20 parts, preferably 4 - 10 parts. The weight part refers to the weight part of the colorant in the total weight of the raw materials of the PU slurry.

[0074] When the auxiliary agent includes a leveling agent, the leveling agent can be a conventional leveling agent in the art, preferably one or more of polyacrylic acid, carboxymethyl cellulose, polymethylphenylsiloxane, and dimethylsiloxane, more preferably dimethylsiloxane.

[0075] When the weight part of PU in the solution containing PU is 100 - 200 parts, for example 100 parts, the weight part of the leveling agent can be 0.1 - 10 parts, preferably 0.3 - 5 parts. The weight part refers to the weight part of the leveling agent in the total weight of the raw materials of the PU slurry.

[0076] When the auxiliary agent includes a matting agent, the matting agent can be a conventional matting agent in the art, preferably one or more of silica gel method silica, diatomaceous earth, titanium dioxide, and calcium carbonate, more preferably silica gel method silica.

[0077] When the weight part of PU in the solution containing PU is 100 - 200 parts, for example 100 parts, the weight part of the matting agent can be 1 - 20 parts, preferably 5 - 10 parts. The weight part refers to the weight part of the matting agent in the total weight of the raw materials of the PU slurry.

[0078] Among them, the mixing method can be a conventional method in the art, such as stirring.

[0079] Among them, after mixing, preferably, there is also a standing process. The standing time can be a conventional standing time in the art, preferably 24 h.

[0080] In step S1 of the present invention, the coating method can be a conventional method in the art, preferably knife coating.

[0081] In step S1 of the present invention, the drying method can be a conventional method in the art, such as drying by baking.

[0082] In the present invention, when preparing the TPU film in step S2, the TPU can be a conventional type of TPU in the art, such as polyester-based TPU, polyether-based TPU, or aliphatic TPU, preferably polyester-based TPU. The TPU film can be prepared from TPU in particle form. The hardness of the TPU in particle form can be 80-95 Shore A, preferably 80-85 Shore A, for example 85 Shore A. The dosage of the TPU can be 50-100%, preferably 100%, and the percentage refers to the percentage of the TPU in the total mass of the TPU film.

[0083] In the present invention, when preparing the PVC film in step S2, the PVC can be a conventional type of PVC in the art, such as polyvinyl chloride copolymer or polyvinyl chloride resin. The dosage of the PVC can be 50-100%, preferably 100%, and the percentage refers to the percentage of the PVC in the total mass of the PVC film.

[0084] In step S2 of the present invention, the film-forming treatment method can be a conventional method in the art, such as plasticizing extrusion for film formation.

[0085] In step S3 of the present invention, the combination method can be a conventional method in the art, such as laminating, preferably online laminating.

[0086] The present invention also provides a method for preparing the type II composite film as described above, which includes the following steps:

[0087] S1. Prepare a PU film: Coat the PU slurry on the super-matte PP synthetic paper and dry it;

[0088] S2. Prepare a TPU film or a PVC film: Perform film-forming treatment on the TPU or PVC;

[0089] S3. Prepare the composite film: Combine the side of the PU film that is not coated with the PU slurry with the TPU film or the PVC film, and remove the super-matte PP synthetic paper.

[0090] In step S1 of the present invention, the type of the super-matte PP synthetic paper is as described above.

[0091] In step S1 of the present invention, the size of the super-matte PP synthetic paper is as described above.

[0092] In step S1 of the present invention, the PU slurry is as described above.

[0093] In step S1 of the present invention, the coating method is as described above.

[0094] In step S1 of the present invention, the drying method is as described above.

[0095] When preparing the TPU film in step S2, the type of the TPU is as described above.

[0096] When preparing the TPU film in step S2, the dosage of the TPU is as described above.

[0097] When preparing the PVC film in step S2, the type of the PVC is as described above.

[0098] When preparing the PVC film in step S2, the dosage of the PVC is as described above.

[0099] In step S2 of the present invention, the film-forming treatment method is as described above.

[0100] In step S3 of the present invention, the combination method is as described above.

[0101] In step S3 of the present invention, the method and conditions for removing the super-matte PP synthetic paper can be the conventional methods and conditions in the art. For example, tearing off the super-matte PP synthetic paper is sufficient.

[0102] In some preferred embodiments of the present invention, the method for preparing the type I composite film as described above includes the following steps: First, mix the components of the PU slurry to form the PU slurry, scrape and coat it on the super-matte PP synthetic paper, and obtain the PU film with the super-matte PP synthetic paper after drying in an oven. Then, laminating the PU film on the TPU film online to obtain the composite film of the PU film with the super-matte PP synthetic paper and the TPU film. Specifically as follows:

[0103] S1. Prepare the PU film

[0104] Adjust the distance between the doctor blades, add the prepared PU slurry to the coating table, evenly coat it on the super-matte PP synthetic paper, enter the oven through the conveyor belt for drying, trim the edges and wind it up to obtain the PU film with the super-matte PP synthetic paper;

[0105] Among them, the preparation steps of the PU slurry are as follows:

[0106] Disperse 100 parts of polyester-type polyurethane resin slurry with 15 - 60 parts of DMF (as a solvent) and dilute it with 45 - 80 parts of MEK (as a diluent), then add 4 - 10 parts of color powder, 0.3 - 5 parts of leveling agent, and 5 - 10 parts of matting agent, stir well and let it stand for defoaming for 24 hours;

[0107] The above polyurethane resin is a polyether-type aromatic polyurethane resin slurry with a solid content of 35%, and its solvents are N,N-dimethylformamide (DMF) and isobutanol (IBA);

[0108] DMF is N,N-dimethylformamide;

[0109] MEK is 2-butanone;

[0110] The toner is high pigment carbon black;

[0111] The leveling agent is polydimethylsiloxane;

[0112] The matting agent is silica gel method silica;

[0113] S2. Preparation of TPU film

[0114] Put TPU particles (particle size 0.3 - 0.5 mm, hardness 85 Shore A) into a drying and dehumidifying machine set at a temperature of 100°C and a dew point of -40°C for drying for 3 hours, add them to an extruder through an automatic feeding system for plasticizing and extrusion, and cast them onto a three-roll through a die head, and cool to obtain a TPU film;

[0115] S3. Preparation of composite film

[0116] The above-mentioned PU film and the above-mentioned TPU film are hot-pressed and laminated online through the three rolls in a casting machine, and finally wound up through an online thickness control system and a cooling system to obtain a composite film of the above-mentioned PU film with super-matte PP synthetic paper and the above-mentioned TPU film.

[0117] In some preferred embodiments of the present invention, the method for preparing the type II composite film as described above includes the following steps: First, mix the components of the PU slurry to form a PU slurry and scrape it on the super-matte PP synthetic paper, and obtain a PU film with super-matte PP synthetic paper after drying. Then, laminate the PU film online on the TPU film to obtain a composite film of the PU film with super-matte PP synthetic paper and the TPU film, and remove the super-matte PP synthetic paper in the composite film. Specifically as follows:

[0118] S1. Preparation of PU film

[0119] Adjust the distance between the doctor blades, add the prepared PU slurry to the scraping table, evenly coat it on the super-matte PP synthetic paper, enter the oven through a conveyor belt for drying, cut the edges and wind up to obtain a PU film with super-matte PP synthetic paper;

[0120] Among them, the preparation steps of the PU slurry are as follows:

[0121] Disperse 100 parts of polyester polyurethane resin slurry with 15 - 60 parts of DMF (as a solvent) and dilute it with 45 - 80 parts of MEK (as a diluent), then add 4 - 10 parts of toner, 0.3 - 5 parts of leveling agent, and 5 - 10 parts of matting agent, stir well and let it stand for defoaming for 24 hours;

[0122] The above polyurethane resin is a polyether-based aromatic polyurethane resin slurry with a solid content of 35%, and its solvent is N,N-dimethylformamide (DMF) and isobutanol (IBA).

[0123] DMF is N,N-dimethylformamide;

[0124] MEK is 2-butanone;

[0125] The color powder is high pigment carbon black;

[0126] The leveling agent is polydimethylsiloxane;

[0127] The matting agent is silica gel method silica;

[0128] S2. Preparation of TPU film

[0129] Put the TPU particles (particle size 0.3 - 0.5 mm, hardness 85 Shore A) into a drying and dehumidifying machine set at a temperature of 100°C and a dew point of -40°C for drying for 3 hours, add them into an extruder through an automatic feeding system for plasticizing and extruding, and cast them onto a three-roll by a die head, and cool to obtain a TPU film;

[0130] S3. Preparation of composite film

[0131] The above PU film and the above TPU film are hot-pressed and laminated online through the three rolls in a casting machine, and through an online thickness control system and a cooling system, finally wind up to obtain a composite film of the above PU film and the above TPU film of the super matte PP synthetic paper, and then tear off the super matte PP synthetic paper therein.

[0132] The present invention also provides an application of the type I composite film or type II composite film as described above as a waterproof material, low-temperature resistant material or scratch-resistant material.

[0133] In the present invention, the waterproof material, low-temperature resistant material or scratch-resistant material can be applied to any field, such as the fields of clothing, home decoration, etc.

[0134] In the present invention, the composite film is preferably applied to the waterproof material.

[0135] In the present invention, the waterproof material is preferably a waterproof zipper.

[0136] On the basis of conforming to the common knowledge in the art, the above preferred conditions can be combined arbitrarily to obtain various preferred examples of the present invention.

[0137] The reagents and raw materials used in the present invention are all commercially available.

[0138] The positive and progressive effects of the present invention are as follows: The composite film prepared by the present invention has a good matte effect, a smoother surface, does not turn white, and can simultaneously possess multiple performance effects such as scratch resistance, environmental friendliness, not being prone to embrittlement, and low temperature resistance (it can withstand a low temperature environment of more than minus 50 degrees Celsius and has a low embrittlement temperature). The application prospect of this composite film is broad. Description of the Drawings

[0139] Figure 1 Schematic cross-sectional view of the type I composite film prepared in Example 2.

[0140] Figure 2 Schematic process flow diagram of the preparation of the type I composite film in Example 1.

[0141] Description of the reference numerals:

[0142] Ultra-matte PP synthetic paper layer A

[0143] PU layer B

[0144] TPU layer C Detailed Description of the Invention

[0145] The present invention will be further described below by way of examples, but the present invention is not limited to the scope of the described examples. For the experimental methods without specific conditions in the following examples, they are carried out according to conventional methods and conditions, or selected according to the product specifications.

[0146] In the following examples and comparative examples, unless otherwise specified, other reagent raw materials are all commercially available as conventional products.

[0147] The production factory brands of the raw materials used in the following examples and comparative examples are as follows:

[0148] Polyurethane resin: Huafeng Group JF-A-WV7020.

[0149] DMF (N,N-dimethylformamide): Aite Chemistry.

[0150] MEK (2-butanone): Jiading Chemistry.

[0151] Color powder (high pigment carbon black): Jin Suyan 6439.

[0152] Leveling agent (polydimethylsiloxane): BYK-9565 of BYK.

[0153] Matting agent (gel method silica): SYLOID C810 of Grace.

[0154] Ultra-matte PP synthetic paper: HYL-020 of Suzhou Libiao Packaging.

[0155] Polyester type TPU particles: S85A15 of BASF.

[0156] The preparation process of Example 1 is as Figure 2 shown.

[0157] Example 1 (preparation of type I composite film)

[0158] Step S1: Prepare the PU film: Install a super matte PP synthetic paper (thickness 0.2 mm, 45° glossiness 20 GU, width 1600 mm, roll length 1000 m) on the conveyor belt of the knife coater, and adjust the distance between the knife and the super matte PP synthetic paper to 0.03 mm; Before knife coating, add the prepared PU slurry (prepared and fully stirred according to the ratio of 100 parts of polyurethane resin, 15 parts of solvent DMF, 45 parts of diluent MEK, 0.3 parts of leveling agent, 5 parts of matting agent, and 4 parts of color powder, and let it stand for defoaming for 24 hours), start the machine, and evenly knife coat the PU slurry on the paper; The synthetic paper coated with the PU slurry is conveyed by the conveyor belt to a continuous online drying system set at a temperature of 120 °C, continuously dried for about 5 minutes to the winding device, and the PU film with the super matte PP synthetic paper is wound (wherein the PU film is a solid PU film left after the solvent and diluent in the PU slurry are evaporated after drying);

[0159] Step S2: Prepare the TPU film: Put polyester-based TPU particles (particle size 0.3 - 0.5 mm, hardness 85 Shore A, the dosage of TPU particles accounts for 100% of the total mass of the TPU film layer and all of this dosage of TPU is still in the finally prepared composite film) into a drying and dehumidifying machine set at a temperature of 100 °C and a dew point of -40 °C for drying for 3 hours, add them into the extruder for plasticizing and extruding through the automatic feeding system, and cast them by the die head onto three rolls to obtain the TPU film. During this period, adjust the film thickness to 0.1 mm by adjusting the opening degree of the die head;

[0160] Step S3: Prepare the composite film: Pass the PU film with the super matte PP synthetic paper prepared in Step S2 and the TPU film prepared in Step S3 together through the three rolls in the casting machine (the manufacturer model of the casting machine can be conventional in this field), and thermally press and laminate them online, so that the PU film with the super matte PP synthetic paper contacts the TPU film, and after cooling and releasing the tension, wind it up to obtain the composite film of the PU film with the super matte PP synthetic paper and the TPU film (wherein, the thickness of the TPU layer is 0.1 mm, the thickness of the PU layer is 0.03 mm, and the thickness of the super matte PP synthetic paper layer is 0.2 mm).

[0161] Example 2 (preparation of type I composite film)

[0162] Compared with Example 1, in Example 2, commercially available polyester-based TPU particles (Zengyiheng Plastics (Shenzhen) Co., Ltd.) without any processing, PU film (Suzhou Wobeide Dust-free Materials Co., Ltd.), and super-matte PP synthetic paper (Suzhou Libiao Packaging HYL-020) were used to prepare a composite film of PU film and TPU film with super-matte PP synthetic paper according to the same process as in step S3 of Example 1. The structure of the composite film is as shown in Figure 1 shown (where the thickness of the TPU layer C is 0.1 mm, the thickness of the PU layer B is 0.03 mm, and the thickness of the super-matte PP synthetic paper layer A is 0.2 mm).

[0163] Example 3 (preparation of type II composite film)

[0164] Tear off the super-matte PP synthetic paper in the composite film prepared in Example 1 to obtain the finished composite film.

[0165] Example 4 (preparation of type II composite film)

[0166] Tear off the super-matte PP synthetic paper in the composite film prepared in Example 2 to obtain the finished composite film.

[0167] Example 5 (preparation of type II composite film)

[0168] Adjust the thickness of the PP synthetic paper to 0.5 mm. For the composite film prepared under other conditions the same as in Example 1, tear off the super-matte PP synthetic paper therein in the same method as in Example 3 to obtain the finished composite film.

[0169] Example 6 (preparation of type II composite film)

[0170] Adjust the solvent DMF to 50 parts, the diluent MEK to 75 parts, and the drying time to 15 min. For the composite film prepared under other conditions the same as in Example 1, tear off the super-matte PP synthetic paper therein in the same method as in Example 3 to obtain the finished composite film.

[0171] Example 7 (preparation of type II composite film)

[0172] Adjust the weight fraction of the matting agent to 8 parts. For the composite film prepared under other conditions the same as in Example 1, tear off the super-matte PP synthetic paper therein in the same method as in Example 3 to obtain the finished composite film.

[0173] Example 8 (preparation of type II composite film)

[0174] Adjust the weight fraction of the matting agent to 10 parts. For the composite film prepared under other conditions the same as in Example 1, tear off the super-matte PP synthetic paper therein in the same method as in Example 3 to obtain the finished composite film.

[0175] Example 9 (Preparation of Type II Composite Film)

[0176] Adjust the weight part of the leveling agent to 1 part. For the composite film prepared under the same conditions as in Example 1, tear off the super matte PP synthetic paper therein according to the same method as in Example 3, and the finished composite film can be obtained.

[0177] Example 10 (Preparation of Type II Composite Film)

[0178] Adjust the weight part of the leveling agent to 3 parts. For the composite film prepared under the same conditions as in Example 1, tear off the super matte PP synthetic paper therein according to the same method as in Example 3, and the finished composite film can be obtained.

[0179] Example 11 (Preparation of Type II Composite Film)

[0180] Adjust the weight part of the toner to 6 parts. For the composite film prepared under the same conditions as in Example 1, tear off the super matte PP synthetic paper therein according to the same method as in Example 3, and the finished composite film can be obtained.

[0181] Example 12 (Preparation of Type II Composite Film)

[0182] Adjust the weight part of the toner to 8 parts. For the composite film prepared under the same conditions as in Example 1, tear off the super matte PP synthetic paper therein according to the same method as in Example 3, and the finished composite film can be obtained.

[0183] Example 13 (Adjust the TPU layer of the Type I composite film to the PVC layer)

[0184] Only adjust the polyester-based TPU in Example 1 to polyvinyl chloride (PVC), and the remaining conditions are the same as in Example 1, and the finished composite film of the PU film and the PVC film can be obtained (wherein, the thickness of the PVC layer is 0.1 mm, and the thickness of the PU layer is 0.03 mm).

[0185] Comparative Example 1 (The composite film does not contain the PU film)

[0186] In Comparative Example 1, the TPU film was prepared by the same method as in Step S2 of Example 1, and then the super matte PP synthetic paper (with a thickness of 0.2 mm and a 45° glossiness of 20 GU) in the composite film of the prepared TPU film and the super matte PP synthetic paper was torn off according to the same method as in Step S3 of Example 1, and the finished film can be obtained (wherein, the thickness of the TPU layer is 0.1 mm, and the thickness of the super matte PP synthetic paper layer is 0.2 mm).

[0187] Comparative Example 2 (Preparation of Type II Composite Film, the composite film does not contain the super matte PP synthetic paper)

[0188] In Comparative Example 2, a PU film and a TPU film were prepared by the same method as in Steps S1 - S2 of Example 1, and then a composite film product of the prepared TPU film and PU film was obtained by the same method as in Step S3 of Example 1 (wherein, the thickness of the TPU layer was 0.1 mm and the thickness of the PU layer was 0.03 mm).

[0189] Comparative Example 3 (preparing a Type II composite film)

[0190] The super - matte PP synthetic paper in the composite film prepared in Comparative Example 1 was torn off to obtain the composite film product.

[0191] Comparative Example 4 (in the composite film for preparing a Type II composite film, the super - matte PP synthetic paper was adjusted to a glassine release paper)

[0192] The super - matte PP synthetic paper was replaced with a glassine release paper, and the other conditions were the same as those of the composite film prepared in Example 1. Then, the glassine release paper in it was torn off by the same method as in Example 3 to obtain the composite film product.

[0193] Effect Example 1

[0194] Test object: The composite film products prepared in Examples 3 - 12 and Comparative Examples 2 - 4. When conducting the following tests, the PU layer of the composite film was the test surface, and no special treatment was required during the test. It could be adjusted to the normal state at the laboratory temperature (23°C ± 2).

[0195] Test method: Use a 45° glossmeter (the model and manufacturer of this device are conventional in the art and do not affect the test results) to measure the 45° gloss of the composite film; the specification size of the composite film selected during the test does not affect the test results and can be the conventional size in the art.

[0196] According to the test standard of GB / T 10006 - 1988, measure the static friction coefficient and dynamic friction coefficient of the composite film; the instrument and equipment used for this test are conventional instruments and equipment in the art.

[0197] According to the test standard of ISO 105 - X12:2016, use a 45° glossmeter to measure the 45° gloss of the scratched position of the composite film after scratching 20 times.

[0198] Test results: As shown in Table 1 below.

[0199] Table 1

[0200]

[0201] It can be obtained from the data analysis in Table 1 that:

[0202] From the 45° glossiness, dynamic friction coefficient, and static friction coefficient of the composite films prepared in Examples 3-13 and Comparative Examples 2-4, it can be seen that the 45° glossiness, static friction coefficient, and dynamic friction coefficient of the composite films prepared in Examples 3-13 are all lower than those of the composite films prepared in Comparative Examples 2-4. This shows that the composite films prepared in Examples 3-13 have a better matte effect and a smoother surface.

[0203] The 45° glossiness of the composite film prepared in Example 4 is comparable to that of Examples 3 and 5-13; the dynamic friction coefficient and static friction coefficient of the composite film prepared in Example 4 are comparable to those of Examples 5 and 6 and higher than those of Examples 3 and 7-13; the 45° glossiness of the composite film prepared in Example 4 becomes higher after being scratched 20 times; the low-temperature embrittlement temperature that the composite film prepared in Example 4 can withstand is comparable to that of Examples 3 and 5-12 at -52°C. This shows that the matte effect, surface smoothness effect, low-temperature resistance, and non-brittle performance requirements of the composite film prepared in Example 4 are comparable to those of Examples 3 and 5-13, but only the scratch resistance performance is relatively poor.

[0204] The 45° glossiness of the composite films prepared in Examples 3, 5-13 and Comparative Examples 2, 4 does not change or decreases after being scratched 20 times; none of the composite films contain plasticizers; all the composite films can withstand low temperatures of over -50°C and have a low embrittlement temperature. This shows that the composite films prepared in Examples 3, 5-13 have a better matte effect and a smoother surface, while also having good scratch resistance, no whitening, being green and environmentally friendly, low-temperature resistance, and non-brittle.

[0205] The 45° glossiness, dynamic friction coefficient, and static friction coefficient of the composite films prepared in Examples 3-12 and Example 13 are comparable, and the 45° glossiness does not change after being scratched 20 times. However, the composite film prepared in Example 13 contains plasticizers, and the composite film prepared in Example 13 can only withstand low temperatures of -28°C and becomes brittle. This shows that although the matte effect and surface smoothness effect of Example 13 are comparable to those of Examples 3-12, the composite film prepared in Example 13 cannot simultaneously meet the performance requirements of being green and environmentally friendly, low-temperature resistance, and non-brittle.

[0206] In addition, due to the presence of super-matte PP synthetic paper in the composite films prepared in Examples 1-2, which plays a certain role in stabilizing, supporting, and protecting in the composite films, compared with Examples 3-13 and Comparative Examples 2-3, the performance of the composite films prepared in Examples 1-2 is more durable and stable, and convenient for storage.

Claims

1. A type II composite film, characterized in that, It includes a B layer and a C layer stacked in sequence; The B layer is a PU layer; The PU layer is prepared by the steps of: coating the PU slurry on the super matte PP synthetic paper layer, drying, and removing the super matte PP synthetic paper layer; The C layer is a TPU layer; The PU slurry includes PU and solvent; the PU is polyester PU; When the weight portion of the PU slurry is 150-200 parts, the weight portion of the PU is 100 parts; the weight portion refers to the weight portion of the PU in the total weight of the PU slurry; The PU slurry also includes additives; the additives are matting agent, leveling agent, diluent and colorant; The diluent is 2-butanone; When the weight percentage of PU in the PU slurry is 100 parts, the content of the diluent is 45-80 parts by weight, where the weight percentage refers to the weight percentage of the diluent in the total weight of the PU slurry; The colorant is toner; When the weight percentage of PU in the PU slurry is 100 parts, the content of the colorant is 1-20 parts by weight, where the weight percentage refers to the weight percentage of the colorant in the total weight of the PU slurry; The leveling agent is one or more of polyacrylic acid, carboxymethyl cellulose, polymethylphenylsiloxane and polydimethylsiloxane; When the weight percentage of PU in the PU slurry is 100 parts, the content of the leveling agent is 0.1-10 parts by weight, where the weight percentage refers to the weight percentage of the leveling agent in the total weight of the PU slurry; The matting agent is one or more of gel-process silicon dioxide, diatomaceous earth and calcium carbonate; When the weight percentage of PU in the PU slurry is 100 parts, the content of the matting agent is 1-20 parts by weight, where the weight percentage refers to the weight percentage of the matting agent in the total weight of the PU slurry; The solvent is N,N-dimethylamide and / or isobutyl alcohol; When the weight percentage of PU in the PU slurry is 100 parts, the amount of the solvent is 10-80 parts, where the weight percentage refers to the weight percentage of the solvent in the total weight of the PU slurry; The TPU in the TPU layer is a polyester TPU; the TPU layer is made of TPU in particle form; The TPU particles have a particle size of 0.3-0.5 mm and a hardness of 85 Shore A; The amount of TPU in the TPU layer is 50-100%; the percentage refers to the percentage of the TPU in the total mass of the TPU layer.

2. The type II composite film according to claim 1, characterized in that: The thickness of the PU layer is 0.01-0.05 mm; The thickness of the TPU layer is 0.05-0.5 mm; And / or, the super matte PP synthetic paper is a super matte PP synthetic paper of model HYL-020, manufactured by Suzhou Libiao Packaging Co., Ltd.; And / or, the width of the super matte PP synthetic paper is 1200-1800 mm; And / or, the roll length of the super matte PP synthetic paper is 100-1000m; And / or, the thickness of the super matte PP synthetic paper is 0.1-0.5 mm; Alternatively, the method of removing the super-matte PP synthetic paper layer is to tear off the super-matte PP synthetic paper; And / or, the PU is polyurethane resin; And / or, when the weight fraction of the PU slurry is 179.3 parts, the weight fraction of the PU is 100 parts, and the weight fraction refers to the weight fraction of the PU in the total weight of the PU slurry; And / or, the toner is one or more of ferric sulfate, cobalt aluminate, lead chromate, iron zincate, and high pigment carbon black; And / or, when the weight fraction of the PU in the PU slurry is 100 parts, the content of the colorant is 4-10 parts by weight, and the weight fraction refers to the weight fraction of the colorant in the total weight of the PU slurry; And / or, the leveling agent is polydimethylsiloxane; And / or, when the weight fraction of the PU in the PU slurry is 100 parts, the content of the leveling agent is 0.3-5 parts by weight, and the weight fraction refers to the weight fraction of the leveling agent in the total weight of the PU slurry; And / or, the matting agent is silica gel method silica; And / or, when the weight fraction of the PU in the PU slurry is 100 parts, the content of the matting agent is 5-10 parts by weight, and the weight fraction refers to the weight fraction of the matting agent in the total weight of the PU slurry; And / or, the solvent is N,N-dimethylformamide and isobutanol; And / or, when the weight fraction of the PU in the PU slurry is 100 parts, the amount of the solvent is 15-60 parts by weight, and the weight fraction refers to the weight fraction of the solvent in the total weight of the PU slurry; And / or, the amount of TPU in the TPU layer is 50-100%, and the percentage refers to the percentage of TPU in the total mass of the TPU layer.

3. The type II composite film according to claim 2, wherein The width of the super-matte PP synthetic paper layer is 1600 mm; And / or, the roll length of the super-matte PP synthetic paper layer is 1000 m; And / or, the thickness of the super-matte PP synthetic paper layer is 0.2-0.5 mm; And / or, the thickness of the PU layer is 0.03-0.05 mm; And / or, the thickness of the TPU layer is 0.05-0.5 mm; And / or, the toner is high pigment carbon black; And / or, the hardness of the particulate TPU is 85 Shore A; And / or, the amount of TPU in the TPU layer is 100%, and the percentage refers to the percentage of TPU in the total mass of the TPU layer.

4. The type II composite film according to claim 2, wherein The thickness of the TPU layer is 0.1-0.5 mm.

5. A method for preparing a type II composite film according to any one of claims 1-4, characterized in that, It includes the following steps: S1. Prepare a PU film: Coat the PU slurry on the super-matte PP synthetic paper and dry it; S2. Prepare a TPU film: Perform film-forming treatment on the TPU; S3. Prepare a composite film: Combine the side of the PU film coated with the PU slurry with the TPU film and remove the super-matte PP synthetic paper.

6. The method for preparing a type II composite film according to claim 5, wherein In step S1, the preparation steps of the PU slurry include: Mix the solution containing PU evenly. And / or, when the weight part of PU in the PU-containing solution is 100 parts, the weight part of the solvent is 15 - 60 parts, and the weight part refers to the weight part of the solvent in the total weight of the PU-containing solution; And / or, in step S1, the coating method is knife coating; And / or, in step S1, the drying method is drying in an oven.

7. The method for preparing the type II composite film according to claim 5, characterized in that, In step S2, the film forming treatment method is plasticizing extrusion film forming; And / or, in step S3, the combination method is laminating; And / or, in step S3, the method for removing the super matte PP synthetic paper is to simply tear off the super matte PP synthetic paper.

8. The method for preparing the type II composite film according to claim 6, characterized in that, The mixing method is stirring; And / or, after the mixing, a standing process is further included.

9. The method for preparing the type II composite film according to claim 7, characterized in that, In step S3, the combination method is online laminating.

10. The method for preparing the type II composite film according to claim 8, characterized in that, The standing time is 24 h.

11. Application of the type II composite film according to any one of claims 1 - 4 as a waterproof material, low temperature resistant material or scratch resistant material.

12. The application according to claim 11, wherein The type II composite film as a waterproof material.

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