A NCO group-containing adhesive-free protective film, a preparation method and application thereof

Abstract

The present application relates to the technical field of automobile glass protective film, in particular to a NCO group-containing adhesive-free protective film and a preparation method and application thereof. The NCO group-containing adhesive-free protective film comprises at least one substrate layer, and the substrate layer is mainly prepared from a material containing a NCO group. The NCO group-containing adhesive-free protective film can be firmly attached to the surface of glass without using adhesive, and has the effect of explosion prevention.

Description

Technical Field

[0001] This invention relates to the field of automotive glass protective film technology, and more specifically, to an adhesive-free protective film containing NCO groups, its preparation method, and its application. Background Technology

[0002] The main functions of current window films are explosion protection and blocking ultraviolet rays and external heat. The main method is to coat one side of the PET film with a metallic reflective layer (anti-UV and heat-blocking additives) and apply an adhesive to the other side, such as patents CN104175664B and CN102229787B. This allows the window film to be firmly adhered to the glass to protect its explosion-proof performance. Most of the adhesives used are acrylic pressure-sensitive adhesives, and most protective films are installed inside the glass, which gives the glass its explosion-proof properties.

[0003] However, while the above methods achieve explosion-proof protection, they also have certain drawbacks and hazards. For example, when a car falls into water, it is difficult to break the side window glass from the inside of the car. The main reason is the installation adhesive. The adhesive is an adhesive with high viscosity and damping, which hinders the transmission of vibration waves when subjected to external impact, preventing the glass from breaking and thus preventing the occupants from escaping. Furthermore, this type of window film, installed inside the car, will release toxic gases from the adhesive after prolonged exposure to sunlight, and the adhesive will age, leading to bubbling or residue, posing a safety hazard.

[0004] In view of this, the present invention is hereby proposed. Summary of the Invention

[0005] The primary objective of this invention is to provide an adhesive-free protective film containing NCO groups. This adhesive-free protective film containing NCO groups can be firmly adhered to the glass surface without the use of adhesives, and also has an explosion-proof function.

[0006] The second objective of this invention is to provide a method for preparing the adhesive-free protective film containing NCO groups.

[0007] A third objective of this invention is to provide the application of the adhesive-free protective film containing NCO groups in automotive glass.

[0008] In order to achieve the above-mentioned objectives of the present invention, the following technical solution is adopted:

[0009] The present invention provides an adhesive-free protective film containing NCO groups, wherein the adhesive-free protective film containing NCO groups includes at least one substrate layer, and the substrate layer is mainly made of a material containing NCO groups.

[0010] This invention further provides a method for preparing the adhesive-free protective film containing NCO groups, comprising the following steps:

[0011] The raw materials for preparing the substrate layer are coated and dried using a coating method. After film formation, the substrate layer is formed, resulting in the adhesive-free protective film containing NCO groups.

[0012] And / or, by using a casting method, the raw materials for preparing the substrate layer are melted, extruded, and cast into a film to form the substrate layer, thereby obtaining the adhesive-free protective film containing NCO groups;

[0013] The raw materials used to prepare the substrate layer include materials containing NCO groups;

[0014] Optionally, the raw materials for preparing the substrate layer also include additives.

[0015] The present invention also provides the application of the adhesive-free protective film containing NCO groups in glass, wherein the adhesive-free protective film containing NCO groups is completely adhered to at least one surface of the glass as a protective film, and there is no adhesive between the adhesive-free protective film containing NCO groups and the glass, and a vacuum layer is formed between the adhesive-free protective film containing NCO groups and the glass.

[0016] Preferably, the glass includes at least one of automotive glass and architectural glass;

[0017] More preferably, the automotive glass includes at least one of automotive window glass and automotive windshield glass;

[0018] More preferably, the architectural glass includes at least one of window and door glass, wall glass, and exterior decorative glass.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0020] (1) The adhesive-free protective film containing NCO groups provided by the present invention can be firmly attached to the glass surface without the use of adhesives, and can replace conventional protective films containing adhesives, making it safer.

[0021] (2) The adhesive-free protective film containing NCO groups provided by the present invention is free of adhesives, which can not only reduce VOC content and be more environmentally friendly, but also reduce costs.

[0022] (3) The adhesive-free protective film containing NCO groups provided by the present invention also has functions such as blocking ultraviolet rays, heat insulation, and reflecting heat and light. Attached Figure Description

[0023] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0024] Figure 1 This is a schematic diagram of the structure of the adhesive-free protective film provided in Embodiment 5 of the present invention;

[0025] Figure 2 This is a schematic diagram of the structure of the adhesive-free protective film provided in Embodiment 13 of the present invention. Detailed Implementation

[0026] The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and specific embodiments. However, those skilled in the art will understand that the embodiments described below are some embodiments of the present invention, but not all embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0027] In a first aspect, the present invention provides an adhesive-free protective film for glass that does not contain mounting adhesive (i.e., adhesive) and contains NCO groups (isocyanate groups, -NCO), the adhesive-free protective film containing NCO groups comprising at least one substrate layer, the substrate layer being mainly made of a material containing NCO groups.

[0028] In other words, the substrate layer of the adhesive-free protective film provided by this invention contains NCO groups. This substrate layer is primarily made from materials containing NCO groups, but it is understood that other raw materials, such as solvents, colorants, or functional additives, may be optionally added during the preparation of the substrate layer.

[0029] It is understandable that materials containing NCO groups may have some unreacted NCO groups remaining after being formed into a substrate layer. This invention utilizes the principle of NCO groups reacting with active hydrogen to form a negative pressure layer, achieving an adhesive bonding effect even without the use of adhesives.

[0030] To address the safety hazards posed by existing window films due to the presence of adhesive, this invention provides an adhesive-free protective film. When used as a protective film on glass, this film eliminates the need for adhesive. Because it contains NCO groups, during application, only an active hydrogen coating material needs to be introduced to react the NCO groups with the active hydrogen. A brushing process then forms a vacuum adsorption layer, firmly adsorbing and bonding the film to the glass. This retains the original explosion-proof function of the protective film without posing any safety hazards.

[0031] At the same time, since the surface of the adhesive-free protective film does not contain installation adhesive, it reduces costs on the one hand and reduces VOC (volatile organic compounds) content on the other.

[0032] Understandably, once the balance is disrupted and the vacuum layer becomes an atmospheric pressure layer, this adsorption force is lost, making it very easy for the adhesive-free protective film to detach from the glass. Therefore, when an adhesive-free protective film is needed, it is only necessary to break a section of the film to allow air to enter, thus breaking the vacuum layer formed between the film and the glass, and the adhesive-free protective film can be separated / removed.

[0033] In some specific implementations, a sharp instrument can be used to puncture or scratch the adhesive-free protective film to allow air to enter.

[0034] Furthermore, since no installation adhesive is used, there will be no adhesive residue on the glass surface after peeling.

[0035] Therefore, the adhesive-free protective film provided by this invention solves the drawbacks of traditional adhesive protective films, making it safer, more environmentally friendly, and cost-effective.

[0036] Taking car window film as an example, the area of ​​window film needed for a car (4 sides + front and rear) is: 10 meters × 0.8 meters = 8 square meters / vehicle; China's car sales volume is 20 million (calculated at 80%) / year, that is, 16 million vehicles × 8 square meters = 130 million square meters / year; the amount of adhesive needed per square meter is 30 microns, 1.2 tons / cubic meter, that is, 36 grams of adhesive per square meter, totaling 36 × 130 million / 1000 = 4680 tons of adhesive.

[0037] Promote source substitution projects for raw materials and products, and implement comprehensive pollution control throughout the entire process. Focusing on industries such as industrial coating and packaging printing, promote the use of coatings, inks, adhesives, and cleaning agents with low volatile organic compound (VOC) content. By 2025, the usage ratio of solvent-based industrial coatings and inks will decrease by 20 percentage points and 10 percentage points respectively, and the usage of solvent-based adhesives will decrease by 20%. Using the adhesive-free protective film of this invention can save at least 2,300 tons of adhesive annually (calculated at 50%).

[0038] In some specific embodiments, the material containing NCO groups includes polyurethane.

[0039] It is understood that the polyurethane mentioned above includes liquid polyurethane and / or particulate polyurethane, and can be produced by any commercially available or conventional method. This invention does not limit the types of polyurethane used.

[0040] In some specific embodiments, the raw materials used to prepare the substrate layer also include additives. These additives include any conventional or commercially available functional additives used in automotive window films or glass films.

[0041] In some specific embodiments, the additive includes at least one of ultraviolet absorbers, light stabilizers, and heat-insulating agents, but is not limited thereto.

[0042] Adding additives to the raw materials during the preparation of the substrate layer can give the resulting adhesive-free protective film the function of blocking ultraviolet rays and / or heat insulation.

[0043] In some specific embodiments, the mass of the ultraviolet absorber added is 0.1% to 0.5% of the mass of the material containing NCO groups, for example, 0.2%, 0.3% or 0.4%.

[0044] In some specific embodiments, the light stabilizer is added at a mass of 0.1% to 0.5% of the mass of the material containing NCO groups, for example, 0.2%, 0.3%, or 0.4%.

[0045] In some specific embodiments, the heat insulation additive (i.e., heat insulation material) is added at a mass of 0.1% to 0.5% of the mass of the material containing NCO groups, for example, 0.2%, 0.3%, or 0.4%.

[0046] The ultraviolet absorber includes any conventional or commercially available ultraviolet absorber, preferably T-571 ultraviolet absorber manufactured by BASF AG, Germany, but is not limited thereto.

[0047] The light stabilizer includes any conventional or commercially available light stabilizer, preferably light stabilizer 292, but is not limited thereto.

[0048] The thermal insulation additive includes any conventional or commercially available thermal insulation additive, preferably N,N,N',N'-tetratetra[4-(dibutylamino)phenyl]-1,4-cyclohexadiene-3,6-diammonium hexafluoroantimonate, but is not limited thereto.

[0049] In some specific embodiments, the adhesive-free protective film containing NCO groups further includes a carrier layer that is stacked and connected to the substrate layer.

[0050] Adding a carrier layer enables the adhesive-free protective film to have better scratch and puncture resistance without affecting the film's adhesion.

[0051] In some specific embodiments, the support layer includes a thermosetting material support layer and / or a thermoplastic material support layer.

[0052] In some specific embodiments, the thermosetting material carrier layer includes at least one of a PET (polyethylene terephthalate) layer, a PTFE (polytetrafluoroethylene) layer, and a PVDF (polyvinylidene fluoride) layer, but is not limited thereto.

[0053] In some specific embodiments, the thermoplastic material support layer includes a polyurethane (PU) layer, but is not limited thereto.

[0054] In some specific embodiments, the thickness of the carrier layer is 10 to 100 μm, including but not limited to any one of 15 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, and 90 μm, or any range between two of them; preferably 19 to 75 μm.

[0055] In some specific embodiments, the adhesive-free protective film containing NCO groups further includes a metal reflective layer, which is disposed on the surface of the substrate layer or the carrier layer. The metal reflective layer primarily serves to reflect heat and light.

[0056] In some specific implementations, the metal reflective layer can be selected based on whether the function of reflecting light and heat is required.

[0057] In some specific embodiments, the metal reflective layer includes a silver layer and / or an aluminum layer.

[0058] In some specific embodiments, a release film is also provided on at least one surface of the substrate layer.

[0059] Release film refers to a film with a distinguishable surface. When in contact with specific materials under limited conditions, the release film exhibits little or no stickiness. The main functions of release film are isolation, filling, protection, and ease of peeling.

[0060] In some specific embodiments, when the adhesive-free protective film includes a carrier layer, the release film is disposed on the surface of the carrier layer.

[0061] In some specific embodiments, when the adhesive-free protective film includes a metal reflective layer, the release film is disposed on the surface of the metal reflective layer.

[0062] The release films mentioned above include any conventional or commercially available release films.

[0063] In some specific embodiments, the adhesive-free protective film consists of a substrate layer and release films disposed on both sides of the substrate layer, wherein the substrate layer is made of a material containing NCO groups.

[0064] In some specific embodiments, the adhesive-free protective film consists of a substrate layer and release films disposed on both sides of the substrate layer, wherein the substrate layer is made of a material containing NCO groups and additives.

[0065] In some specific embodiments, the adhesive-free protective film consists of two interconnected substrate layers and release films disposed on the upper and lower surfaces of the two substrate layers, respectively. Both substrate layers are made of materials containing NCO groups.

[0066] In some specific embodiments, the adhesive-free protective film consists of two interconnected substrate layers and release films disposed on the upper and lower surfaces of the two substrate layers, respectively. Both substrate layers are made of materials containing NCO groups and additives.

[0067] In some specific embodiments, the adhesive-free protective film consists of two interconnected substrate layers and release films disposed on the upper and lower surfaces of the two substrate layers respectively. One substrate layer is made of a material containing NCO groups, and the other substrate layer is made of a material containing NCO groups and additives.

[0068] In some specific embodiments, the adhesive-free protective film consists of a first release film, a first substrate layer, a second substrate layer, and a second release film stacked sequentially. The first substrate layer is made of a material containing NCO groups, and the second substrate layer is made of a material containing NCO groups and additives.

[0069] In some specific embodiments, the adhesive-free protective film comprises a first release film, a first substrate layer, a metal reflective layer, a second substrate layer, and a second release film, which are sequentially stacked. The first substrate layer is made of a material containing NCO groups, and the second substrate layer is made of a material containing NCO groups and additives.

[0070] In some specific embodiments, the adhesive-free protective film comprises a first release film, a first substrate layer, a carrier layer, a second substrate layer, and a second release film, which are sequentially stacked. The first substrate layer is made of a material containing NCO groups, and the second substrate layer is made of a material containing NCO groups and additives.

[0071] In some specific embodiments, the adhesive-free protective film comprises a first release film, a first substrate layer, a carrier layer, a metal reflective layer, a second substrate layer, and a second release film, which are sequentially stacked. The first substrate layer is made of a material containing NCO groups, and the second substrate layer is made of a material containing NCO groups and additives.

[0072] It is understandable that the substrate layer obtained after adding the above-mentioned additives is a functional material layer with certain functions.

[0073] In some specific embodiments, the thickness of the substrate layer is 10 to 150 μm, including but not limited to any one of 15 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 120 μm, and 130 μm, or a range between any two; preferably 25 to 100 μm.

[0074] In some specific implementations, the release film includes a non-silicone release film.

[0075] In some specific implementations, the non-silicone release film includes a PET non-silicone release film.

[0076] In some specific embodiments, the thickness of the release film is 10 to 150 μm, including but not limited to any one of 15 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 130 μm, and 140 μm, or a range between any two; preferably 19 to 100 μm.

[0077] In some specific embodiments, the release force of the release film is 1 to 10g, including but not limited to a point value of any one of 2g, 3g, 4g, 5g, 6g, 7g, 8g, and 9g, or a range between any two.

[0078] Secondly, the present invention provides a method for preparing the adhesive-free protective film containing NCO groups, including a coating method and a casting method, specifically including the following steps:

[0079] The coating method is used: the raw materials for preparing the substrate layer are coated and dried, and the substrate layer is formed after film formation, thus obtaining the adhesive-free protective film containing NCO groups.

[0080] And / or, using a casting method: the raw materials for preparing the substrate layer are melted, extruded, and cast into a film to form the substrate layer, thereby obtaining the adhesive-free protective film containing NCO groups.

[0081] The raw materials for preparing the substrate layer include materials containing NCO groups; optionally, the raw materials for preparing the substrate layer also include additives. Here, "optional" means that additives may or may not be added to the raw materials for preparing the substrate layer.

[0082] The method for preparing an adhesive-free protective film containing NCO groups provided by this invention is simple to operate, has a short process flow, and is suitable for mass production. Furthermore, the adhesive-free protective film obtained by the above method contains a large number of free NCO groups, which is beneficial for improving the adhesion between the adhesive-free protective film and glass.

[0083] Preferably, the adhesive-free protective film is prepared by coating. This is because adhesive-free protective films prepared by coating have higher transparency, more free NCO groups, and better adhesion to glass than those prepared by casting.

[0084] In some specific embodiments, the coating method includes the following steps: coating the raw materials for preparing the substrate layer onto the surface of the release film, drying it to form a substrate layer, and obtaining the adhesive-free protective film containing NCO groups.

[0085] In some specific embodiments, the coating method includes the following steps: coating the raw material for preparing the substrate layer onto the surface of the release film, and drying it to form a first substrate layer; (a) coating the raw material for preparing the substrate layer onto the surface of the first substrate layer, and drying it to form a second substrate layer; repeating step (a) at least once to form at least two substrate layers to obtain the adhesive-free protective film containing NCO groups.

[0086] In some specific embodiments, the coating method includes the following steps: coating the raw materials for preparing the substrate layer onto the surface of the carrier layer, and drying to obtain the adhesive-free protective film containing NCO groups, which includes a substrate layer and a carrier layer.

[0087] In some specific embodiments, the coating method includes the following steps: coating the raw materials for preparing the substrate layer onto the two surfaces of the carrier layer respectively, and drying them to form substrate layers respectively disposed on both sides of the carrier layer, thereby obtaining the adhesive-free protective film containing NCO groups comprising two substrate layers and one carrier layer.

[0088] In some specific embodiments, the method for preparing the adhesive-free protective film containing NCO groups further includes: performing magnetron sputtering or vacuum evaporation on the surface of the substrate layer to form a metal reflective layer; or performing magnetron sputtering or vacuum evaporation on the surface of the carrier layer to form a metal reflective layer.

[0089] In some specific implementations, the metal targets used in magnetron sputtering include silver targets and / or aluminum targets.

[0090] Thirdly, the present invention provides the application of the adhesive-free protective film containing NCO groups in glass, wherein the adhesive-free protective film containing NCO groups is completely adhered to at least one surface of the glass as a protective film, and there is no adhesive between the adhesive-free protective film containing NCO groups and the glass, and a vacuum layer is formed between the adhesive-free protective film containing NCO groups and the glass.

[0091] This invention utilizes the principle of reaction between materials containing NCO groups and active hydrogen materials. The active hydrogen material acts as a curing agent, reacting with the NCO-containing material to form a curing reaction. Taking water as an example, one water molecule reacts with two NCO groups to generate substituted urea and carbon dioxide. The original NCO groups are replaced by substituted urea, while the carbon dioxide is displaced due to atmospheric pressure and gravity. Simultaneously, a vacuum / negative pressure is created where the water was. Under atmospheric pressure, the adhesive-free protective film containing NCO groups and the glass utilize the difference between atmospheric pressure and negative pressure to generate adsorption force, thus forming a vacuum layer after the reaction. Atmospheric pressure tightly bonds the adhesive-free protective film containing NCO groups and the glass together, thereby achieving the explosion-proof function.

[0092] Understandably, when it is necessary to break a car window, it is only necessary to damage the adhesive-free protective film containing NCO groups. Once air enters, the vacuum layer is broken, and the adhesive-free protective film containing NCO groups can be separated from the car window.

[0093] Furthermore, when additives are added during the preparation of the substrate layer, the adhesive-free protective film provided by this invention also has the function of blocking ultraviolet rays and / or heat insulation.

[0094] In some specific embodiments, the glass includes at least one of automotive glass and architectural glass, but is not limited thereto.

[0095] In some specific embodiments, the automotive glass includes at least one of automotive window glass and automotive windshield glass, but is not limited thereto.

[0096] In some specific embodiments, the architectural glass includes at least one of window and door glass, wall glass, and exterior decorative glass, but is not limited thereto.

[0097] In some specific embodiments, the method of complete bonding includes: coating the surface of the adhesive-free protective film containing NCO groups and / or the glass with an active hydrogen material, then bonding the adhesive-free protective film containing NCO groups and the glass together, while simultaneously reacting the NCO groups and the active hydrogen, and then expelling the active hydrogen material and air to form the vacuum layer, thereby completing the bonding.

[0098] In some specific embodiments, the active hydrogen material includes at least one of water, alcohol, and acid, but is not limited thereto.

[0099] When the active hydrogen material is reacted with water, the above reaction principle is: 2RNCO + H2O → RNHCONHR + CO2.

[0100] In some specific embodiments, the alcohols mentioned above include any kind of alcohols, such as methanol, ethanol, propanol, butanol, octanol, pentanol, hexanol, heptanol, decanol, ethylene glycol, glycerol, propylene glycol, pentaerythritol, propylene alcohol, vinyl alcohol, etc., but are not limited thereto.

[0101] In some specific embodiments, the acid includes any kind of acid, including organic acids and inorganic acids. Organic acids include, but are not limited to, formic acid, acetic acid, propionic acid, butyric acid, octanoic acid, adipic acid, oxalic acid, malonic acid, succinic acid, maleic acid, tartaric acid, benzoic acid, phenylacetic acid, valeric acid, hexanoic acid, and decanoic acid. Inorganic acids include, but are not limited to, hydrochloric acid, sulfuric acid, and nitric acid.

[0102] The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer are followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0103] Example 1

[0104] The adhesive-free protective film provided in this embodiment consists of a carrier layer, a substrate layer, and a release film stacked sequentially.

[0105] The adhesive-free protective film provided in this embodiment is prepared by a coating method, specifically including the following steps: Liquid polyurethane (Liaoning Fubai High-Tech Materials Co., Ltd., FBK-TB120325) is uniformly coated onto one side surface of the carrier layer (optical PET film produced by Kanghui New Materials Technology Co., Ltd., with a thickness of 50μm) using a coating machine, and then baked in an oven at 120℃ for 15 minutes to form a polyurethane film with a dry film thickness of 60μm, i.e., the substrate layer. Then, a PET non-silicone release film (with a thickness of 50μm and a release force of 5g) is attached to the surface of the substrate layer (the side away from the carrier layer), and then wound up. After winding, it is placed in a curing chamber at 60℃ for 60 hours to obtain the adhesive-free protective film.

[0106] Example 2

[0107] The preparation method of the adhesive-free protective film provided in this embodiment is basically the same as that in Example 1. The difference is that, before coating, liquid polyurethane is mixed evenly with T-571 ultraviolet absorber produced by BASF AG, Germany; wherein, the mass of T-571 ultraviolet absorber is 0.3% of the mass of liquid polyurethane.

[0108] Example 3

[0109] The preparation method of the adhesive-free protective film provided in this embodiment is basically the same as that in Example 1, except that before coating, the liquid polyurethane and light stabilizer 292 are mixed evenly; wherein, the mass of light stabilizer 292 is 0.1% of the mass of liquid polyurethane.

[0110] Example 4

[0111] The preparation method of the adhesive-free protective film provided in this embodiment is basically the same as that in Example 1. The difference is that, before coating, liquid polyurethane and heat insulation additive N,N,N',N'-tetratetra[4-(dibutylamino)phenyl]-1,4-cyclohexadiene-3,6-diammonium hexafluoroantimonate are mixed evenly; wherein, the mass of the heat insulation additive is 0.5% of the mass of liquid polyurethane.

[0112] Example 5

[0113] The adhesive-free protective film provided in this embodiment consists of a first release film, a first substrate layer, a carrier layer, a second substrate layer, and a second release film stacked sequentially.

[0114] The method for preparing the adhesive-free protective film provided in this embodiment is a coating method, which specifically includes the following steps:

[0115] (1) Liquid polyurethane (produced by Liaoning Fubai High-Tech Materials Co., Ltd., FBK-TB120325) was uniformly coated on one side of the carrier layer (optical PET film produced by Kanghui New Materials Technology Co., Ltd., with a thickness of 30μm) using a coating machine. Then, it was placed in an oven at 120℃ and baked for 15 minutes to form a polyurethane film with a dry film thickness of 40μm, which is the first substrate layer. Then, a PET non-silicone release film (with a thickness of 50μm and a release force of 5g, i.e., the first release film) was attached to the surface of the first substrate layer (the side away from the carrier layer). Then, it was wound up and placed in a curing chamber at 50℃ for 72 hours to obtain the composite layer.

[0116] (2) Acrylic-modified polyurethane (Liaoning FBK-NKTSH) was uniformly coated on the other side of the carrier layer of the composite layer obtained in step (1) (the side away from the first substrate layer) using a coating machine. Then, it was baked in an oven at 110°C for 10 minutes to form a second substrate layer with a dry film thickness of 20 μm. Then, a PET non-silicone release film (thickness of 30 μm, release force of 3g, i.e., the second release film) was attached to the surface of the second substrate layer and wound up. After winding, it was placed in a curing chamber at 60°C for 72 hours to obtain an adhesive-free protective film.

[0117] See the schematic diagram of the layer structure of the adhesive-free protective film prepared in this embodiment. Figure 1 As shown.

[0118] Example 6

[0119] The preparation method of the adhesive-free protective film provided in this embodiment is basically the same as that in Example 5. The difference is that in step (2), before coating, the acrylic modified polyurethane is mixed evenly with T-571 ultraviolet absorber and heat insulation agent N,N,N',N'-tetratetra[4-(dibutylamino)phenyl]-1,4-cyclohexadiene-3,6-diammonium hexafluoroantimonate produced by BASF AG, Germany; wherein, the mass of T-571 ultraviolet absorber is 0.2% of the mass of acrylic modified polyurethane, and the mass of heat insulation agent is 0.2% of the mass of acrylic modified polyurethane.

[0120] Example 7

[0121] The adhesive-free protective film provided in this embodiment consists of a first release film, a first substrate layer, a carrier layer, a metal reflective layer (metallic silver layer), a second substrate layer, and a second release film, which are stacked sequentially.

[0122] The preparation method of the adhesive-free protective film provided in this embodiment is basically the same as that in embodiment 5. The difference is that in step (2), before coating, on the other side surface of the carrier layer of the composite layer obtained in step (1) (the side away from the first substrate layer), a metal magnetron sputtering is performed with a silver target to form a metal reflective layer; then acrylic modified polyurethane is coated on the metal reflective layer and the subsequent steps are continued.

[0123] Example 8

[0124] The preparation method of the adhesive-free protective film provided in this embodiment is basically the same as that in embodiment 7. The difference is that in step (2), the silver target material is replaced with an aluminum target material, that is, a metal aluminum layer is formed.

[0125] Example 9

[0126] The adhesive-free protective film provided in this embodiment consists of a carrier layer, a substrate layer, and a release film stacked sequentially.

[0127] The method for preparing the adhesive-free protective film provided in this embodiment is a casting method, which specifically includes the following steps:

[0128] Using BASF aliphatic non-yellowing polyurethane resin L 785A 10000, after being heated and melted by the screw, extrudes a polyurethane film through a die and casts it onto the surface of a carrier layer (optical PET film produced by Kanghui New Material Technology Co., Ltd., with a thickness of 70μm). After being cooled by a cooling roller, a substrate layer is formed. Then, a PET non-silicone release film (with a thickness of 60μm and a release force of 5g) is attached to the surface of the substrate layer (the side away from the carrier layer) and then wound up. The thickness of the polyurethane is 60μm. The barrel temperature of the casting machine is set as follows: Zone 1 125℃, Zone 2 175℃, Zone 3 185℃, Zone 4 195℃. The die temperature is set to 205℃. After winding, a non-adhesive protective film is obtained.

[0129] Example 10

[0130] The preparation method of the adhesive-free protective film provided in this embodiment is basically the same as that in Example 9. The difference is that, before heating and melting, BASF aliphatic non-yellowing polyurethane resin is mixed with T-571 ultraviolet absorber produced by BASF AG and granulated, wherein the mass of T-571 ultraviolet absorber is 0.5% of the mass of liquid polyurethane. Then the granulated material is melted, extruded and cast.

[0131] Example 11

[0132] The adhesive-free protective film provided in this embodiment consists of a first release film, a first substrate layer, a carrier layer, a second substrate layer, and a second release film stacked sequentially.

[0133] The method for preparing the adhesive-free protective film provided in this embodiment is a casting method and a coating method, specifically including the following steps:

[0134] (1) BASF aliphatic non-yellowing polyurethane resin is used. After being heated and melted by the screw, the polyurethane film is extruded through the die and cast onto one side of the carrier layer (optical PET film produced by Yihua Toray Polyester Film Co., Ltd., with a thickness of 50μm). After being cooled by the cooling roller, the first substrate layer is formed. Then, a PET non-silicone release film (with a thickness of 50μm and a release force of 5g) is attached to the surface of the first substrate layer (the side away from the carrier layer). The thickness of the polyurethane is 50μm. The barrel temperature of the casting machine is set as follows: Zone 1 125℃, Zone 2 175℃, Zone 3 185℃, Zone 4 195℃. The die temperature is set as 205℃ to obtain the composite layer.

[0135] (2) After uniformly mixing acrylic modified polyurethane (Liaoning FBK-NKTSH ​​High-Tech Materials Co., Ltd., FBK-NKTSH) with light stabilizer 292 (where the mass of light stabilizer 292 is 0.25% of the mass of liquid polyurethane), the mixture is evenly coated on the other side of the carrier layer of the composite layer obtained in step (1) (the side away from the first substrate layer) using a coating machine. Then, it is baked in an oven at 110°C for 10 minutes to form a second substrate layer with a dry film thickness of 20 μm. Then, a PET non-silicone release film (thickness of 50 μm, release force of 3g, i.e., the second release film) is attached to the surface of the second substrate layer and wound up. After winding, it is placed in a curing chamber at 55°C for 72 hours to obtain an adhesive-free protective film.

[0136] Example 12

[0137] The adhesive-free protective film provided in this embodiment consists of a first release film, a substrate layer, and a second release film stacked sequentially.

[0138] The adhesive-free protective film provided in this embodiment is prepared by a coating method, specifically including the following steps: Liquid polyurethane (produced by Liaoning Fubai High-Tech Materials Co., Ltd., FBK-TB120325) is uniformly coated onto one side surface of a PET non-silicone release film (thickness of 80μm, release force of 3g, i.e., the first release film) using a coating machine. Then, it is placed in an oven at 120℃ and baked for 15 minutes to form a polyurethane film with a dry film thickness of 50μm, i.e., the substrate layer. Next, a PET non-silicone release film (thickness of 80μm, release force of 3g, i.e., the second release film) is attached to the surface of the substrate layer (the side away from the first release film). The film is then wound up, and after winding, it is placed in a curing chamber at 70℃ for 48 hours to obtain the adhesive-free protective film.

[0139] Example 13

[0140] The adhesive-free protective film provided in this embodiment consists of a first release film, a first substrate layer, a second substrate layer, and a second release film stacked sequentially.

[0141] The method for preparing the adhesive-free protective film provided in this embodiment is a coating method, which specifically includes the following steps:

[0142] (1) Liquid polyurethane (produced by Liaoning Fubai High-tech Materials Co., Ltd., FBK-TB120325) is evenly coated on one side of a PET non-silicone release film (thickness of 50μm, release force of 3g, i.e. the first release film) using a coating machine, and then placed in an oven at 120℃ for 15min to form a polyurethane film with a dry film thickness of 70μm, i.e. the first substrate layer, thus obtaining the composite layer.

[0143] (2) Acrylic-modified polyurethane (Liaoning FBK-NKTSH) was uniformly coated onto the surface of the first substrate layer of the composite layer obtained in step (1) (the side away from the first release film) using a coating machine. Then, it was baked in an oven at 110°C for 10 minutes to form a second substrate layer with a dry film thickness of 20 μm. Then, a PET non-silicone release film (thickness of 50 μm, release force of 3g, i.e., the second release film) was attached to the surface of the second substrate layer and wound up. After winding, it was placed in a curing chamber at 50°C for 72 hours to obtain an adhesive-free protective film.

[0144] See the schematic diagram of the layer structure of the adhesive-free protective film prepared in this embodiment. Figure 2 As shown.

[0145] Example 14

[0146] The adhesive-free protective film provided in this embodiment consists of a first release film, a substrate layer, and a second release film stacked sequentially.

[0147] The method for preparing the adhesive-free protective film provided in this embodiment is a casting method, which specifically includes the following steps: BASF aliphatic non-yellowing polyurethane resin is used, which is heated and melted by a screw and then extruded through a die to form a polyurethane film, which is then cast onto the surface of a PET non-silicone release film (thickness of 60μm, release force of 3g, i.e., the first release film). After being cooled by a cooling roller, a substrate layer is formed. Then, a PET non-silicone release film (thickness of 60μm, release force of 3g, i.e., the second release film) is attached to the surface of the substrate layer (the side away from the carrier layer) and wound up. The thickness of the polyurethane is 30μm. The barrel temperature of the casting machine is set as follows: Zone 1 125℃, Zone 2 175℃, Zone 3 185℃, Zone 4 195℃. The die temperature is set to 205℃. After winding, an adhesive-free protective film is obtained.

[0148] Example 15

[0149] This embodiment provides a method for applying a non-adhesive protective film. The non-adhesive protective films prepared in Examples 1 to 14 are used for application. The specific steps include: cleaning and drying the car window glass, peeling off the release film on the surface of the non-adhesive protective film, spraying water evenly on the surface of the car window glass, then adhering the non-adhesive protective film and the glass together, and using a squeegee to remove the water. Let it stand for 24 hours before use.

[0150] Comparative Example 1

[0151] The commercially available Johnson Fields side and rear (center concealed) car window tint (with adhesive) is applied to the car window using conventional tinting methods.

[0152] Experimental Example

[0153] Performance tests were conducted on the automotive window glass with the adhesive-free protective film of Example 5, the automotive window glass with the adhesive-free protective film of Example 13, and the automotive window glass with the automotive film of Comparative Example 1. The results are shown in Table 1.

[0154] Table 1 Performance Test Results

[0155]

[0156] As can be seen from the test results in Table 1 above, the adhesive-free protective film containing NCO groups and the ordinary window film are almost identical in terms of functionality, but the NCO-free protective film has a clear advantage in terms of glass strength and residual adhesive rate.

[0157] The adhesive-free protective film containing NCO groups provided by this invention can completely replace protective films with adhesives, and also reduces the safety hazards of cars falling into water or needing to break windows.

[0158] Although the present invention has been illustrated and described with specific embodiments, it should be understood that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; those skilled in the art should understand that modifications can be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein, without departing from the spirit and scope of the present invention; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention; therefore, this means that all such substitutions and modifications that fall within the scope of the present invention are included in the appended claims.

Claims

1. A non-adhesive protective film containing NCO groups, characterized in that, The adhesive-free protective film containing NCO groups includes at least one substrate layer, which is mainly made of a material containing NCO groups; the adhesive-free protective film does not contain any mounting adhesive; the adhesive-free protective film is used as a protective film for glass, and during the application process, a material coated with active hydrogen is introduced to allow the NCO groups to react with the active hydrogen, and then brushing is performed to form a vacuum adsorption layer, so that the adhesive-free protective film and the glass are bonded together. The thickness of the substrate layer is 40~150μm.

2. The adhesive-free protective film containing NCO groups according to claim 1, characterized in that, The material containing NCO groups includes polyurethane.

3. The adhesive-free protective film containing NCO groups according to claim 1, characterized in that, The raw materials used to prepare the substrate layer also include additives.

4. The adhesive-free protective film containing NCO groups according to claim 3, characterized in that, The additives include at least one of ultraviolet absorbers, light stabilizers, and heat insulation agents.

5. The adhesive-free protective film containing NCO groups according to claim 1, characterized in that, The adhesive-free protective film containing NCO groups also includes a carrier layer that is stacked and connected to the substrate layer.

6. The adhesive-free protective film containing NCO groups according to claim 5, characterized in that, The supporting layer includes a thermosetting material supporting layer and / or a thermoplastic material supporting layer.

7. The adhesive-free protective film containing NCO groups according to claim 6, characterized in that, The thermosetting material support layer includes at least one of a PET layer, a PTFE layer, and a PVDF layer.

8. The adhesive-free protective film containing NCO groups according to claim 6, characterized in that, The thermoplastic material support layer includes a polyurethane layer.

9. The adhesive-free protective film containing NCO groups according to claim 5, characterized in that, The adhesive-free protective film containing NCO groups further includes a metal reflective layer, which is disposed on the surface of the substrate layer or the carrier layer.

10. The adhesive-free protective film containing NCO groups according to claim 9, characterized in that, The metal reflective layer includes a silver layer and / or an aluminum layer.

11. The method for preparing the adhesive-free protective film containing NCO groups as described in any one of claims 1 to 10, characterized in that, Includes the following steps: The raw materials for preparing the substrate layer are coated and dried using a coating method. After film formation, the substrate layer is formed, resulting in the adhesive-free protective film containing NCO groups. And / or, by using a casting method, the raw materials for preparing the substrate layer are melted, extruded, and cast into a film to form the substrate layer, thereby obtaining the adhesive-free protective film containing NCO groups; The raw materials used to prepare the substrate layer include materials containing NCO groups; Optionally, the raw materials for preparing the substrate layer also include additives.

12. The method for preparing the adhesive-free protective film containing NCO groups according to claim 11, characterized in that, The coating method includes at least one of the following methods (1) to (4): (1) The raw materials for preparing the substrate layer are coated on the surface of the release film and dried to form a substrate layer, thereby obtaining the adhesive-free protective film containing NCO groups; (2) The raw materials for preparing the substrate layer are coated on the surface of the release film and dried to form the first substrate layer; (a) The raw materials for preparing the substrate layer are coated on the surface of the first substrate layer and dried to form the second substrate layer; Step (a) is repeated at least once to form at least two substrate layers to obtain the adhesive-free protective film containing NCO groups. (3) The raw materials for preparing the substrate layer are coated on the surface of the carrier layer and dried to obtain the adhesive-free protective film containing NCO groups, which includes a substrate layer and a carrier layer; (4) The raw materials for preparing the substrate layer are respectively coated on the two surfaces of the carrier layer and dried to form a substrate layer respectively disposed on both sides of the carrier layer, thereby obtaining the adhesive-free protective film containing NCO groups, which includes two substrate layers and one carrier layer.

13. The method for preparing the adhesive-free protective film containing NCO groups according to claim 12, characterized in that, The method for preparing the adhesive-free protective film containing NCO groups further includes: performing magnetron sputtering or vacuum evaporation on the surface of the substrate layer to form a metal reflective layer; or performing magnetron sputtering or vacuum evaporation on the surface of the carrier layer to form a metal reflective layer.

14. The application of the adhesive-free protective film containing NCO groups as described in any one of claims 1 to 10 in glass, characterized in that, The adhesive-free protective film containing NCO groups is completely adhered to at least one surface of the glass as a protective film, and there is no adhesive between the adhesive-free protective film containing NCO groups and the glass, forming a vacuum layer between the adhesive-free protective film containing NCO groups and the glass.

15. The application of the adhesive-free protective film containing NCO groups according to claim 14 in glass, characterized in that, The glass includes at least one of automotive glass and architectural glass.

16. The application of the adhesive-free protective film containing NCO groups according to claim 15 in glass, characterized in that, The automotive glass includes at least one of automotive window glass and automotive windshield glass.

17. The application of the adhesive-free protective film containing NCO groups according to claim 15 in glass, characterized in that, The architectural glass includes at least one of window and door glass, wall glass, and exterior decorative glass.

18. The application of the adhesive-free protective film containing NCO groups according to claim 14 in automotive glass, characterized in that, The method for complete bonding includes: coating the surface of the adhesive-free protective film containing NCO groups and / or the glass with an active hydrogen material, then bonding the adhesive-free protective film containing NCO groups and the glass together, while simultaneously reacting the NCO groups and the active hydrogen, and then expelling the active hydrogen material and air to form the vacuum layer, thus completing the bonding.

19. The application of the adhesive-free protective film containing NCO groups according to claim 18 in glass, characterized in that, The active hydrogen material includes at least one of water, alcohol, and acid.

Images