A sound insulation PVB film and its preparation method and application

Abstract

The present invention discloses a sound-insulating PVB film, its preparation method, and application. A sound-insulating PVB film comprises: a first PVB resin layer comprising the following components in parts by mass: 100 parts PVB resin, 33-47 parts plasticizer, 0.2-1 part antioxidant, 0.1-1.2 parts UV absorber, and 0.05-1 part adhesion regulator; a TPU resin layer disposed on the surface of the first PVB resin layer, comprising the following components in parts by mass: 8-24 parts TPU resin, 0.01-0.2 parts antioxidant, and 0.02-0.15 parts UV absorber; and a second PVB resin layer disposed on the surface of the TPU resin layer, the components of the second PVB resin layer being the same as those of the first PVB resin layer. The sound-insulating PVB film of the present invention uses TPU material for the middle layer, eliminating the need to add plasticizer to the middle layer. This prevents the plasticizer from seeping out of the PVB film and suppresses the generation of bubbles in laminated glass. The film also has uniform thickness and good optical properties.

Description

Technical Field

[0001] The present invention relates to the field of polymer sheets, and in particular to a sound-insulating PVB film and a preparation method and application thereof. Background Art

[0002] Due to its high safety performance, PVB laminated glass has been widely used in the fields of construction and automobiles. With the problem of noise pollution, the PVB laminated glass industry has actively explored the development of sound insulation materials in recent years. Chinese patent CN106543612A discloses a method of improving the sound insulation effect by increasing the melt index of the PVB middle layer, but the control of the melt index is mainly increased by increasing the proportion of plasticizers. Japanese patent JP2007331964A discloses a method of manufacturing sound insulation PVB film by adjusting the acetylation degree, acetalization degree and plasticizer ratio in the PVB resin to improve the defect of whitening when exposed to water. The main technology of sound insulation PVB film is to improve the sound insulation performance of PVB film by increasing the plasticizer content in the middle layer of PVB film.

[0003] Currently, all sound-insulating PVB films used in laminated glass utilize a multi-layer composite structure, with the middle sound-insulating layer utilizing modified PVB resin. By adjusting the ratio of hydroxyl, acetal, and acetyl groups in the PVB resin, the compatibility of the plasticizer with the PVB resin is increased, and the sound-insulating performance of the PVB film is thereby enhanced by increasing the plasticizer ratio. While this method can improve the sound-insulating performance of laminated glass, increasing the plasticizer content can lead to plasticizer leakage from the film, the formation of bubbles after the laminated glass is assembled, and excessive plasticizer content in the sound-insulating layer can easily cause excessive fluidity of the interlayer melt during extrusion, resulting in uneven thickness of the interlayer and localized optical non-uniformity, which can cause significant optical distortion in the laminated glass. Summary of the Invention

[0004] In order to overcome the problems of existing sound insulation PVB film such as plasticizer leakage, bubble generation after glass lamination, and light distortion, one of the purposes of the present invention is to provide a sound insulation PVB film; the second purpose of the present invention is to provide a method for preparing such a sound insulation PVB film; and the third purpose of the present invention is to provide applications of such a sound insulation PVB film.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is:

[0006] A first aspect of the present invention provides a sound-insulating PVB film, comprising:

[0007] A first PVB resin layer, the first PVB layer comprising the following components in parts by weight: 100 parts of PVB resin, 33-47 parts of plasticizer, 0.2-1 part of antioxidant, 0.1-1.2 parts of ultraviolet absorber, and 0.05-1 part of adhesion regulator;

[0008] A TPU resin layer, the TPU resin layer being disposed on the surface of the first PVB resin layer; the TPU resin layer comprising the following components in parts by weight: 8 to 24 parts of TPU resin, 0.01 to 0.2 parts of antioxidant, and 0.02 to 0.15 parts of ultraviolet absorber;

[0009] A second PVB resin layer is provided on the surface of the TPU resin layer; and the components of the second PVB resin layer are the same as those of the first PVB resin layer.

[0010] The sound-insulating PVB film of the present invention is composed of three layers, and its specific structure is an A / B / A structure, which is respectively formed by stacking a surface layer A, an intermediate layer B, and a surface layer A in sequence; wherein the surface layer A contains polyvinyl butyral and a plasticizer; and the intermediate layer B contains a thermoplastic polyurethane elastomer (TPU).

[0011] Preferably, the thickness of the sound-insulating PVB film is 0.74-1.16 mm.

[0012] Preferably, the ratio of the thickness of the TPU resin layer to the sum of the thicknesses of the first PVB resin layer and the second PVB resin layer is (0.05-0.2):1.

[0013] Preferably, the parameters of the PVB resin are as follows: hydroxyl content of 17 wt% to 20 wt%; viscosity of 200 cp to 260 cp at 20° C.; and melt index of 6.0 g / 10 min to 7.5 g / 10 min at a test temperature of 140° C. and a load of 21.6 kg.

[0014] Preferably, the plasticizer includes at least one of phthalates, adipates, sebacic acid esters, triethylene glycol esters, and tetraethylene glycol esters. Further preferably, the plasticizer includes at least one of triethylene glycol esters and tetraethylene glycol esters. In some preferred embodiments of the present invention, the plasticizer is triethylene glycol diisooctanoate (3GO). Triethylene glycol diisooctanoate (3GO) is a specific plasticizer for polyvinyl butyral and is a cold-resistant plasticizer with excellent light resistance, low-temperature properties, adhesion, toughness, flexibility, moisture resistance, and durability.

[0015] Preferably, the antioxidant is at least one of a hindered phenol antioxidant and a phosphite antioxidant; further preferably, the antioxidant is a mixture of hindered phenol antioxidants and phosphite antioxidants; in some preferred embodiments of the present invention, the antioxidant is a mixture of antioxidant 1010 and antioxidant 168. Antioxidant 1010 is a chain-terminating antioxidant with low volatility, pollution-free, and water-extractable properties. It has excellent compatibility with various polymers and is one of the most high-performing phenolic antioxidants currently available. Antioxidant 168 is a secondary antioxidant that decomposes high-molecular-weight hydroperoxides, thereby preventing thermal oxidative aging. It is often used in conjunction with the primary antioxidant to impart long-term thermal stability to PVB after processing and prevent yellowing during processing.

[0016] Preferably, the adhesion modifier includes at least one of an alkali metal or alkaline earth metal salt; more preferably, the adhesion modifier includes at least one of potassium acetate, magnesium acetate, potassium formate, magnesium formate, sodium acetate, magnesium propionate, magnesium 2-ethylhexanoate, and potassium 2-ethyl acetate; and even more preferably, the adhesion modifier includes a mixture of magnesium acetate and potassium acetate. The addition of potassium acetate can ensure uniform and stable adhesion across the PVB laminated glass, while the addition of magnesium acetate can improve the water resistance of the PVB laminated glass and reduce the whitening of the edges of the laminated glass due to water absorption.

[0017] Preferably, the UV absorber is a benzotriazole UV absorber; further preferably, the UV absorber includes at least one of UV-326, UV-P, and UV-329; and even more preferably, the UV absorber is UV-326. UV-326 strongly absorbs UV rays with a wavelength of 270-380 nm, has low volatility, good compatibility with resins, and antioxidant properties, and exhibits a synergistic effect when used with antioxidants.

[0018] A second aspect of the present invention provides a method for preparing the above-mentioned sound-insulating PVB film, comprising the following steps:

[0019] (1) mixing the components of the first PVB resin layer, and plasticizing and extruding the mixture through a first extruder to obtain a surface layer melt;

[0020] (2) mixing the components of the TPU resin layer, and plasticizing and extruding the mixture through a second extruder to obtain an intermediate layer melt;

[0021] (3) The surface layer melt and the intermediate layer melt are formed into a multilayer structure through a distributor, and then extruded to obtain the sound insulation PVB film.

[0022] Preferably, in step (1), the vacuum degree of the exhaust port of the first extruder is -0.03 MPa to -0.1 MPa.

[0023] Preferably, in step (2), the vacuum degree of the exhaust port of the second extruder is -0.03 MPa to -0.1 MPa.

[0024] Within a certain vacuum range, water vapor and other volatile substances in the film can be extracted, effectively reducing surface bubbles on the film. However, the vacuum degree cannot be too high. If the vacuum is too high, the extraction force will be too strong, and the PVB melt will easily climb the wall of the extruder exhaust port and even be extracted.

[0025] A third aspect of the present invention provides application of the above-mentioned sound-insulating PVB film in laminated glass.

[0026] The beneficial effects of the present invention are:

[0027] The sound-insulating PVB film of this invention uses TPU as the middle layer, eliminating the need for plasticizers. This prevents plasticizer exudation from the PVB film and suppresses bubble formation in laminated glass. Furthermore, the film offers uniform thickness and excellent optical properties. Because polyurethane is a polymer with a high number of urethane groups, its unique structure imparts excellent adhesion to organic materials, superior mechanical properties, and high and low-temperature adaptability. Compared to PVB film, it has a wider temperature range of application. Furthermore, it exhibits viscoelasticity and good damping properties. Therefore, using thermoplastic polyurethane (TPU) as the middle sound-insulating layer in sound-insulating PVB film improves the sound insulation performance of laminated glass. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 Schematic diagram of the structure of the sound insulation PVB film according to an embodiment of the present invention.

[0029] Figure 2 Schematic diagram of the sound insulation test room used for sound insulation testing in performance testing. DETAILED DESCRIPTION

[0030] The present invention is further described in detail below using specific examples. Unless otherwise specified, the raw materials, reagents, and apparatus used in the examples and comparative examples are available from conventional commercial sources or by conventional methods. Unless otherwise specified, all experimental or testing methods are conventional in the art.

[0031] As attached Figure 1 As shown, the sound insulation PVB film of an embodiment of the present invention consists of a three-layer structure, wherein two surface layers A (a first PVB resin layer and a second PVB resin layer) are composed of a polyvinyl butyral resin (PVB resin) composition, the hydroxyl content of the PVB resin is 18.0wt%, the viscosity is 220cp / 20℃, and the melt index of the PVB resin composition is 7.0g / 10min (140℃); the middle layer B is composed of a TPU resin composition.

[0032] Example 1

[0033] As attached Figure 1 As shown, the sound insulation PVB film of this embodiment consists of a three-layer structure with a total thickness of 0.76 mm, a thickness of the middle layer B of 0.12 mm, and the thickness of the two surface layers is the same. The specific preparation method is as follows:

[0034] Preparation of the surface layer:

[0035] 0.16 parts by weight of antioxidant 1010, 0.16 parts by weight of antioxidant 168, and 0.3 parts by weight of ultraviolet absorber UV-326 were dissolved in 38.8 parts by weight of 3GO plasticizer to prepare a 3GO composition solution; 0.08 parts by weight of potassium acetate and 0.01 parts by weight of magnesium acetate were mixed and dissolved in 0.6 parts by weight of deionized water to prepare a metal ion aqueous solution; the 3GO solution composition, metal ion aqueous solution, and 100 parts by weight of PVB resin prepared above were plasticized and mixed at 150° C. in a 90-type twin-screw extruder, and the vacuum degree (exhaust pressure) of the exhaust port of the extruder was set to -0.08 MPa to remove volatiles.

[0036] Preparation of the middle layer:

[0037] 20 parts by weight of TPU resin, 0.06 parts by weight of antioxidant 1010, 0.06 parts by weight of antioxidant 168, and 0.1 parts by weight of ultraviolet absorber UV-326 were added to a mixing tank. After high-speed stirring for 30 minutes to mix evenly, the mixture was plasticized and extruded through a 50-type vented twin-screw extruder at a plasticizing temperature of 180°C. The vacuum degree at the exhaust port of the extruder was -0.03 MPa.

[0038] The surface layer and the middle layer melt pass through the flow channel of the distributor to form a three-layer structure, and then pass through a 160°C die head to extrude into a 0.76mm thick film.

[0039] Example 2

[0040] The total thickness of the sound insulation PVB film of this embodiment is 0.76 mm, and the thickness of the middle layer is 0.1 mm. The preparation method is the same as that of Example 1, except that the amount of TPU resin used in the middle layer is 15 parts by weight, as shown in Table 1 below.

[0041] Example 3

[0042] The total thickness of the sound insulation PVB film of this embodiment is 0.76 mm, and the thickness of the middle layer is 0.07 mm. The preparation method refers to that of Example 1, except that the amount of TPU resin used in the middle layer is 10 parts by weight, as shown in Table 1 below.

[0043] Example 4

[0044] The total thickness of the sound insulation PVB film in this embodiment is 0.76 mm, the thickness of the middle layer is 0.1 mm, and the preparation method refers to Example 1, except that the amount of TPU resin used in the middle layer is 15 parts by weight, and the exhaust pressure during the preparation of the surface layer is -0.05 MPa, as shown in Table 1 below.

[0045] Example 5

[0046] The total thickness of the sound insulation PVB film in this embodiment is 0.76 mm, the thickness of the middle layer is 0.1 mm, and the preparation method refers to Example 1, except that the amount of TPU resin used in the middle layer is 15 parts by weight, and the exhaust pressure during the preparation of the surface layer is -0.03 MPa, as shown in Table 1 below.

[0047] Comparative Example 1

[0048] The total thickness of the sound insulation PVB film in this comparative example is 0.76 mm, and the thickness of the middle layer is 0.04 mm. The preparation method refers to Example 1, except that the amount of TPU resin used in the middle layer is 7 parts by weight, as shown in Table 1 below.

[0049] Comparative Example 2

[0050] The total thickness of the sound insulation PVB film in this comparative example is 0.76 mm, the thickness of the middle layer is 0.1 mm, and the preparation method refers to Example 1, except that the exhaust pressure during the preparation of the middle layer is 0 MPa, and the exhaust pressure during the preparation of the surface layer is -0.01 MPa, as shown in Table 1 below.

[0051] Comparative Example 3

[0052] The total thickness of the sound insulation PVB film in this comparative example is 0.76 mm, and the thickness of the middle layer is 0.12 mm. The preparation method refers to Example 1, except that the 20 parts by weight of TPU resin in the middle layer is replaced by 10 parts by weight of PVB and 10 parts by weight of 3GO plasticizer, as shown in Table 1 below.

[0053] The PVB resin used in the intermediate layer has a hydroxyl content of 12% by weight and a viscosity of 600 cp / 20°C.

[0054] In this comparative example, a PVB resin middle layer is used, and the proportion of plasticizer is 50%, which is larger than the amount of plasticizer used in the surface layer. Therefore, it is necessary to reduce the hydroxyl group in order to increase the compatibility of PVB and the plasticizer.

[0055] Comparative Example 4

[0056] This comparative example prepared a single-layer sound-insulating PVB film with a thickness of 0.76 mm. The specific preparation method is as follows:

[0057] 0.16 parts by weight of antioxidant 1010, 0.16 parts by weight of antioxidant 168, and 0.3 parts by weight of ultraviolet absorber UV-326 were dissolved in 38.8 parts by weight of 3GO plasticizer to prepare a 3GO composition solution; 0.08 parts by weight of potassium acetate and 0.01 parts by weight of magnesium acetate were mixed and dissolved in 0.6 parts by weight of deionized water to prepare a metal ion aqueous solution; the 3GO solution composition, metal ion aqueous solution, and 100 parts by weight of PVB resin prepared above were plasticized and mixed at 150°C in a 90-type twin-screw extruder. The vacuum degree of the exhaust port of the extruder was set to -0.08 MPa to remove volatiles, and then extruded through a 160°C die head to form a single-layer PVB film with a thickness of 0.76 mm.

[0058] Comparative Example 5

[0059] This comparative example prepared a single-layer sound-insulating TPU film with a thickness of 0.76 mm. The specific preparation method is as follows

[0060] 138 parts by weight of TPU resin, 0.16 parts by weight of antioxidant 1010, 0.16 parts by weight of antioxidant 168, and 0.3 parts by weight of ultraviolet absorber UV-326 were added to a mixing tank and mixed uniformly with high-speed stirring for 30 minutes. 0.08 parts by weight of potassium acetate and 0.01 parts by weight of magnesium acetate were mixed and dissolved in 0.6 parts by weight of deionized water to prepare a metal ion aqueous solution. The above metal ion aqueous solution and TPU resin composition were plasticized and extruded through a 90-type vented twin-screw extruder at a plasticizing temperature of 180°C. The vacuum degree at the extruder exhaust port was -0.08 MPa, and then extruded through a 160°C die head to form a 0.76mm thick single-layer TPU film.

[0061] Comparative Example 6

[0062] This comparative example prepared a three-layer sound insulation PVB film with a total thickness of 0.76 mm. The specific preparation method is as follows:

[0063] Preparation of the surface layer:

[0064] 138 parts by weight of TPU resin, 0.16 parts by weight of antioxidant 1010, 0.16 parts by weight of antioxidant 168, and 0.3 parts by weight of ultraviolet absorber UV-326 were added to a mixing tank and mixed uniformly by high-speed stirring for 30 minutes. 0.08 parts by weight of potassium acetate and 0.01 parts by weight of magnesium acetate were mixed and dissolved in 0.6 parts by weight of deionized water to prepare a metal ion aqueous solution. The metal ion aqueous solution and TPU resin composition were plasticized and extruded through a 90-type vented twin-screw extruder at a plasticizing temperature of 180°C. The vacuum degree at the extruder exhaust port was -0.08 MPa.

[0065] Preparation of the middle layer:

[0066] 0.04 parts by weight of antioxidant 1010, 0.04 parts by weight of antioxidant 168, and 0.16 parts by weight of ultraviolet absorber UV-326 were dissolved in 10 parts by weight of 3GO plasticizer to prepare a 3GO composition solution; the 3GO solution composition prepared above and 10 parts by weight of PVB resin were plasticized and mixed at 150°C in a 50-type twin-screw extruder, and the vacuum degree of the exhaust port of the extruder was set at -0.03 MPa to remove volatiles.

[0067] The surface layer and the middle layer melt pass through a distributor to form a three-layer structure, and then pass through a 160°C die to extrude a 0.76mm thick film.

[0068] The raw material dosage, exhaust pressure, total thickness and film structure of the sound insulation PVB film of the above embodiment and comparative example are shown in Table 1 below:

[0069] Table 1

[0070]

[0071] The performance tests of the sound insulation PVB films prepared in the above examples and comparative examples were carried out:

[0072] (1) Optical distortion

[0073] The light distortion test of the laminated glass synthesized with the PVB film in the experimental example was performed to evaluate the light distortion. The results are shown in Table 2 below.

[0074] (2) Bubbles on the film surface

[0075] Place a 50cm*50cm film on a 100W LED light box and visually observe the bubbles on the surface of the film.

[0076] (3) Baking test

[0077] This test evaluates whether safety glass develops bubbles after being subjected to high-temperature operation for a certain period of time. Three samples of PVB film are placed in an autoclave to form 300mm x 300mm laminated glass. The three glass samples are placed vertically on an iron frame in an oven and heated to 100°C for 2 hours. The samples are then cooled to room temperature and visually inspected to note any bubbles or other defects.

[0078] (4) Sound insulation test:

[0079] 1. Test equipment: sound level meter, power amplifier, loudspeaker, microphone.

[0080] 2. Test method: Take 1000*1000mm PVB film and pass it through an autoclave to synthesize PVB laminated glass. After passing through the autoclave, place the laminated glass on the wall between the sound source room and the receiving room of the sound insulation laboratory, and seal the four sides with cement. After the cement hardens, the test can be carried out. The sound insulation test room is as follows Figure 2 shown.

[0081] Before the experiment, the air conditioner should be turned on and the temperature should be adjusted to (20±3)℃ and the humidity should be adjusted to 35%-85% for at least 48 hours.

[0082] Connect and place the power amplifier, speaker, and microphone. Connect the sound level meter to the power amplifier, microphone, and computer respectively.

[0083] (5) Plasticizer precipitation

[0084] PVB film samples from the experimental example were placed in a desiccator filled with sulfuric acid for 5 days. After 5 days, the samples were removed and weighed, each weighed as m1. The dried (and weighed) samples were then placed in a desiccator filled with water for 7 days. Filter paper was used to absorb any surface moisture from the samples, and the samples were placed in a sulfuric acid desiccator for another 5 days. The samples were then removed and weighed, each weighed as m2.

[0085] Plasticizer precipitation amount = (m1-m2) / m1×100%, and the average value of the plasticizer precipitation amount of the four samples is taken as the test result.

[0086] (6) Knock value

[0087] The impact value of film laminated glass is evaluated according to GB / T 32020-2015.

[0088] Table 2 Performance test results

[0089]

[0090] As shown in Table 2 above, the extruder exhaust port should maintain appropriate exhaust pressure. When the extruder has no exhaust pressure or the exhaust pressure is too low, the volatile components in the film cannot be effectively discharged, which can easily cause defects such as bubbles and baked-in bubbles in the film during extrusion. Adding TPU to the film can improve the film's sound insulation, but TPU has poor adhesion to glass. When TPU is used as the surface layer of the film, laminated glass will fall off after a level 0 tap, indicating extremely poor adhesion between the film and glass.

[0091] The above embodiments are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A sound insulation PVB film, characterized in that: It consists of a first PVB resin layer, a TPU resin layer arranged on the surface of the first PVB resin layer, and a second PVB resin layer arranged on the surface of the TPU resin layer; The first PVB resin layer comprises, by mass, 100 parts of PVB resin, 33-47 parts of plasticizer, 0.2-1 part of antioxidant, 0.1-1.2 parts of ultraviolet absorber, and 0.05-1 part of adhesion regulator. The components of the TPU resin layer are: 8-24 parts of TPU resin, 0.01-0.2 parts of antioxidant, and 0.02-0.15 parts of ultraviolet absorber; The component of the second PVB resin layer is the same as that of the first PVB resin layer; The sound-insulating PVB film is prepared by a method comprising the following steps: (1) mixing the components of the first PVB resin layer, and plasticizing and extruding the mixture through a first extruder to obtain a surface layer melt; (2) mixing the components of the TPU resin layer, and plasticizing and extruding the mixture through a second extruder to obtain an intermediate layer melt; (3) forming a multilayer structure by passing the surface layer melt and the intermediate layer melt through a distributor, and then extruding to obtain the sound insulation PVB film; Wherein, in step (1), the vacuum degree of the exhaust port of the first extruder is -0.03MPa to -0.1MPa; In step (2), the vacuum degree of the exhaust port of the second extruder is -0.03MPa to -0.1MPa.

2. The sound insulation PVB film according to claim 1, characterized in that: The thickness of the sound-insulating PVB film is 0.74-1.16 mm.

3. The sound insulation PVB film according to claim 2, characterized in that: The ratio of the thickness of the TPU resin layer to the sum of the thicknesses of the first PVB resin layer and the second PVB resin layer is (0.05-0.2):

1.

4. The sound insulation PVB film according to claim 1, characterized in that: The parameters of the PVB resin are as follows: a hydroxyl content of 17 wt% to 20 wt%; a viscosity of 200 cp to 260 cp at 20° C.; and a melt index of 6.0 g / 10 min to 7.5 g / 10 min at a test temperature of 140° C. and a load of 21.6 kg.

5. The sound insulation PVB film according to claim 1, characterized in that: The antioxidant is at least one of a hindered phenol antioxidant and a phosphite antioxidant.

6. The sound insulation PVB film according to claim 1, characterized in that: The adhesion regulator includes at least one of alkali metal and alkaline earth metal salts.

7. Use of the sound-insulating PVB film according to any one of claims 1 to 6 in laminated glass.

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