Interlayer synergistic anti-aging pvc composite interlayer and preparation method and application thereof

Abstract

The present application relates to the technical field of laminated glass interlayer film, and particularly relates to a kind of interlayer synergistic anti-aging PVB composite interlayer film and its preparation method and application.The present application is based on the technical route of interlayer synergistic antioxidant system, adopts the multilayer structure of "core sound insulation layer+double surface layer", and constructs interlayer synergistic antioxidant system by precisely distributing different types of antioxidants, realizes interlayer function synergy, improves the compatibility of antioxidant and heat shielding material, while ensuring sound insulation and thermal insulation performance, significantly improves the anti-aging stability of interlayer synergistic anti-aging PVB composite interlayer film, solves the technical problems that the existing PVB interlayer film has single antioxidant adding mode or unreasonable distribution, poor compatibility with heat shielding material, leading to sound insulation performance attenuation, serious yellowing and heat insulation efficiency decline during long-term use, and has wide application prospect.

Description

Technical Field

[0001] This invention relates to the field of interlayer glass interlayer technology, and in particular to an interlayer synergistic aging-resistant PVB composite interlayer, its preparation method, and its application. Background Technology

[0002] Polyvinyl butyral (PVB) interlayer is the core material of safety laminated glass. It prevents glass fragments from scattering by bonding them together, while also providing certain sound and heat insulation properties. It is widely used in construction, automotive, and other fields. As market demands for the functionality of safety laminated glass increase, long-lasting aging resistance, high-efficiency heat insulation, and excellent sound insulation have become important development directions for safety laminated glass.

[0003] Existing PVB interlayer films often suffer from the following technical challenges: First, the method of adding antioxidants is crude, with most adding only a single type of antioxidant, which cannot adapt to the functional requirements of different layers in a multilayer structure (for example, the core sound insulation layer needs to protect the thermoplastic elastomer, while the surface layer needs to consider both adhesion to the glass and weather resistance), leading to problems such as sound insulation performance degradation and yellowing during long-term use; Second, the compatibility between heat shielding materials (such as cesium tungsten bronze CWO and indium tin oxide ITO) and antioxidants is poor, with some antioxidants adsorbing onto the surface of the heat shielding material, reducing heat insulation efficiency, and the heat shielding material may catalyze PVB oxidation, accelerating aging; Third, there is a lack of precise formulation systems designed to address the functional differences between layers, making it difficult to achieve a balance in overall performance.

[0004] To address these issues, technicians have attempted to increase the amount of antioxidants added or to incorporate additional protective layers. However, this often leads to decreased light transmittance of the PVB interlayer, increased costs, and fails to fundamentally resolve interlayer functional conflicts and material compatibility problems. Therefore, improving the compatibility between antioxidants and heat-shielding materials in PVB interlayers has become an urgent need in this field. Summary of the Invention

[0005] In view of this, the present invention provides an interlayer synergistic aging-resistant PVB composite intermediate film, its preparation method and application. The interlayer synergistic aging-resistant PVB composite intermediate film provided by the present invention has good compatibility between antioxidants and heat shielding materials, and significantly improves aging resistance stability while ensuring sound insulation and heat insulation performance.

[0006] This invention provides an interlayer synergistic aging-resistant PVB composite interlayer, comprising a core sound-insulating layer and surface layers composited on both sides of the core sound-insulating layer; the core sound-insulating layer comprises a thermoplastic elastomer and a composite antioxidant; the thermoplastic elastomer is a hydrogenated product of a block copolymer containing aromatic vinyl monomer units and conjugated diene monomer units, with a residual carbon-carbon double bond content of 2-40 mol%; the composite antioxidant comprises a sulfur-based antioxidant and a phosphorus-based auxiliary antioxidant; the surface layer comprises PVB resin, a plasticizer, an adhesion modifier, and a compound antioxidant; the compound antioxidant comprises a low-migration phenolic antioxidant and a hindered amine light stabilizer; at least one of the core sound-insulating layers or the surface layer further comprises a heat-shielding material.

[0007] Preferably, the core sound insulation layer has one or more layers; the surface layer has two or more layers; and the thickness ratio of a single core sound insulation layer to a single surface layer is 100~120:300~350.

[0008] Preferably, the sulfur-based antioxidant includes one or more of dilauryl 3,3'-thiodipropionate (DLTP) and distearate 3,3'-thiodipropionate (DSTP); the phosphorus-based auxiliary antioxidant includes one or more of tris(2,4-di-tert-butylphenyl) phosphite and bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite; the mass ratio of the sulfur-based antioxidant to the phosphorus-based auxiliary antioxidant is 0.08~0.2:0.02~0.1; and the mass ratio of the thermoplastic elastomer to the composite antioxidant is 100:0.1~0.3.

[0009] Preferably, the core sound insulation layer further includes an adhesive strength modifier; the adhesive strength modifier is maleic anhydride-modified polypropylene; and the mass ratio of the thermoplastic elastomer to the adhesive strength modifier is 100:0~5.

[0010] Preferably, the low-migration phenolic antioxidant in the surface layer includes one or two of 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; the hindered amine light stabilizer in the surface layer includes poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine- The product is selected from one or both of the following: [2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexamethylenediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino] and bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate; the mass ratio of the low-migration phenolic antioxidant to the hindered amine light stabilizer is 0.3~0.7:0.2~0.3; the mass ratio of the PVB resin to the compounded antioxidant is 100:0.5~1.

[0011] Preferably, the surface layer further comprises an ultraviolet absorber; the ultraviolet absorber includes one or both of 2-(5-chloro-2-benzotriazolyl)-6-tert-butyl-p-cresol and 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole.

[0012] Preferably, the ratio of the total mass of the composite antioxidant and the compound antioxidant to the total mass of the heat shielding material is 1 to 3:1.

[0013] This invention also provides a method for preparing the interlayer synergistic aging-resistant PVB composite intermediate film described above, comprising the following steps: The raw materials of the core sound insulation layer are mixed to obtain the first raw material, and the raw materials of the surface layer are mixed to obtain the second raw material. The first and second raw materials are melted and then subjected to multi-layer co-extrusion, hot pressing and cooling shaping in sequence to obtain the interlayer synergistic aging-resistant PVB composite intermediate film.

[0014] The present invention also provides the application of the interlayer synergistic aging-resistant PVB composite interlayer film described in the above-described scheme or the interlayer synergistic aging-resistant PVB composite interlayer film obtained by the preparation method described in the above-described scheme in the field of laminated glass.

[0015] The present invention also provides a laminated glass comprising an interlayer and glass sandwiched on both sides of the interlayer, wherein the interlayer is the interlayer synergistic aging-resistant PVB composite interlayer described in the above-described scheme or the interlayer synergistic aging-resistant PVB composite interlayer obtained by the preparation method described in the above-described scheme.

[0016] Compared with the prior art, the present invention has achieved the following beneficial effects: This invention is based on a technical approach of constructing an antioxidant system through interlayer synergy. It adopts a multi-layer structure of "core sound insulation layer + double-sided surface layer" and constructs an interlayer synergistic antioxidant system by precisely distributing different types of antioxidants (a compound system of sulfur-based antioxidants and phosphorus-based auxiliary antioxidants added to the core sound insulation layer, and a compound system of low-migration phenolic antioxidants and hindered amine light stabilizers added to the surface layer). This achieves interlayer functional synergy, improves the compatibility of antioxidants with heat shielding materials, and significantly enhances the aging stability of the interlayer synergistic aging-resistant PVB composite interlayer while ensuring sound insulation and heat insulation performance. It solves the technical problems of existing PVB interlayer films, such as single or unreasonable antioxidant addition methods and poor compatibility with heat shielding materials, which lead to sound insulation performance degradation, severe yellowing, and decreased heat insulation efficiency after long-term use. It has broad application prospects.

[0017] The interlayer synergistic aging-resistant PVB composite interlayer provided by this invention, when used in laminated glass, exhibits a visible light transmittance ≥85%, an average infrared light transmittance ≤70% in the 800~1100nm range, a color difference ΔE*ab ≤1.5 after 200 hours of xenon lamp aging, and a sound transmission loss ≥39dB at 4000Hz. It is particularly suitable for scenarios with high requirements for sound insulation, heat insulation, and aging resistance, such as building curtain walls, automotive glass, and safety laminated glass.

[0018] Specifically, the interlayer synergistic anti-aging PVB composite intermediate film, its preparation method, and its application provided by this invention have the following advantages: 1) Interlayer synergistic anti-oxidation: Based on the functional differences between the core sound insulation layer and the surface layer, different types of antioxidants are precisely allocated to avoid performance conflicts caused by single addition, while achieving synergistic effects of anti-oxidation, anti-ultraviolet and anti-thermal oxidation, significantly improving aging resistance and stability.

[0019] 2) Good material compatibility: By controlling the ratio of antioxidant to heat shield material, as well as the particle size of heat shield material, the compatibility problem between the two is solved, ensuring heat insulation efficiency while avoiding catalytic oxidation.

[0020] 3) Excellent overall performance: It combines excellent sound insulation (sound transmission loss ≥39dB at 4000Hz), heat insulation (average transmittance of infrared light ≤72% at 800~1100nm), printability (ink adhesion grade ≤1) and aging resistance (color difference ΔE*ab ≤1.5 after aging), meeting the needs of high-end laminated glass.

[0021] 4) High efficiency and environmental protection: The co-extrusion integrated molding process eliminates the need for additional compounding processes, making the process simple, easy to operate, and highly efficient. It also reduces the risk of interface failure and eliminates the release of volatile harmful substances. Detailed Implementation

[0022] This invention provides an interlayer synergistic aging-resistant PVB composite interlayer, comprising a core sound-insulating layer and surface layers composited on both sides of the core sound-insulating layer; the core sound-insulating layer comprises a thermoplastic elastomer and a composite antioxidant; the thermoplastic elastomer is a hydrogenated product of a block copolymer containing aromatic vinyl monomer units and conjugated diene monomer units, with a residual carbon-carbon double bond content of 2-40 mol%; the composite antioxidant comprises a sulfur-based antioxidant and a phosphorus-based auxiliary antioxidant; the surface layer comprises PVB resin, a plasticizer, an adhesion modifier, and a compound antioxidant; the compound antioxidant comprises a low-migration phenolic antioxidant and a hindered amine light stabilizer; at least one of the core sound-insulating layers or the surface layer further comprises a heat-shielding material.

[0023] The interlayer synergistic aging-resistant PVB composite intermediate membrane provided by the present invention includes a core sound insulation layer; the core sound insulation layer preferably has one or more layers.

[0024] In this invention, the residual carbon-carbon double bond content of the thermoplastic elastomer is preferably 5-35 mol%, more preferably 10-30 mol%, and even more preferably 15-20 mol%. Controlling the residual carbon-carbon double bond content of the thermoplastic elastomer within the above range ensures excellent sound insulation and damping performance.

[0025] In this invention, the thermoplastic elastomer is preferably a hydrogenated styrene-based thermoplastic elastomer; more preferably, the thermoplastic elastomer is a hydrogenated product of polystyrene-poly(isoprene / butadiene)-polystyrene triblock copolymer.

[0026] In this invention, the mass ratio of the thermoplastic elastomer to the composite antioxidant is preferably 100:0.1~0.3, more preferably 100:0.15~0.25, and even more preferably 100:0.2.

[0027] In this invention, the sulfur-based antioxidant preferably includes one or more of dilauryl 3,3'-thiodipropionate (DLTP) and distearate 3,3'-thiodipropionate (DSTP); the phosphorus-based auxiliary antioxidant preferably includes one or more of tris(2,4-di-tert-butylphenyl) phosphite and bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite. This invention provides long-lasting anti-aging properties through sulfur-based antioxidants and repairs free radicals; the two work synergistically to protect thermoplastic elastomers from oxidative degradation. When the amount added is controlled within the aforementioned range, sound insulation performance can be guaranteed.

[0028] In this invention, the mass ratio of the sulfur-based antioxidant to the phosphorus-based auxiliary antioxidant is preferably 0.08~0.2:0.02~0.1, more preferably 0.1~0.17:0.04~0.08, and even more preferably 0.12:0.06.

[0029] In this invention, the core sound insulation layer preferably further includes an adhesive strength modifier; the adhesive strength modifier is preferably maleic anhydride-modified polypropylene. This invention improves interlayer adhesive strength by modifying polypropylene with maleic anhydride.

[0030] In this invention, the mass ratio of the thermoplastic elastomer to the adhesive strength modifier is preferably 100:0~5, more preferably 100:1~4, and even more preferably 100:2~3.

[0031] In this invention, when the core sound insulation layer comprises a heat shielding material, the mass ratio of the thermoplastic elastomer to the heat shielding material is preferably 100:0.1~0.5, more preferably 100:0.2~0.4, and even more preferably 100:0.3.

[0032] In this invention, the areal density of the heat-shielding material in the core sound insulation layer is preferably 0.10~0.50 g / m². 2 More preferably, it is 0.20~0.40 g / m 2 More preferably 0.30 g / m 2 .

[0033] In this invention, the core sound insulation layer preferably comprises: 100 parts of thermoplastic elastomer, 0.08-0.2 parts of sulfur-based antioxidant, 0.02-0.1 parts of phosphorus-based auxiliary antioxidant, 0.1-0.5 parts of heat shielding material, and 0-5 parts of adhesive strength modifier.

[0034] The interlayer synergistic aging-resistant PVB composite intermediate film provided by the present invention includes a surface layer; preferably, the surface layer has two or more layers.

[0035] In this invention, the average degree of polymerization of the PVB resin in the surface layer is preferably 1500-2500, the hydroxyl content is preferably 16-22 wt%, and the acetal degree is preferably 60-75 mol%. This invention uses PVB resin of the above specifications to ensure good adhesion between the interlayer synergistic aging-resistant PVB composite intermediate film and the glass.

[0036] In this invention, the plasticizer in the surface layer preferably includes one or more of triethylene glycol di-2-ethylhexanoate (3GO), tetraethylene glycol di-2-ethylhexanoate (4GO), and triethylene glycol diisonononate. This invention uses the above-mentioned plasticizer to improve the flexibility of the interlayer synergistic aging-resistant PVB composite interlayer.

[0037] In this invention, the mass ratio of PVB resin to plasticizer is preferably 100:30~50, more preferably 100:35~45, and even more preferably 100:40.

[0038] In this invention, the adhesion modifier in the surface layer preferably includes one or more of magnesium salts and calcium salts; the magnesium salt is preferably magnesium acetate; and the calcium salt is preferably calcium acetate.

[0039] In this invention, the mass ratio of the PVB resin to the adhesion modifier is preferably 100:0.01~0.05, more preferably 100:0.02~0.04, and even more preferably 100:0.03.

[0040] In this invention, the low-migration phenolic antioxidant in the surface layer preferably includes one or two of 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and pentaerythritol tetrakis[β-(3,5-ditert-butyl-4-hydroxyphenyl)propionic acid].

[0041] In this invention, the hindered amine light stabilizer in the surface layer preferably includes one or both of poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexadiyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]] and bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate. This invention uses low-migration phenolic antioxidants to prevent migration to the glass surface that could lead to adhesion failure, and hindered amine light stabilizers to improve UV aging resistance.

[0042] In this invention, the mass ratio of the low-migration phenolic antioxidant to the hindered amine light stabilizer is preferably 0.3~0.7:0.2~0.3, more preferably 0.4~0.6:0.25, and even more preferably 0.5:0.25.

[0043] In this invention, the mass ratio of the PVB resin to the compounded antioxidant is preferably 100:0.5~1, more preferably 100:0.6~0.9, and even more preferably 100:0.7~0.8. The addition amount of the compounded antioxidant in this invention is within the above range, which can balance weather resistance and adhesion stability.

[0044] In this invention, the surface layer preferably further comprises an ultraviolet absorber; the ultraviolet absorber preferably comprises one or both of 2-(5-chloro-2-benzotriazolyl)-6-tert-butyl-p-cresol and 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole.

[0045] In this invention, the mass ratio of the PVB resin to the ultraviolet absorber is preferably 100:0.05~0.2, more preferably 100:0.08~0.16, and even more preferably 100:0.1~0.12.

[0046] In this invention, when the surface layer includes a heat-shielding material, the mass ratio of the PVB resin to the heat-shielding material is preferably 100:0.1~0.7, more preferably 100:0.3~0.5.

[0047] In this invention, the areal density of the heat-shielding material in the surface layer is preferably 0.10~0.70 g / m³. 2 More preferably, it is 0.30~0.60 g / m 2 More preferably 0.50 g / m 2 .

[0048] In this invention, the surface layer preferably comprises: 100 parts of PVB resin, 30-50 parts of plasticizer, 0.01-0.05 parts of adhesion modifier, 0.3-0.7 parts of low-migration phenolic antioxidant, 0.2-0.3 parts of hindered amine light stabilizer, 0.1-0.7 parts of heat shielding material, and 0.05-0.2 parts of ultraviolet absorber.

[0049] In this invention, the thickness ratio of the single-layer core sound insulation layer to the single-layer surface layer is preferably 100~120:300~350, more preferably 100~110:330.

[0050] In this invention, the heat shielding material is preferably an inorganic heat shielding material; the inorganic heat shielding material preferably includes one or more of cesium-doped tungsten oxide (CWO), tin-doped indium oxide (ITO), and antimony-doped tin oxide (ATO). At least one of the core sound insulation layer or surface layer also includes the heat shielding material, forming a heat shielding system.

[0051] In this invention, the average particle size of the heat-shielding material is preferably no greater than 50 nm, more preferably 30-50 nm. This invention uses the above-mentioned types and specifications of heat-shielding materials to ensure light transmittance.

[0052] In this invention, the ratio of the total mass of the composite antioxidant and the compounded antioxidant to the total mass of the heat shielding material is preferably 1 to 3:1, more preferably 2:1. This invention controls the above ratio to avoid excessive adsorption of antioxidants onto the surface of the heat shielding material, while simultaneously inhibiting the catalytic oxidation of the heat shielding material and improving compatibility.

[0053] This invention also provides a method for preparing the interlayer synergistic aging-resistant PVB composite intermediate film described above, comprising the following steps: The raw materials of the core sound insulation layer are mixed to obtain the first raw material, and the raw materials of the surface layer are mixed to obtain the second raw material. The first and second raw materials are melted and then subjected to multi-layer co-extrusion, hot pressing and cooling shaping in sequence to obtain the interlayer synergistic aging-resistant PVB composite intermediate film.

[0054] This invention involves mixing the raw materials of the core sound insulation layer (denoted as the first mixture) to obtain the first raw material. In this invention, the raw material of the core sound insulation layer preferably maintains the same composition as the core sound insulation layer itself; further details will not be elaborated here.

[0055] In this invention, the first mixing is preferably stirring mixing, and the parameters of the stirring mixing preferably include: using a high-speed mixer with a rotation speed of 500~1500 rpm, a mixing time of 15~30 minutes, and a mixing temperature of 40~60℃.

[0056] This invention involves mixing the raw materials of the surface layer to obtain a second raw material. In this invention, the raw materials of the surface layer preferably have the same composition as the surface layer itself, which will not be elaborated further here. This invention ensures the uniform dispersion of various antioxidants and heat-shielding materials by strictly controlling the proportions of each component.

[0057] In this invention, the second mixing is preferably agitated mixing, and the parameters of agitated mixing preferably include: using a low-speed mixer with a rotation speed of 200-500 rpm, a mixing time of 20-40 minutes, and a mixing temperature of 50-70°C.

[0058] After obtaining the first and second raw materials, the present invention melts the first and second raw materials respectively and then sequentially performs multilayer co-extrusion, hot pressing, and cooling shaping to obtain the interlayer synergistic aging-resistant PVB composite intermediate film. In the present invention, the preferred melting parameters include using a twin-screw extruder.

[0059] In this invention, for the first raw material (core sound insulation layer), the temperatures of each section of the extruder are preferably set as follows: 150~170℃ for the feeding section, 180~200℃ for the compression section, and 190~210℃ for the metering section; the screw speed is 80~150 rpm.

[0060] In this invention, for the second raw material (surface layer), the temperatures of each section of the extruder are preferably set as follows: 100~120℃ for the feeding section, 140~160℃ for the compression section, and 160~180℃ for the metering section; and the screw speed is 60~120 rpm.

[0061] In this invention, the preferred parameters for the multilayer co-extrusion include: the equipment comprising a screw extruder and a multilayer co-extrusion die; the extrusion temperature of the first raw material being 170~210℃, more preferably 180~200℃; and the extrusion temperature of the second raw material being 150~180℃, more preferably 160~170℃. This invention feeds the first and second raw materials into independent screw extruders, and the multilayer co-extrusion die causes the melt laminar flow to converge and overlap before extrusion. The independent screw extruders control the processing temperature of different layers to prevent material degradation, while the multilayer co-extrusion die ensures the convergence of the melt laminar flow, preventing interlayer mixing.

[0062] In this invention, the preferred parameters for hot pressing include: the equipment includes a hot press roller; the temperature is 140~170℃, more preferably 150~160℃; the pressure is 5~15MPa, more preferably 8~12MPa; and the holding time is preferably 5~15 seconds, more preferably 8~10 seconds. This invention, through the aforementioned hot pressing, promotes the diffusion and entanglement of interlayer molecular chains, forming a robust gradient interface region, thereby enabling the fusion of the multilayer co-extruded composite melt sheet.

[0063] In this invention, the cooling and shaping parameters preferably include: the equipment includes a cooling roller, the temperature of which is 20~40℃, and the final temperature is not higher than the glass transition temperature. This invention ensures the dimensional stability and performance uniformity of the interlayer synergistic aging-resistant PVB composite interlayer through rapid cooling.

[0064] In this invention, the cooling and shaping process preferably further includes trimming the edges and winding the resulting product in sequence.

[0065] The preparation method provided by this invention adopts a co-extrusion integrated process to ensure strong interlayer bonding.

[0066] The present invention also provides the application of the interlayer synergistic aging-resistant PVB composite interlayer film described in the above-described scheme or the interlayer synergistic aging-resistant PVB composite interlayer film obtained by the preparation method described in the above-described scheme in the field of laminated glass.

[0067] The interlayer synergistic aging-resistant PVB composite interlayer provided by this invention can be used in the field of laminated glass, such as building curtain walls, automotive windshields, safety laminated glass, or HUD display glass.

[0068] The present invention also provides a laminated glass comprising an interlayer and glass sandwiched on both sides of the interlayer, wherein the interlayer is the interlayer synergistic aging-resistant PVB composite interlayer described in the above-described scheme or the interlayer synergistic aging-resistant PVB composite interlayer obtained by the preparation method described in the above-described scheme.

[0069] The laminated glass provided by this invention has a visible light transmittance of ≥85%, an average infrared light transmittance of ≤70% in the 800~1100nm range, and a sound transmission loss of ≥39dB at 4000Hz.

[0070] To further illustrate the present invention, the technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments thereof.

[0071] In a specific embodiment of the present invention, the raw materials used are as follows: Thermoplastic elastomer: hydrogenated product of polystyrene-poly(isoprene / butadiene)-polystyrene triblock copolymer (residual carbon-carbon double bond content is 8.5 mol%), commercially available product, which is one or more of Sinopec Baling Petrochemical SEBS YH-503T, Kraton G1642H from the United States and Kuraray Septon 2063 from Japan; PVB resin: average viscosity, degree of polymerization 2000, hydroxyl content 18.5wt%, acetal degree 68mol%; Sulfur-based antioxidants: DLTP, DSTP; Phosphorus-based auxiliary antioxidants: tris(2,4-di-tert-butylphenyl) phosphite (IRGAFOS 168), bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite (ULTRANOX 626); Low-migration phenolic antioxidants: 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (CYANOX 2777), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (IRGANOX 1010); Hindered amine light stabilizers: poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexadiyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]] (CHIMASSORB 944), bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (TINUVIN 770); Heat shielding materials: CWO, ITO, average particle size 30nm; Plasticizers: 3GO, 4GO; Bond strength modifier: maleic anhydride modified polypropylene; Adhesion modifiers: magnesium acetate, calcium acetate; UV absorbers: 2-(5-chloro-2-benzotriazolyl)-6-tert-butyl-p-cresol (TINUVIN 326), 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole (TINUVIN 329).

[0072] Example 1: The raw material ratio (parts by weight) of the core sound insulation layer is as follows: 100 parts of thermoplastic elastomer (Sinopec Baling Petrochemical SEBS YH-503T), 0.15 parts of DLTP, 0.1 parts of IRGAFOS 168, 0.25 parts of CWO and 5 parts of maleic anhydride modified polypropylene. The raw material ratio of the surface layer (parts by weight): 100 parts PVB resin, 38 parts 3GO, 0.02 parts magnesium acetate, 0.7 parts CYANOX2777, 0.3 parts CHIMASSORB 944, 0.28 parts CWO and 0.1 parts TINUVIN 326; Material preparation: Mix the raw materials of the core sound insulation layer (using a high-speed mixer, speed of 500 rpm, mixing time of 30 minutes, mixing temperature of 60℃) and the raw materials of the surface layer (using a low-speed mixer, speed of 200 rpm, mixing time of 40 minutes, mixing temperature of 70℃) according to the above proportions, and stir evenly to obtain the first raw material and the second raw material respectively; Co-extrusion molding: The first and second raw materials are fed into independent screw extruders. For the first raw material (core sound insulation layer), the extruder temperatures are set as follows: feeding section 160℃, compression section 185℃, metering section 190℃, and screw speed 120 rpm. For the second raw material (surface layer), the extruder temperatures are set as follows: feeding section 120℃, compression section 155℃, metering section 165℃, and screw speed 90 rpm. The melt is then extruded after laminar flow merging and overlapping through a multi-layer co-extrusion die. Hot pressing fusion: The extruded composite melt sheet is treated with a hot press roller at 155℃ and 10MPa for 10 seconds; Cooling and shaping: After cooling with a 30℃ cooling roller, the edges are trimmed and the film is wound up to obtain a layer-synergistic aging-resistant PVB composite intermediate film.

[0073] Product specifications for interlayer synergistic aging-resistant PVB composite intermediate film: The thickness of the core sound insulation layer is 100μm, the thickness of the single layer of the surface layer is 330μm, and the total thickness of the interlayer synergistic aging-resistant PVB composite intermediate film is 760μm.

[0074] Example 2: The raw material ratio (parts by weight) of the core sound insulation layer is as follows: 100 parts of thermoplastic elastomer (Kraton G1642H, USA), 0.2 parts of DSTP, 0.08 parts of ULTRANOX 626, 0.4 parts of ITO, and 3 parts of maleic anhydride modified polypropylene. The raw material ratio of the surface layer (parts by weight): 100 parts PVB resin, 45 parts 4GO, 0.04 parts calcium acetate, 0.5 parts IRGANOX 1010, 0.25 parts TINUVIN 770, 0.6 parts ITO, and 0.15 parts TINUVIN 329; Material preparation: Mix the raw materials of the core sound insulation layer (using a high-speed mixer, speed of 1500 rpm, mixing time of 15 minutes, mixing temperature of 40℃) and the raw materials of the surface layer (using a low-speed mixer, speed of 500 rpm, mixing time of 20 minutes, mixing temperature of 50℃) according to the above proportions, and stir evenly to obtain the first raw material and the second raw material respectively; Co-extrusion molding: The first and second raw materials are fed into independent screw extruders. For the first raw material (core sound insulation layer), the extruder temperatures are set as follows: feeding section 155℃, compression section 185℃, metering section 200℃; screw speed 120 rpm. For the second raw material (surface layer), the extruder temperatures are set as follows: feeding section 110℃, compression section 150℃, metering section 170℃; screw speed 100 rpm. The melt is then extruded after laminar flow merging and superimposing through a multi-layer co-extrusion die. Hot pressing fusion: The extruded composite melt sheet is treated with a hot press roller at 160℃ and 12MPa for 8 seconds; Cooling and shaping: After cooling with a 35℃ cooling roller, the edges are trimmed and the film is rolled up to obtain a synergistic aging-resistant PVB composite intermediate film.

[0075] Product specifications for interlayer synergistic aging-resistant PVB composite intermediate film: The thickness of the core sound insulation layer is 120μm, the thickness of the single layer of the surface layer is 300μm, and the total thickness of the interlayer synergistic aging-resistant PVB composite intermediate film is 720μm.

[0076] Comparative Example 1: The preparation method of this comparative example is the same as that of Example 1, except that a single phenolic antioxidant (CYANOX 2777) is added, and the sulfur antioxidant, phosphorus auxiliary antioxidant and hindered amine light stabilizer are replaced by 0.5 parts of CYANOX 2777 respectively.

[0077] Comparative Example 2: The preparation method of this comparative example is the same as that of Example 1, except that the mass ratio of all antioxidants (low-migration phenolic antioxidants, sulfur antioxidants, phosphorus auxiliary antioxidants and hindered amine light stabilizers) to the heat shielding material is 1:3.

[0078] Test Example 1: The interlayer synergistic aging-resistant PVB composite intermediate films prepared in Examples 1-2 and Comparative Examples 1-2 were subjected to performance tests. The test standards and methods are as follows: Visible light transmittance: measured using a spectrophotometer U-4100 according to JIS R 3106. The test sample was prepared by sandwiching the interlayer synergistic aging-resistant PVB composite interlayer between two 2mm thick transparent float glass sheets and then hot-pressing them together.

[0079] Average infrared transmittance of 800~1100nm: measured using a U-4100 spectrophotometer according to ASTM E903; 4000Hz acoustic transmission loss: Measured using an acoustic testing system according to ASTM E90-09; Color difference (ΔE*ab) after xenon lamp aging: According to JIS Z 8781-4, after 200 hours of xenon lamp aging (illuminance 180W / m²) 2 After the black panel temperature is 60℃ and the relative humidity is 50%, the color difference is measured using an SM-T colorimeter. Shear strength retention rate after damp heat aging: According to ANSI Z97.1 Appendix, after aging at 85℃ / 85% RH for 1000 hours, the shear strength of the glass and interlayer synergistic aging-resistant PVB composite interlayer was tested, and the ratio to the initial shear strength was calculated. Dispersion of heat shielding materials (haze): According to JIS K 7105, the haze of the interlayer synergistic aging-resistant PVB composite intermediate film was measured using a haze meter.

[0080] The test results are shown in Table 1.

[0081] Table 1 Performance test results of Test Example 1:

[0082] As shown in Table 1, the test results of Examples 1 and 2 demonstrate that the present invention significantly improves the aging resistance, heat insulation efficiency, and structural stability of the interlayer synergistic aging-resistant PVB composite interlayer by precisely distributing the antioxidant synergistically and improving the compatibility between the antioxidant and the heat shielding material. Compared with Comparative Example 1 (single antioxidant), the interlayer synergistic aging-resistant PVB composite interlayer of the present invention exhibits smaller color difference and higher shear strength retention after aging. Compared with Comparative Example 2 (improper ratio of antioxidant to heat shielding material), the interlayer synergistic aging-resistant PVB composite interlayer of the present invention has lower infrared transmittance (better heat insulation effect) and lower haze (better dispersion), and all performance characteristics meet the requirements for high-end laminated glass.

[0083] The embodiments of the present invention have been described above; however, these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. All other embodiments obtained by those skilled in the art based on the above embodiments of the present invention without inventive effort are within the protection scope of the present invention.

Claims

1. A layer-by-layer synergistic aging-resistant PVB composite interlayer, characterized in that, It includes a core sound insulation layer and a surface layer composited on both sides of the core sound insulation layer; The core sound insulation layer comprises thermoplastic elastomer and composite antioxidants; The thermoplastic elastomer is a hydrogenated product of a block copolymer containing aromatic vinyl monomer units and conjugated diene monomer units, with a residual carbon-carbon double bond content of 2-40 mol%. The composite antioxidant includes sulfur-based antioxidants and phosphorus-based auxiliary antioxidants; The surface layer comprises PVB resin, plasticizer, adhesion modifier, and compounded antioxidant; The compound antioxidants include low-migratory phenolic antioxidants and hindered amine light stabilizers; The composition of at least one of the core sound insulation layers or surface layers also includes heat shielding materials.

2. The interlayer synergistic aging-resistant PVB composite intermediate film according to claim 1, characterized in that, The core sound insulation layer has one or more layers; The surface layer has two or more layers; The thickness ratio of the single-layer core sound insulation layer to the single-layer surface layer is 100~120:300~350.

3. The interlayer synergistic aging-resistant PVB composite intermediate film according to claim 1, characterized in that, The sulfur-based antioxidants include one or more of dilauryl 3,3'-thiodipropionate and distearate 3,3'-thiodipropionate. The phosphorus-based auxiliary antioxidants include one or more of tris(2,4-di-tert-butylphenyl) phosphite and bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite; The mass ratio of the sulfur-based antioxidant to the phosphorus-based auxiliary antioxidant is 0.08~0.2:0.02~0.1; The mass ratio of the thermoplastic elastomer to the composite antioxidant is 100:0.1~0.

3.

4. The interlayer synergistic aging-resistant PVB composite intermediate film according to claim 1, characterized in that, The core sound insulation layer also includes an adhesive strength modifier; The mass ratio of the thermoplastic elastomer to the adhesive strength modifier is 100:0~5.

5. The interlayer synergistic aging-resistant PVB composite intermediate film according to claim 1, characterized in that, In the surface layer, the low-migration phenolic antioxidants include one or two of 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; In the surface layer, the hindered amine light stabilizer includes one or two of poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexadiyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]] and bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate; The mass ratio of the low-migration phenolic antioxidant to the hindered amine light stabilizer is 0.3~0.7:0.2~0.3; The mass ratio of the PVB resin to the compound antioxidant is 100:0.5~1.

6. The interlayer synergistic aging-resistant PVB composite intermediate film according to claim 1, characterized in that, The surface layer also includes ultraviolet absorbers; The ultraviolet absorber includes one or both of 2-(5-chloro-2-benzotriazolyl)-6-tert-butyl-p-cresol and 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole.

7. The interlayer synergistic aging-resistant PVB composite intermediate film according to claim 1, characterized in that, The ratio of the total mass of the composite antioxidant and the compound antioxidant to the total mass of the heat shielding material is 1 to 3:

1.

8. A method for preparing an interlayer synergistic aging-resistant PVB composite intermediate film, characterized in that, The interlayer synergistic aging-resistant PVB composite interlayer is the interlayer synergistic aging-resistant PVB composite interlayer as described in any one of claims 1 to 7, and includes the following steps: The raw materials of the core sound insulation layer are mixed to obtain the first raw material, and the raw materials of the surface layer are mixed to obtain the second raw material. The first and second raw materials are melted and then subjected to multi-layer co-extrusion, hot pressing and cooling shaping in sequence to obtain the interlayer synergistic aging-resistant PVB composite intermediate film.

9. The application of a layer-by-layer synergistic aging-resistant PVB composite interlayer in the field of laminated glass, characterized in that, The interlayer synergistic aging-resistant PVB composite intermediate film is the interlayer synergistic aging-resistant PVB composite intermediate film according to any one of claims 1 to 7 or the interlayer synergistic aging-resistant PVB composite intermediate film obtained by the preparation method according to claim 8.

10. A laminated glass, characterized in that, It includes an interlayer film and glass sandwiched on both sides of the interlayer film, wherein the interlayer film is the interlayer synergistic aging-resistant PVB composite interlayer film according to any one of claims 1 to 7 or the interlayer synergistic aging-resistant PVB composite interlayer film obtained by the preparation method according to claim 8.

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