CN110255930B - High-strength laminated glass containing PVB and preparation method thereof - Google Patents

High-strength laminated glass containing PVB and preparation method thereof Download PDF

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CN110255930B
CN110255930B CN201910609699.4A CN201910609699A CN110255930B CN 110255930 B CN110255930 B CN 110255930B CN 201910609699 A CN201910609699 A CN 201910609699A CN 110255930 B CN110255930 B CN 110255930B
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layer
acetalization degree
mol
pvb
transition temperature
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CN110255930A (en
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赵明
凡广生
刘艳丽
孙学习
刘萌
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Zhengzhou Institute of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/05—5 or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/42—Alternating layers, e.g. ABAB(C), AABBAABB(C)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules

Abstract

The invention discloses high-strength laminated glass containing PVB, which sequentially comprises the following components from inside to outside: the first glass layer, the first PVB layer, the first PET layer, the second PVB layer, the second PET layer, the third PVB layer, the third PET layer, the fourth PVB layer and the second glass layer, wherein the first PVB layer has a first hydroxyl content measured according to JIS K6728, the second PVB layer has a second hydroxyl content measured according to JIS K6728, the third PVB layer has a second hydroxyl content measured according to JIS K6728, the fourth PVB layer has a fourth hydroxyl content measured according to JIS K6728, the first hydroxyl content is smaller than the second hydroxyl content, the second hydroxyl content is smaller than the second hydroxyl content, and the second hydroxyl content is smaller than the fourth hydroxyl content. The high-strength laminated glass can obviously increase multiple strength indexes of the layer under the condition of not increasing the thickness of the layer.

Description

High-strength laminated glass containing PVB and preparation method thereof
Technical Field
The invention relates to the technical field of laminated glass, in particular to high-strength laminated glass containing PVB and a preparation method thereof.
Background
The laminated glass is a composite glass product which is formed by two or more pieces of glass, wherein one or more layers of organic polymer intermediate films are sandwiched between the two or more pieces of glass, and the glass and the intermediate films are permanently bonded into a whole after special high-temperature prepressing (or vacuumizing) and high-temperature high-pressure processing. The composite glass product is a product which is widely applied in the chemical field.
Prior art CN105939979B discloses an interlayer film for laminated glass, which is less likely to cause voids at the ends of the laminated glass and can suppress an increase in YI value at the ends of the laminated glass. The interlayer film for laminated glass of the present invention has a one-layer structure or a structure having two or more layers, wherein the entire interlayer film contains a polyvinyl acetal resin, a plasticizer, a hindered amine light stabilizer and a phosphorus-containing antioxidant, and when the interlayer film has only a first layer, the glass transition temperature of the first layer is 32 ℃ or higher, and when the interlayer film has the first layer and a second layer, and with or without a third layer, the glass transition temperature of at least one of the second layer and the third layer is 32 ℃ or higher.
Prior art CN105682917B discloses an interlayer comprising a high flow, low molecular weight thermoplastic resin, and at least one plasticizer. The use of high flow, low molecular weight thermoplastic resins and plasticizers produces a synergistic effect that can increase the flow of the interlayer without sacrificing other characteristics typically associated with increased flow (e.g., increased blocking, decreased mechanical strength, and decreased manufacturing capability). In this regard, the high flow, low molecular weight thermoplastic resin provides improved flow properties, forming a high flow interlayer.
Prior art CN105431394B discloses a windshield for a vehicle, which has a laminated glass structure in which an interlayer film for a laminated glass is sandwiched between at least a pair of glass plates, wherein the interlayer film for a laminated glass comprises a laminate in which two or more resin layers are laminated, and the windshield for a vehicle has excellent appearance with few bubbles remaining between the glass plates and the interlayer film for a laminated glass, and is less likely to generate ghost images when external light is visually recognized through the windshield for a vehicle. The windshield glass for a vehicle has a laminated glass structure in which an interlayer film for a laminated glass is sandwiched between at least a pair of glass plates, the interlayer film for a laminated glass includes a laminate in which two or more resin layers are laminated, and has a plurality of recesses and a plurality of protrusions on at least one surface, the recesses have a groove shape with a continuous bottom, and the adjacent recesses are arranged in parallel and regularly, the groove depth (Rzg) of the recess measured according to JIS B-0601(1994) of the surface having the plurality of recesses and the plurality of protrusions of the interlayer film for a laminated glass is 10 to 40 [ mu ] m, and the direction of the groove shape with a continuous bottom of the recess on the surface of the interlayer film for a laminated glass is arranged so as to form an angle of 30 DEG or less with respect to the vertical direction of the windshield glass for a vehicle.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
It is an object of the present invention to provide a high strength laminated glass comprising PVB and a method for making the same that overcomes the disadvantages of the prior art.
In order to achieve the above object, the present invention provides a high strength laminated glass comprising PVB, which comprises, in order from the inside to the outside: the first glass layer, the first PVB layer, the first PET layer, the second PVB layer, the second PET layer, the third PVB layer, the third PET layer, the fourth PVB layer and the second glass layer, wherein the first PVB layer has a first hydroxyl content measured according to JIS K6728, the second PVB layer has a second hydroxyl content measured according to JIS K6728, the third PVB layer has a second hydroxyl content measured according to JIS K6728, the fourth PVB layer has a fourth hydroxyl content measured according to JIS K6728, the first hydroxyl content is smaller than the second hydroxyl content, the second hydroxyl content is smaller than the second hydroxyl content, and the second hydroxyl content is smaller than the fourth hydroxyl content.
Preferably, in the above scheme, the first PVB layer has a first acetalization degree measured according to JIS K6728, the second PVB layer has a second acetalization degree measured according to JIS K6728, the third PVB layer has a third acetalization degree measured according to JIS K6728, and the fourth PVB layer has a fourth acetalization degree measured according to JIS K6728, wherein the first acetalization degree is greater than the second acetalization degree, the second acetalization degree is greater than the third acetalization degree, and the third acetalization degree is greater than the fourth acetalization degree.
Preferably, in the above embodiment, the first hydroxyl group content is 10 to 15 mol%, the second hydroxyl group content is 11 to 16 mol%, the second hydroxyl group content is 12 to 17 mol%, and the fourth hydroxyl group content is 13 to 18 mol%.
Preferably, in the above scheme, the first acetalization degree is 75 to 80 mol%, the second acetalization degree is 74 to 79 mol%, the third acetalization degree is 73 to 78 mol%, and the fourth acetalization degree is 72 to 77 mol%.
Preferably, in the above embodiment, the first PET layer has a first glass transition temperature as determined by ASTM E1356 differential scanning calorimetry, the second PET layer has a second glass transition temperature as determined by ASTM E1356 differential scanning calorimetry, and the third PET layer has a third glass transition temperature as determined by ASTM E1356 differential scanning calorimetry, the first glass transition temperature being greater than the second glass transition temperature, and the second glass transition temperature being greater than the third glass transition temperature.
Preferably, in the above embodiment, the difference between the first hydroxyl group content and the second hydroxyl group content is less than 3 mol%, the difference between the second hydroxyl group content and the second hydroxyl group content is less than 2 mol%, and the difference between the second hydroxyl group content and the fourth hydroxyl group content is less than 2 mol%.
Preferably, in the above embodiment, the difference between the first acetalization degree and the second acetalization degree is less than 2 mol%, the difference between the second acetalization degree and the third acetalization degree is less than 3 mol%, and the difference between the third acetalization degree and the fourth acetalization degree is less than 3 mol%.
Preferably, in the above aspect, the difference between the first glass transition temperature and the second glass transition temperature is less than 5 ℃, and the difference between the second glass transition temperature and the third glass transition temperature is less than 5 ℃.
The invention also provides a preparation method of the high-strength laminated glass containing the PVB, which comprises the following steps: laminating the first PVB layer, the first PET layer, the second PVB layer, the second PET layer, the third PVB layer, the third PET layer and the fourth PVB layer into a polymer laminated body through hot pressing; and placing the polymer laminate between two layers of glass and hot pressing the resulting laminate.
Compared with the prior art, the high-strength laminated glass containing PVB and the preparation method thereof have the following advantages: laminated glass has wide application, and how to improve the strength of the laminated glass is always the focus of attention in the industry. The means of increasing the strength of laminated glass generally involves either increasing the strength of the glass layer or increasing the strength of the intermediate polymer layer. While methods of increasing the strength of the intermediate polymer layer generally include increasing the layer thickness, changing the layer composition, and the like. However, increasing the layer thickness generally greatly reduces the optical transmission of the glass, which is a problem that the industry always hopes to avoid, changing the layer composition requires a lot of experiments, and blindly changing the layer composition will cause uncontrollable increase of the development cost without guidance of the prior art. The invention provides high-strength laminated glass aiming at the problems in the prior art, and according to the layer design of the application, the invention can obviously increase multiple strength indexes of a layer under the condition of not increasing the thickness of the layer.
Drawings
Fig. 1 is a schematic structural diagram of a high-strength laminated glass according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The single-layer polymer film can be purchased directly from manufacturers, the manufacturers can provide single-layer polymer films meeting parameter requirements, the thickness of each layer can be adjusted according to the requirements of automobile manufacturers, and the single-layer polymer film can be designed according to the known film thickness in the field. The tests of the present invention are a tap adhesion test and a peel adhesion test according to ASTM related standards, the standard comparative example being a commercially available brand of laminated glass (with the values of tap adhesion and peel adhesion being 100% in the standard, and the thickness of the glass layer in the examples of the present application being equal to the thickness of the glass layer of the standard comparative example, and the total thickness of the polymer layers being equal to the total thickness of the polymer layers of the standard comparative example).
Fig. 1 is a schematic structural diagram according to an embodiment of the present invention. As shown, the high strength laminated glass comprising PVB sequentially comprises from inside to outside: first glass layer 109, first PVB layer 108, first PET layer 107, second PVB layer 106, second PET layer 105, third PVB layer 104, third PET layer 103, fourth PVB layer 102, and second glass layer 101.
Example 1
High strength laminated glass who contains PVB includes from inside to outside in proper order: the first glass layer, the first PVB layer, the first PET layer, the second PVB layer, the second PET layer, the third PVB layer, the third PET layer, the fourth PVB layer and the second glass layer, wherein the first PVB layer has a first hydroxyl content measured according to JIS K6728, the second PVB layer has a second hydroxyl content measured according to JIS K6728, the third PVB layer has a second hydroxyl content measured according to JIS K6728, the fourth PVB layer has a fourth hydroxyl content measured according to JIS K6728, the first hydroxyl content is smaller than the second hydroxyl content, the second hydroxyl content is smaller than the second hydroxyl content, and the second hydroxyl content is smaller than the fourth hydroxyl content. The first PVB layer has a first acetalization degree measured according to JIS K6728, the second PVB layer has a second acetalization degree measured according to JIS K6728, the third PVB layer has a third acetalization degree measured according to JIS K6728, and the fourth PVB layer has a fourth acetalization degree measured according to JIS K6728, wherein the first acetalization degree is greater than the second acetalization degree, the second acetalization degree is greater than the third acetalization degree, and the third acetalization degree is greater than the fourth acetalization degree. The first hydroxyl group content was 10 mol%, the second hydroxyl group content was 11 mol%, the second hydroxyl group content was 12 mol%, and the fourth hydroxyl group content was 13 mol%. The first acetalization degree is 75 mol%, the second acetalization degree is 74 mol%, the third acetalization degree is 73 mol%, and the fourth acetalization degree is 72 mol%. The first PET layer has a first glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the second PET layer has a second glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the third PET layer has a third glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the first glass transition temperature is greater than the second glass transition temperature, and the second glass transition temperature is greater than the third glass transition temperature. The difference between the first hydroxyl group content and the second hydroxyl group content is less than 3 mol%, the difference between the second hydroxyl group content and the second hydroxyl group content is less than 2 mol%, and the difference between the second hydroxyl group content and the fourth hydroxyl group content is less than 2 mol%. The difference between the first acetalization degree and the second acetalization degree is less than 2 mol%, the difference between the second acetalization degree and the third acetalization degree is less than 3 mol%, and the difference between the third acetalization degree and the fourth acetalization degree is less than 3 mol%. The difference between the first glass transition temperature and the second glass transition temperature is less than 5 ℃, and the difference between the second glass transition temperature and the third glass transition temperature is less than 5 ℃. The tap adhesion was 130% and the peel adhesion was 140%.
Example 2
High strength laminated glass who contains PVB includes from inside to outside in proper order: the first glass layer, the first PVB layer, the first PET layer, the second PVB layer, the second PET layer, the third PVB layer, the third PET layer, the fourth PVB layer and the second glass layer, wherein the first PVB layer has a first hydroxyl content measured according to JIS K6728, the second PVB layer has a second hydroxyl content measured according to JIS K6728, the third PVB layer has a second hydroxyl content measured according to JIS K6728, the fourth PVB layer has a fourth hydroxyl content measured according to JIS K6728, the first hydroxyl content is smaller than the second hydroxyl content, the second hydroxyl content is smaller than the second hydroxyl content, and the second hydroxyl content is smaller than the fourth hydroxyl content. The first PVB layer has a first acetalization degree measured according to JIS K6728, the second PVB layer has a second acetalization degree measured according to JIS K6728, the third PVB layer has a third acetalization degree measured according to JIS K6728, and the fourth PVB layer has a fourth acetalization degree measured according to JIS K6728, wherein the first acetalization degree is greater than the second acetalization degree, the second acetalization degree is greater than the third acetalization degree, and the third acetalization degree is greater than the fourth acetalization degree. The first hydroxyl group content was 15 mol%, the second hydroxyl group content was 16 mol%, the second hydroxyl group content was 17 mol%, and the fourth hydroxyl group content was 18 mol%. The first acetalization degree is 80 mol%, the second acetalization degree is 79 mol%, the third acetalization degree is 78 mol%, and the fourth acetalization degree is 77 mol%. The first PET layer has a first glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the second PET layer has a second glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the third PET layer has a third glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the first glass transition temperature is greater than the second glass transition temperature, and the second glass transition temperature is greater than the third glass transition temperature. The difference between the first hydroxyl group content and the second hydroxyl group content is less than 3 mol%, the difference between the second hydroxyl group content and the second hydroxyl group content is less than 2 mol%, and the difference between the second hydroxyl group content and the fourth hydroxyl group content is less than 2 mol%. The difference between the first acetalization degree and the second acetalization degree is less than 2 mol%, the difference between the second acetalization degree and the third acetalization degree is less than 3 mol%, and the difference between the third acetalization degree and the fourth acetalization degree is less than 3 mol%. The difference between the first glass transition temperature and the second glass transition temperature is less than 5 ℃, and the difference between the second glass transition temperature and the third glass transition temperature is less than 5 ℃. Tack adhesion 135% and peel adhesion 145%.
Example 3
High strength laminated glass who contains PVB includes from inside to outside in proper order: the first glass layer, the first PVB layer, the first PET layer, the second PVB layer, the second PET layer, the third PVB layer, the third PET layer, the fourth PVB layer and the second glass layer, wherein the first PVB layer has a first hydroxyl content measured according to JIS K6728, the second PVB layer has a second hydroxyl content measured according to JIS K6728, the third PVB layer has a second hydroxyl content measured according to JIS K6728, the fourth PVB layer has a fourth hydroxyl content measured according to JIS K6728, the first hydroxyl content is smaller than the second hydroxyl content, the second hydroxyl content is smaller than the second hydroxyl content, and the second hydroxyl content is smaller than the fourth hydroxyl content. The first PVB layer has a first acetalization degree measured according to JIS K6728, the second PVB layer has a second acetalization degree measured according to JIS K6728, the third PVB layer has a third acetalization degree measured according to JIS K6728, and the fourth PVB layer has a fourth acetalization degree measured according to JIS K6728, wherein the first acetalization degree is greater than the second acetalization degree, the second acetalization degree is greater than the third acetalization degree, and the third acetalization degree is greater than the fourth acetalization degree. The first hydroxyl group content was 12 mol%, the second hydroxyl group content was 13 mol%, the second hydroxyl group content was 14 mol%, and the fourth hydroxyl group content was 15 mol%. The first acetalization degree is 77 mol%, the second acetalization degree is 76 mol%, the third acetalization degree is 75 mol%, and the fourth acetalization degree is 74 mol%. The first PET layer has a first glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the second PET layer has a second glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the third PET layer has a third glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the first glass transition temperature is greater than the second glass transition temperature, and the second glass transition temperature is greater than the third glass transition temperature. The difference between the first hydroxyl group content and the second hydroxyl group content is less than 3 mol%, the difference between the second hydroxyl group content and the second hydroxyl group content is less than 2 mol%, and the difference between the second hydroxyl group content and the fourth hydroxyl group content is less than 2 mol%. The difference between the first acetalization degree and the second acetalization degree is less than 2 mol%, the difference between the second acetalization degree and the third acetalization degree is less than 3 mol%, and the difference between the third acetalization degree and the fourth acetalization degree is less than 3 mol%. The difference between the first glass transition temperature and the second glass transition temperature is less than 5 ℃, and the difference between the second glass transition temperature and the third glass transition temperature is less than 5 ℃. The tap adhesion was 125% and the peel adhesion was 150%.
Example 4
High strength laminated glass who contains PVB includes from inside to outside in proper order: the first glass layer, the first PVB layer, the first PET layer, the second PVB layer, the second PET layer, the third PVB layer, the third PET layer, the fourth PVB layer and the second glass layer, wherein the first PVB layer has a first hydroxyl content measured according to JIS K6728, the second PVB layer has a second hydroxyl content measured according to JIS K6728, the third PVB layer has a second hydroxyl content measured according to JIS K6728, the fourth PVB layer has a fourth hydroxyl content measured according to JIS K6728, the first hydroxyl content is smaller than the second hydroxyl content, the second hydroxyl content is smaller than the second hydroxyl content, and the second hydroxyl content is smaller than the fourth hydroxyl content. The first PVB layer has a first acetalization degree measured according to JIS K6728, the second PVB layer has a second acetalization degree measured according to JIS K6728, the third PVB layer has a third acetalization degree measured according to JIS K6728, and the fourth PVB layer has a fourth acetalization degree measured according to JIS K6728, wherein the first acetalization degree is greater than the second acetalization degree, the second acetalization degree is greater than the third acetalization degree, and the third acetalization degree is greater than the fourth acetalization degree. The first hydroxyl group content was 13 mol%, the second hydroxyl group content was 13 mol%, and the fourth hydroxyl group content was 13 mol%. The first acetalization degree is 75 mol%, the second acetalization degree is 74 mol%, the third acetalization degree is 73 mol%, and the fourth acetalization degree is 72 mol%. The first PET layer has a first glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the second PET layer has a second glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the third PET layer has a third glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the first glass transition temperature is greater than the second glass transition temperature, and the second glass transition temperature is greater than the third glass transition temperature. The difference between the first glass transition temperature and the second glass transition temperature is less than 5 ℃, and the difference between the second glass transition temperature and the third glass transition temperature is less than 5 ℃. The tap adhesion was 80% and the peel adhesion was 75%.
Example 5
High strength laminated glass who contains PVB includes from inside to outside in proper order: the first glass layer, the first PVB layer, the first PET layer, the second PVB layer, the second PET layer, the third PVB layer, the third PET layer, the fourth PVB layer and the second glass layer, wherein the first PVB layer has a first hydroxyl content measured according to JIS K6728, the second PVB layer has a second hydroxyl content measured according to JIS K6728, the third PVB layer has a second hydroxyl content measured according to JIS K6728, the fourth PVB layer has a fourth hydroxyl content measured according to JIS K6728, the first hydroxyl content is smaller than the second hydroxyl content, the second hydroxyl content is smaller than the second hydroxyl content, and the second hydroxyl content is smaller than the fourth hydroxyl content. The first PVB layer has a first acetalization degree measured according to JIS K6728, the second PVB layer has a second acetalization degree measured according to JIS K6728, the third PVB layer has a third acetalization degree measured according to JIS K6728, and the fourth PVB layer has a fourth acetalization degree measured according to JIS K6728, wherein the first acetalization degree is greater than the second acetalization degree, the second acetalization degree is greater than the third acetalization degree, and the third acetalization degree is greater than the fourth acetalization degree. The first hydroxyl group content was 10 mol%, the second hydroxyl group content was 15 mol%, the second hydroxyl group content was 20 mol%, and the fourth hydroxyl group content was 25 mol%. The first acetalization degree is 75 mol%, the second acetalization degree is 74 mol%, the third acetalization degree is 73 mol%, and the fourth acetalization degree is 72 mol%. The first PET layer has a first glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the second PET layer has a second glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the third PET layer has a third glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the first glass transition temperature is greater than the second glass transition temperature, and the second glass transition temperature is greater than the third glass transition temperature. The difference between the first glass transition temperature and the second glass transition temperature is less than 5 ℃, and the difference between the second glass transition temperature and the third glass transition temperature is less than 5 ℃. The tap adhesion was 75% and the peel adhesion was 85%.
Example 6
High strength laminated glass who contains PVB includes from inside to outside in proper order: the first glass layer, the first PVB layer, the first PET layer, the second PVB layer, the second PET layer, the third PVB layer, the third PET layer, the fourth PVB layer and the second glass layer, wherein the first PVB layer has a first hydroxyl content measured according to JIS K6728, the second PVB layer has a second hydroxyl content measured according to JIS K6728, the third PVB layer has a second hydroxyl content measured according to JIS K6728, the fourth PVB layer has a fourth hydroxyl content measured according to JIS K6728, the first hydroxyl content is smaller than the second hydroxyl content, the second hydroxyl content is smaller than the second hydroxyl content, and the second hydroxyl content is smaller than the fourth hydroxyl content. The first PVB layer has a first acetalization degree measured according to JIS K6728, the second PVB layer has a second acetalization degree measured according to JIS K6728, the third PVB layer has a third acetalization degree measured according to JIS K6728, and the fourth PVB layer has a fourth acetalization degree measured according to JIS K6728, wherein the first acetalization degree is greater than the second acetalization degree, the second acetalization degree is greater than the third acetalization degree, and the third acetalization degree is greater than the fourth acetalization degree. The first hydroxyl group content was 10 mol%, the second hydroxyl group content was 11 mol%, the second hydroxyl group content was 12 mol%, and the fourth hydroxyl group content was 13 mol%. The first acetalization degree is 75 mol%, the second acetalization degree is 75 mol%, the third acetalization degree is 75 mol%, and the fourth acetalization degree is 75 mol%. The first PET layer has a first glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the second PET layer has a second glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the third PET layer has a third glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the first glass transition temperature is greater than the second glass transition temperature, and the second glass transition temperature is greater than the third glass transition temperature. The difference between the first glass transition temperature and the second glass transition temperature is less than 5 ℃, and the difference between the second glass transition temperature and the third glass transition temperature is less than 5 ℃. The tap adhesion was 60% and the peel adhesion was 110%.
Example 7
High strength laminated glass who contains PVB includes from inside to outside in proper order: the first glass layer, the first PVB layer, the first PET layer, the second PVB layer, the second PET layer, the third PVB layer, the third PET layer, the fourth PVB layer and the second glass layer, wherein the first PVB layer has a first hydroxyl content measured according to JIS K6728, the second PVB layer has a second hydroxyl content measured according to JIS K6728, the third PVB layer has a second hydroxyl content measured according to JIS K6728, the fourth PVB layer has a fourth hydroxyl content measured according to JIS K6728, the first hydroxyl content is smaller than the second hydroxyl content, the second hydroxyl content is smaller than the second hydroxyl content, and the second hydroxyl content is smaller than the fourth hydroxyl content. The first PVB layer has a first acetalization degree measured according to JIS K6728, the second PVB layer has a second acetalization degree measured according to JIS K6728, the third PVB layer has a third acetalization degree measured according to JIS K6728, and the fourth PVB layer has a fourth acetalization degree measured according to JIS K6728, wherein the first acetalization degree is greater than the second acetalization degree, the second acetalization degree is greater than the third acetalization degree, and the third acetalization degree is greater than the fourth acetalization degree. The first hydroxyl group content was 10 mol%, the second hydroxyl group content was 11 mol%, the second hydroxyl group content was 12 mol%, and the fourth hydroxyl group content was 13 mol%. The first acetalization degree was 75 mol%, the second acetalization degree was 79 mol%, the third acetalization degree was 83 mol%, and the fourth acetalization degree was 87 mol%. The first PET layer has a first glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the second PET layer has a second glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the third PET layer has a third glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the first glass transition temperature is greater than the second glass transition temperature, and the second glass transition temperature is greater than the third glass transition temperature. The difference between the first glass transition temperature and the second glass transition temperature is less than 5 ℃, and the difference between the second glass transition temperature and the third glass transition temperature is less than 5 ℃. The tap adhesion was 70% and the peel adhesion was 115%.
Example 8
High strength laminated glass who contains PVB includes from inside to outside in proper order: the first glass layer, the first PVB layer, the first PET layer, the second PVB layer, the second PET layer, the third PVB layer, the third PET layer, the fourth PVB layer and the second glass layer, wherein the first PVB layer has a first hydroxyl content measured according to JIS K6728, the second PVB layer has a second hydroxyl content measured according to JIS K6728, the third PVB layer has a second hydroxyl content measured according to JIS K6728, the fourth PVB layer has a fourth hydroxyl content measured according to JIS K6728, the first hydroxyl content is smaller than the second hydroxyl content, the second hydroxyl content is smaller than the second hydroxyl content, and the second hydroxyl content is smaller than the fourth hydroxyl content. The first PVB layer has a first acetalization degree measured according to JIS K6728, the second PVB layer has a second acetalization degree measured according to JIS K6728, the third PVB layer has a third acetalization degree measured according to JIS K6728, and the fourth PVB layer has a fourth acetalization degree measured according to JIS K6728, wherein the first acetalization degree is greater than the second acetalization degree, the second acetalization degree is greater than the third acetalization degree, and the third acetalization degree is greater than the fourth acetalization degree. The first hydroxyl group content was 12 mol%, the second hydroxyl group content was 13 mol%, the second hydroxyl group content was 14 mol%, and the fourth hydroxyl group content was 15 mol%. The first acetalization degree is 77 mol%, the second acetalization degree is 76 mol%, the third acetalization degree is 75 mol%, and the fourth acetalization degree is 74 mol%. The first PET layer has a first glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the second PET layer has a second glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the third PET layer has a third glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the first glass transition temperature is greater than the second glass transition temperature, and the second glass transition temperature is greater than the third glass transition temperature. The difference between the first hydroxyl group content and the second hydroxyl group content is less than 3 mol%, the difference between the second hydroxyl group content and the second hydroxyl group content is less than 2 mol%, and the difference between the second hydroxyl group content and the fourth hydroxyl group content is less than 2 mol%. The difference between the first acetalization degree and the second acetalization degree is less than 2 mol%, the difference between the second acetalization degree and the third acetalization degree is less than 3 mol%, and the difference between the third acetalization degree and the fourth acetalization degree is less than 3 mol%. The difference between the first glass transition temperature and the second glass transition temperature is approximately equal to 8 ℃, and the difference between the second glass transition temperature and the third glass transition temperature is approximately equal to 8 ℃. The tap adhesion was 80%, and the peel adhesion was 105%.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.

Claims (2)

1. A high strength laminated glass comprising PVB, comprising in order from the inside to the outside: a first glass layer, a first PVB layer, a first PET layer, a second PVB layer, a second PET layer, a third PVB layer, a third PET layer, a fourth PVB layer and a second glass layer, wherein the first PVB layer has a first hydroxyl content determined according to JIS K6728, the second PVB layer has a second hydroxyl content determined according to JIS K6728, the third PVB layer has a second hydroxyl content determined according to JIS K6728, the fourth PVB layer has a fourth hydroxyl content determined according to JIS K6728, wherein the first hydroxyl content is less than the second hydroxyl content, the second hydroxyl content is less than the second hydroxyl content, and the second hydroxyl content is less than the fourth hydroxyl content;
the first PVB layer has a first acetalization degree measured according to JIS K6728, the second PVB layer has a second acetalization degree measured according to JIS K6728, the third PVB layer has a third acetalization degree measured according to JIS K6728, the fourth PVB layer has a fourth acetalization degree measured according to JIS K6728, wherein the first acetalization degree is greater than the second acetalization degree, the second acetalization degree is greater than the third acetalization degree, and the third acetalization degree is greater than the fourth acetalization degree;
the first hydroxyl group content is 10-15 mol%, the second hydroxyl group content is 11-16 mol%, the second hydroxyl group content is 12-17 mol%, and the fourth hydroxyl group content is 13-18 mol%; the first acetalization degree is 75-80 mol%, the second acetalization degree is 74-79 mol%, the third acetalization degree is 73-78 mol%, and the fourth acetalization degree is 72-77 mol%;
the first PET layer has a first glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the second PET layer has a second glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the third PET layer has a third glass transition temperature determined according to ASTM E1356 differential scanning calorimetry, the first glass transition temperature is greater than the second glass transition temperature, the second glass transition temperature is greater than the third glass transition temperature;
a difference between the first hydroxyl group content and the second hydroxyl group content is less than 3 mol%, a difference between the second hydroxyl group content and the second hydroxyl group content is less than 2 mol%, and a difference between the second hydroxyl group content and the fourth hydroxyl group content is less than 2 mol%; a difference between the first acetalization degree and the second acetalization degree is less than 2 mol%, a difference between the second acetalization degree and the third acetalization degree is less than 3 mol%, and a difference between the third acetalization degree and the fourth acetalization degree is less than 3 mol%;
the difference between the first glass transition temperature and the second glass transition temperature is less than 5 ℃, and the difference between the second glass transition temperature and the third glass transition temperature is less than 5 ℃.
2. A method of making a high strength laminated glass comprising PVB according to claim 1 wherein: the preparation method comprises the following steps:
laminating the first PVB layer, the first PET layer, the second PVB layer, the second PET layer, the third PVB layer, the third PET layer and the fourth PVB layer into a polymer laminated body through hot pressing; and
the polymer laminate was placed between two layers of glass and the resulting laminate was hot pressed.
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