TWI748295B - Polymer film and uses of the same - Google Patents

Abstract

A polymer film comprising polyvinylacetal and a laminated glass manufactured using the same are provided. At least one surface of the polymer film has a void volume (Vv) value at a material ratio of 10% ranging from 3 μm³ /μm² to 34.3 μm³ /μm² , wherein the void volume (Vv) and material ratio are defined in accordance with ISO 25178-2:2012.

Description

Polymer film and its application

The present invention relates to a polymer film, in particular to a polymer that has a specific void volume (Vv) value under a specific material ratio (material ratio) and is suitable for the preparation of laminated glass (laminated glass) membrane.

Laminated glass is a kind of glass material with a composite structure formed by sandwiching a polymer film between two glass sheets and tightly joining the glass sheet and the polymer film by means of thermocompression bonding. Laminated glass is widely used in the automobile industry and construction industry because of its better impact resistance and sound insulation.

Generally speaking, laminated glass is obtained by sandwiching a polymer film between two glass sheets to obtain a laminate, pre-pressing the laminate to expel the air between the glass sheet and the polymer film, and then pre-pressing The combined laminate is placed in an autoclave and placed for a period of time under high temperature and high pressure conditions to obtain laminated glass. When the laminated glass is a non-planar laminated glass, the pre-compression bonding is usually carried out by placing the laminate in a vacuum bag and evacuating under elevated temperature conditions.

Since the preparation of laminated glass involves thermal compression bonding between the glass sheet and the polymer film, how to avoid air remaining between the glass sheet and the polymer film of the laminated glass to improve the yield is actually an important issue. A known method to avoid air remaining between the glass sheet and the polymer film of the laminated glass is to design a concave-convex structure on the surface of the polymer film to facilitate the exhaust during the hot pressing. However, the existing polymer film is still insufficient Provide sufficient exhaust performance, and often occur the defects of edge delamination (ie, separation of the glass edge and the polymer film), so that the manufacturing yield of laminated glass still cannot reach a satisfactory level.

The present invention aims to provide a polymer film, in particular, a polymer film with a specific void volume (Vv) value under a specific load area ratio, which uses vacuum pre-compression laminated glass During the preparation, excellent results are shown, the polymer film can be closely and completely attached to the glass, and the laminated glass can obtain excellent and good results in the bubble residue test without edge degumming. Therefore, the polymer film of the present invention is particularly suitable for the preparation of laminated glass for automobiles.

Therefore, one object of the present invention is to provide a polymer film comprising polyvinylacetal, wherein at least one surface of the polymer film has a load area rate of 10%, which is 3 cubic micrometers/square micrometer. (Μm ³ /μm ² ) to 34.3 cubic microns/square micron void volume (Vv) value, where the definition of load area ratio and void volume is based on ISO 25178-2:2012.

In some embodiments of the present invention, the two surfaces of the polymer film independently have a void volume (Vv) value of 3 cubic micrometers/square micrometer to 34.3 cubic micrometers/square micrometer when the load area ratio is 10%.

In some embodiments of the present invention, the polyvinyl acetal contained in the polymer film is selected from the following group: poly(vinyl formal), poly(vinyl formal), poly(vinyl formal) Aldehydes), poly(vinyl butyral), poly(vinyl butyral), poly(vinyl hexanal), and combinations thereof.

In some embodiments of the present invention, at least one surface of the polymer film further has a surface roughness Rz value of 15 μm to 55 μm.

In some embodiments of the present invention, the two surfaces of the polymer film independently have a surface roughness Rz value of 15 μm to 55 μm.

In some embodiments of the present invention, the glass transition temperature (Tg) of the polymer film may be 10°C to 22°C.

In some embodiments of the present invention, the weight average molecular weight (Mw) of the polyvinyl acetal contained in the polymer film may be 150,000 daltons to 250,000 daltons.

In some embodiments of the present invention, the polymer film further contains a plasticizer, and based on 100 parts by weight of polyvinyl acetal, the content of the plasticizer may be 30 to 60 parts by weight.

In some embodiments of the present invention, the polymer film has a thickness of 0.5 mm to 1.5 mm.

In some embodiments of the present invention, the polymer film is a multilayer film.

In some embodiments of the present invention, the polymer film further contains additives selected from the following groups: dyes, pigments, stabilizers, antioxidants, flame retardants, infrared absorbers, infrared blocking agents, ultraviolet absorbers, UV stabilizers, lubricants, dispersants, surfactants, chelating agents, coupling agents, bonding agents, adhesion control agents, and combinations thereof.

Another object of the present invention is to provide a laminated glass comprising a first glass sheet, a second glass sheet, and the aforementioned polymer film disposed between the first glass sheet and the second glass sheet.

In order to make the above objectives, technical features and advantages of the present invention more obvious and understandable, the following is a detailed description of some specific implementation aspects.

The following will specifically describe some specific implementation aspects according to the present invention; however, without departing from the spirit of the present invention, the present invention can still be practiced in many different forms, and the protection scope of the present invention should not be limited to the specific embodiments. Implementation status.

Unless otherwise specified, the terms "a", "the" and similar terms used in this specification and the scope of the patent application shall be understood to include both singular and plural forms.

Unless otherwise stated, the terms "first", "second" and similar terms used in this specification and the scope of the patent application are only used to distinguish the described elements or components, and have no special meanings themselves, especially not used In the order of representatives.

Unless otherwise stated, in this specification and the scope of the patent application, the term "load area ratio" is defined in accordance with ISO 25178-2:2012. The load area curve is the function curve of the surface height to the area covered by it, and the load area ratio refers to the area covered by a specified height or higher.

Unless otherwise stated, in this specification and the scope of the patent application, the term "void volume (Vv)" is defined in accordance with ISO 25178-2:2012. Void volume (Vv) refers to the volume of voids per unit area at a specific load area rate.

Unless otherwise stated, in this specification and the scope of the patent application, the term "surface roughness Rz value" refers to the ten-point average roughness of the surface and is measured according to JIS B 0601 (1994).

Compared with the prior art, the effect of the present invention is to provide a polymer film with a specific void volume (Vv) value under a specific load area rate, and to use the polymer film to provide excellent performance in the bubble residue test. Laminated glass with good results and no edge degumming defects, especially for automotive laminated glass. The following provides a detailed description of the polymer film of the present invention and its related applications.

1. Polymer film

1.1. Composition of polymer film

The polymer film of the present invention contains polyvinyl acetal as an essential component, and may further contain other optional components, such as plasticizers or other conventional additives, if necessary. In some embodiments of the present invention, the polymer film includes polyvinyl acetal and plasticizer or is composed of polyvinyl acetal and plasticizer.

Examples of polyvinyl acetals include, but are not limited to, poly(vinyl formal), poly(vinyl acetal), poly(vinyl butyral), poly(vinyl pentanal), and poly(vinyl acetal). Hexalacetal. The aforementioned polyvinyl acetals can be used alone or in combination of multiple types. In the following examples of the present invention, poly(vinyl butyral) is used.

In this context, plasticizers refer to chemical substances that can change the plasticity of thermoplastic resins, and can also be referred to as plasticizers. Examples of plasticizers include, but are not limited to, esters of polybasic acids or polyols, such as triethylene glycol bis(2-ethylhexanoate), tetraethylene glycol bis(2-ethylhexanoate), and tetraethylene glycol bis(2-ethylhexanoate). -Ethylhexanoate), triethylene glycol bis(2-ethylbutyrate), tetraethylene glycol bis(2-ethylbutyrate), triethylene glycol diheptanoate, tetraethylenedi Alcohol diheptanoate, dihexyl adipate, dioctyl adipate, hexyl cyclohexyl adipate, diisononyl adipate, heptylnonyl adipate, dibutyl sebacate , Bis[2-(2-butoxyethoxy) ethyl adipate], polymeric adipate (polymeric adipate), dipropylene glycol dibenzoate, tripropylene glycol dibenzoate, polypropylene glycol Dibenzoate, isodecyl benzoate, 2-ethylhexyl benzoate, propylene glycol dibenzoate, diisononyl phthalate, dibutoxyethyl terephthalate, castor Sesame oil, methyl ricinoleate, soybean oil, epoxidized soybean oil, and combinations thereof.

The conventional additives may include any substance that can adapt to improve the processability of the polymer film in the manufacturing process, or impart a specific function to the polymer film. Examples of conventional additives include, but are not limited to, dyes, pigments, stabilizers, antioxidants, flame retardants, infrared absorbers, infrared blockers, ultraviolet absorbers, ultraviolet stabilizers, lubricants, dispersants, surfactants, chelating agents. Mixtures, coupling agents, bonding agents, and adhesion control agents. The aforementioned additives can be used alone or in combination of multiple types. For example, the polymer film may include dyes or pigments to form a colored polymer film, or include an ultraviolet absorber or an infrared absorber to form a polymer film with an anti-ultraviolet function or to form a polymer film with an anti-infrared function.

Under the condition that the specified void volume (Vv) value is met, the thickness of the polymer film of the present invention can be adjusted according to actual needs. Generally speaking, the thickness of the polymer film can be 0.5 mm to 1.5 mm, such as 0.51 mm, 0.52 mm, 0.53 mm, 0.54 mm, 0.55 mm, 0.56 mm, 0.57 mm, 0.58 mm, 0.59 mm, 0.6 mm, 0.61 mm , 0.62mm, 0.63mm, 0.64mm, 0.65mm, 0.66mm, 0.67mm, 0.68mm, 0.69mm, 0.7mm, 0.71mm, 0.72mm, 0.73mm, 0.74mm, 0.75mm, 0.76mm, 0.77mm, 0.78 Mm, 0.79 mm, 0.8 mm, 0.81 mm, 0.82 mm, 0.83 mm, 0.84 mm, 0.85 mm, 0.86 mm, 0.87 mm, 0.88 mm, 0.89 mm, 0.9 mm, 0.91 mm, 0.92 mm, 0.93 mm, 0.94 mm, 0.95mm, 0.96mm, 0.97mm, 0.98mm, 0.99mm, 1.0mm, 1.01mm, 1.02mm, 1.03mm, 1.04mm, 1.05mm, 1.06mm, 1.07mm, 1.08mm, 1.09mm, 1.1mm, 1.11mm , 1.12mm, 1.13mm, 1.14mm, 1.15mm, 1.16mm, 1.17mm, 1.18mm, 1.19mm, 1.2mm, 1.21mm, 1.22mm, 1.23mm, 1.24mm, 1.25mm, 1.26mm, 1.27mm, 1.28 Mm, 1.29 mm, 1.3 mm, 1.31 mm, 1.32 mm, 1.33 mm, 1.34 mm, 1.35 mm, 1.36 mm, 1.37 mm, 1.38 mm, 1.39 mm, 1.4 mm, 1.41 mm, 1.42 mm, 1.43 mm, 1.44 mm, 1.45 mm, 1.46 mm, 1.47 mm, 1.48 mm, or 1.49 mm, but not limited thereto.

The polymer film of the present invention may be a single layer film composed of a single layer, or a multilayer film composed of multiple layers, as long as the polymer film as a whole meets the specified void volume (Vv) value. In the case where the polymer film is a multilayer film, the materials of each layer of the polymer film may be the same or different, and each plays the same or different functional layer. The functional layer is, for example, a layer that can provide one or more of the following functions : Sound insulation function, heat insulation function, reflection function, anti-reflection function, refraction function, anti-refraction function, light splitting function, or dimming function.

1.2. Properties of polymer film

The uneven structure of the surface of the polymer film can be presented by measuring the three-dimensional image of the surface morphology. ISO 25178-2:2012 is a measurement specification for evaluating surface topography, which reveals a parameter related to surface topography, namely, void volume (Vv). The void volume (Vv) is defined as the void volume per unit area under a specified material ratio (material ratio), and can be calculated from a regional load area graph, where the Y axis of the regional load area graph represents the surface For height, the X-axis represents the load area rate. When the X-axis load area rate is 0%, the Y-axis surface height is the maximum value. When the X-axis load area rate is 100%, the Y-axis surface height is 0. For example, the void volume (Vv) when the load area rate is 10% represents the value below the horizontal cutting plane (horizontal cutting plane) set at the height of the Y-axis surface corresponding to the load area rate of 10% on the X axis. The size of the void volume covered. Therefore, when the load area rate is 0%, the void volume (Vv) value is the maximum, and when the load area rate is 100%, the void volume (Vv) value is 0. For the relevant description of the void volume (Vv) parameter, please refer to ISO 25178-2:2012, the full text of which is incorporated here for reference.

The inventors have surprisingly discovered that by controlling the void volume (Vv) value of the polymer film under a specific load area rate, it is possible to provide a laminated glass that can obtain excellent and good results in the bubble residue test and does not have edge degumming defects. , Especially laminated glass for vehicles. ^{Specifically, the polymer film of the present invention has a void volume (Vv) value of 3 cubic micrometers/square micrometer (μm 3} /μm ² ) to 34.3 cubic micrometers/square micrometer on at least one surface when the load area rate is 10%. , Such as 3.5 cubic micrometers/square micrometer, 4 cubic micrometers/square micrometer, 4.5 cubic micrometers/square micrometer, 5 cubic micrometers/square micrometer, 5.5 cubic micrometers/square micrometer, 6 cubic micrometers/square micrometer, 6.5 cubic micrometers/square micrometer , 7 cubic micron/square micron, 7.5 cubic micron/square micron, 8 cubic micron/square micron, 8.5 cubic micron/square micron, 9 cubic micron/square micron, 9.5 cubic micron/square micron, 10 cubic micron/square micron, 10 Cubic micrometers/square micrometer, 14.5 cubic micrometers/square micrometer, 15 cubic micrometers/square micrometer, 15.5 cubic micrometers/square micrometer, 16 cubic micrometers/square micrometer, 16.5 cubic micrometers/square micrometer, 17 cubic micrometers/square micrometer, 17.5 cubic micrometers Micron/square micron, 18 cubic micron/square micron, 18.5 cubic micron/square micron, 19 cubic micron/square micron, 19.5 cubic micron/square micron, 20 cubic micron/square micron, 20.5 cubic micron/square micron, 21 cubic micron / Square micron, 21.5 cubic micron / square micron, 22 cubic micron / square micron, 22.5 cubic micron / square micron, 23 cubic micron / square micron, 23.5 cubic micron / square micron, 24 cubic micron / square micron, 24.5 cubic micron / Square microns, 25 cubic microns/square microns, 25.5 cubic microns/square microns, 26 cubic microns/square microns, 26.5 cubic microns/square microns, 27 cubic microns/square microns, 27.5 cubic microns/square microns, 28 cubic microns/square Micron, 28.5 cubic micron/square micron, 29 cubic micron/square micron, 29.5 cubic micron/square micron, 30 cubic micron/square micron, 30.5 cubic micron/square micron, 31 cubic micron/square micron, 31.5 cubic micron/square micron , 32 cubic micrometers/square micrometer, 32.5 cubic micrometers/square micrometer, 33 cubic micrometers/square micrometer, 33.5 cubic micrometers/square micrometer, or 34 cubic micrometers/square micrometer, where the definition system of load area ratio and void volume (Vv) According to ISO 25178-2:2012. In a preferred embodiment of the present invention, the polymer film of the present invention independently has a void volume of 3 cubic micrometers/square micrometer to 34.3 cubic micrometers/square micrometer ( Vv) value.

In some embodiments of the present invention, at least one surface of the polymer film of the present invention further has a surface roughness Rz value of 15 microns to 55 microns. Preferably, the two surfaces of the polymer film independently have 15 microns to 55 microns. Rz value of the surface roughness, such as 16 microns, 17 microns, 18 microns, 19 microns, 20 microns, 21 microns, 22 microns, 23 microns, 24 microns, 25 microns, 26 microns, 27 microns, 28 microns, 29 microns, 30 microns, 31 microns, 32 microns, 33 microns, 34 microns, 35 microns, 36 microns, 37 microns, 38 microns, 39 microns, 40 microns, 41 microns, 42 microns, 43 microns, 44 microns, 45 microns, 46 microns , 47 microns, 48 microns, 49 microns, 50 microns, 51 microns, 52 microns, 53 microns, or 54 microns. The Rz value is measured according to JIS B 0601 (1994).

The surface of the polymer film of the present invention can provide the desired void volume (Vv) value and surface roughness Rz value through any conventional means. For example, the surface of the polymer film can be mechanically embossed to form an uneven structure on the surface of the polymer film, and the composition of the polymer film or mechanical embossing conditions can be adjusted to provide a specified void volume (Vv) value And the surface roughness Rz value. In this article, mechanical pressing refers to the use of rollers to create textures on the surface of the formed polymer film. The methods of mechanical pressing include but are not limited to pressing wheel method and pressing wheel method, among which pressing wheel method is better. There are no special restrictions on the pattern of mechanical pressed flowers, such as diamonds, lines, zigzags, squares, cones, circles, approximate circles, and irregular shapes. Each of the aforementioned grain patterns can exist alone, or more than one can exist at the same time. For example, the relative properties of the polymer film or the mechanical embossing conditions can be adjusted according to one or more of the following conditions to provide a specified void volume (Vv) value and surface roughness Rz value: (1) Weight average of polyvinyl acetal The molecular weight (Mw) can be 150,000 Daltons to 250,000 Daltons, such as 155,000 Daltons, 160,000 Daltons, 165,000 Daltons, 170,000 Daltons, 175,000 Daltons, 180,000 Daltons, 185,000 Daltons Dayton, 190,000 Dalton, 195,000 Dalton, 200,000 Dalton, 205,000 Dalton, 210,000 Dalton, 215,000 Dalton, 220,000 Dalton, 225,000 Dalton, 230,000 Dalton, 235,000 Dalton Ton, 240,000 Dalton, or 245,000 Dalton. In some embodiments of the present invention, the weight average molecular weight (Mw) of the polyvinyl acetal is 180,000 Daltons to 205,000 Daltons. (2) The glass transition temperature (Tg) of the polymer film can be 10°C to 22°C, such as 10.5°C, 11°C, 11.5°C, 12°C, 12.5°C, 13°C, 13.5° C, 14°C, 14.5°C, 15°C, 15.5°C, 16°C, 16.5°C, 17°C, 17.5°C, 18°C, 18.5°C, 19°C, 19.5°C, 20°C, 20.5°C, 21°C, or 21.5°C. (3) The amount of plasticizer in the polymer film is based on 100 parts by weight of polyvinyl acetal, which can be 30 to 60 parts by weight, for example, 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight are added Parts, 35 parts by weight, 36 parts by weight, 37 parts by weight, 38 parts by weight, 39 parts by weight, 40 parts by weight, 41 parts by weight, 42 parts by weight, 43 parts by weight, 44 parts by weight, 45 parts by weight, 46 parts by weight, 47 parts by weight, 48 parts by weight, 49 parts by weight, 50 parts by weight, 51 parts by weight, 52 parts by weight, 53 parts by weight, 54 parts by weight, 55 parts by weight, 56 parts by weight, 57 parts by weight, 58 parts by weight, or 59 Parts by weight of plasticizer. (4) The pressure of the pressed flower wheel can range from 2 kg/cm 2 (kg/cm ² ) to 50 kg/cm², preferably from 5 kg/cm² to 40 kg/cm², and more specifically, 10 kg/cm². Cm² to 30 kg/cm², such as 11 kg/cm², 12 kg/cm², 13 kg/cm², 14 kg/cm², 15 kg/cm², 16 kg/cm², 17 kg/cm² Cm, 18 kg/cm², 19 kg/cm², 20 kg/cm², 21 kg/cm², 22 kg/cm², 23 kg/cm², 24 kg/cm², 25 kg/cm², 26 kg/cm², 27 kg/cm², 28 kg/cm², or 29 kg/cm². (5) The temperature of the pressed flower wheel can be 80°C to 150°C, preferably 90°C to 140°C, more specifically 100°C to 130°C, such as 101°C, 102°C, 103°C, 104°C, 105°C, 106°C, 107°C, 108°C, 109°C, 110°C, 111°C, 112°C, 113°C, 114°C, 115° C, 116°C, 117°C, 118°C, 119°C, 120°C, 121°C, 122°C, 123°C, 124°C, 125°C, 126°C, 127°C, 128°C, or 129°C. When the temperature of the pressed flower wheel falls outside the specified range, the polymer film may not be able to obtain the desired void volume (Vv) value.

1.3. Preparation of polymer film

The preparation method of the polymer film of the present invention is not particularly limited. For example, polyvinyl acetal and optional ingredients (such as plasticizer) can be mixed and kneaded to obtain a polymer composition, and then a conventional film preparation method can be used to polymerize it. The composition is formed into a film, and if necessary, mechanical embossing is performed to provide the desired void volume (Vv) and surface roughness Rz value on the surface of the polymer film. Examples of the film preparation method include, but are not limited to, calendering method, casting method, extrusion tentering method, direct extrusion method, and extrusion blow molding method.

In some embodiments of the present invention, the preparation method of the polymer film is as follows: Use a mixer to combine the resinous polyvinyl acetal and plasticizer at a temperature of 100°C to 150°C and 10 rpm Mix and knead at a speed of 50 rpm for 5 minutes to 30 minutes to obtain a polymer composition. After the polymer composition is cooled to room temperature, place the polymer composition in a hot press at 100°C. To form a film under a temperature of 200°C and a pressure of 2 kg to 5 kg for 1 to 10 minutes. If necessary, repeat the above-mentioned film forming steps and adjust the composition of the polymer composition to provide films with different functions, and laminate the films to form a polymer film with a multilayer structure; finally, the polymer film is mechanically pressed to provide all The desired void volume (Vv) value and surface roughness Rz value, among which the mechanical press flower parameter conditions are as follows: the pressure of the press flower wheel is 10 kg/cm² to 30 kg/cm², and the temperature of the press flower wheel is 100°C to 130 °C.

2. Laminated glass

The polymer film of the present invention can be used to prepare laminated glass. Therefore, the present invention also provides a laminated glass, which includes a first glass sheet, a second glass sheet, and a polymer film as described above disposed between the first glass sheet and the second glass sheet.

The first glass sheet and the second glass sheet may be the same or different, and may be any glass sheet conventionally used to prepare laminated glass, such as float glass, tempered glass, wired glass, or ordinary flat glass. The invention is not limited to this. In the following embodiments, float glass is used as the first glass sheet and the second glass sheet.

The laminated glass of the present invention can be prepared by a conventional method for preparing laminated glass in the related technical field. For example, the preparation of laminated glass can be carried out in the following manner: a polymer film is sandwiched between two glass sheets to obtain a laminate, and the laminate is placed in a vacuum bag and placed at a temperature of 20°C to 30°C Pull down the vacuum (vacuum degree>500 mmHg (mmHg)) for at least 10 minutes, then put the vacuum bag with the laminate into the heating furnace, and slowly raise the temperature from 60°C to 130°C, after at least 30 minutes , Take out the vacuum bag from the heating furnace and complete the pre-compression. Then, the pre-compressed laminate is placed in an autoclave and hot-pressed under high temperature and high pressure conditions for 100 minutes to 150 minutes to obtain laminated glass. The high temperature and high pressure conditions are a pressure of 10 bar to 15 bar and a temperature of 100°C to 150°C.

3. Example

3.1. Measurement method description

The following specific implementations are used to further illustrate the present invention, in which the measuring instruments and methods used are as follows:

[Measurement of the molecular weight of polyvinyl acetal]

Use gel permeation chromatography (GPC) to measure the molecular weight distribution of polyvinyl acetal, in which polyvinyl acetal is dissolved in tetrahydrofuran (THF), and GPC analysis is performed under the following conditions , And calculate its molecular weight based on the ratio of the area of the corresponding polystyrene standard (Waters PS STD). Device: Waters 1515 PUMP system Detector: Waters 2414 RI Extraction conditions: 1.0 ml/min (mL/min), THF Column: Waters Styragel HR5 THF, Waters Styragel HR4 THF, Waters Styragel HR3 THF, Waters Styragel HR1 THF

[Measurement of void volume (Vv)]

The void volume (Vv) value of the polymer film surface load area ratio at 10% is using a laser confocal microscope (model: LEXT OLS5000-SAF, purchased from Olympus) Measured in accordance with ISO 25178-2:2012 at a temperature of 24±3°C and a relative humidity of 63±3%. The measurement conditions are as follows: the light source has a wavelength of 405 nm, the objective lens is 100 times (MPLAPON-100xLEXT), the optical zoom (optical zoom) is 50 times, the observation area is 1500 microns × 1500 microns, and the resolution is 1024 pixels × 1024. Pixels, the operating conditions are set to auto tilt removal, and no filter is used. In the obtained load area graph, the core void volume (Vvc) value and the trough void volume (Vvv) value can be obtained. The void volume (Vv) value is the value of the trough void volume (Vvv) and the core part The sum of the values of void volume (Vvc). The unit of the void volume (Vv) value is cubic micrometer/square micrometer.

[Measurement of surface roughness Rz value]

The surface roughness Rz value is measured using a roughness tester (model: SE 300, purchased from Kosaka Laboratory Ltd.) and measured in accordance with JIS B 0601 (1994). First, cut the polymer film into a size of 8 cm×30 cm as a test sample. Set the measurement conditions as follows: the vertical magnification is set to automatic, the horizontal magnification is set to 25 mm/λ _c , and the cut off distance is set to 2.5 mm (that is, calculated every 2.5 mm Once), the evaluation length is seven times the cut-off distance, the reference length is set to 17.5 mm, and the measurement direction is the machine direction.

[Measurement of glass transition temperature (Tg)]

A differential scanning calorimeter (model: TA DSC 25, purchased from TA Instruments) was used to measure the Tg of the polymer film under a nitrogen atmosphere. First, take 7 mg of the polymer film as a sample and place it on the sample stage of the differential scanning calorimeter, raise the temperature to 150°C at a heating rate of 10°C/min, and then keep it at this temperature for 5 minutes. Then, the sample is equilibrated at -50°C and kept at this temperature for 5 minutes, and then heated to 100°C at a temperature rise rate of 10°C/min to obtain a graph of temperature versus heat flow (X-axis) Is the temperature, and the Y axis is the heat flow), and the temperature corresponding to the midpoint of the glass transition is recorded as Tg.

[Bubble residual test]

Cut the laminated glass into a test sample with a width of 30 cm and a length of 30 cm. Put the test sample in an oven at 120°C in a vertical position for 14 days, and observe with the naked eye whether there are bubbles remaining in the test sample. The bubbles refer to the presence between the glass and the polymer film and are not exposed to the outside air. Air bubbles in contact. The evaluation criteria are as follows: if the test sample has no air bubbles remaining, the record is "◎", which means the result of the air bubble test is excellent; if there is a bubble with a diameter of less than 0.5 mm remaining in the test sample and the number of air bubbles is one, the record is "○", which means The bubble test result is good; and if there are bubbles with a diameter of less than 0.5 mm remaining in the test sample and the number of bubbles is more than two, or there are bubbles with a diameter greater than 0.5 mm, the record is "×", which means the bubble test result is not good.

[Edge Degumming Test]

Cut the laminated glass into a test sample with a width of 30 cm and a length of 30 cm. Put the test sample vertically in an oven at 50°C and 95% relative humidity for 14 days, and observe with the naked eye whether the test sample has edge degumming. The evaluation criteria are as follows: if the test sample does not have edge degumming (that is, the glass and the polymer film are tightly bonded), the record is "◎", which means that the edge degumming test has passed; on the contrary, if the test sample has edge degumming (that is, glass and polymer film) The film is not tightly bonded), recorded as "×", which means that the edge degumming test has not passed.

3.2. List of raw material information used in Examples and Comparative Examples

Table 1: List of raw material information Raw material model or abbreviation Description and source of purchase PVB Poly(vinyl butyral), purchased from Changchun Petrochemical Co., Ltd. 3GO Plasticizer, triethylene glycol bis(2-ethylhexanoate)

3.3. Preparation and quality testing of polymer film

The polymer films of Examples 1 to 9 and Comparative Examples 1 to 7 were prepared, and the preparation methods are described as follows. First, 100 parts by weight of PVB and 38.5 parts by weight of 3GO are mixed to obtain a mixture. After kneading the mixture for 15 minutes at 120°C with a rotation speed of 35 rpm, the mixture is cooled to room temperature to obtain a polymerized mixture.物膜组合物 Film composition. Next, the polymer film composition is placed in a hot press, and hot-compression bonding is performed at 150°C and a pressure of 3 kg for 3 minutes to obtain a polymer film.

Afterwards, if necessary, a pressing machine is used to mechanically press the two surfaces of the polymer film. The implementation conditions of the mechanical pressed flower are shown in Tables 2-1 to 2-2, and the linear speed of the polymer film passing between the pressed flower wheels is 10 meters per minute (m/min) to 18 meters per minute.

Measure the molecular weight of PVB of Examples 1 to 9 and Comparative Examples 1 to 7, as well as the thickness of the polymer film, Tg, surface roughness Rz, and void volume at 10% load area ratio (Vv ), and record the results in Table 2-1 to Table 2-2.

Table 2-1: Composition and properties of PVB and polymer films of Examples 1 to 9 unit Example 1 2 3 4 5 6 7 8 9 Press flower wheel pressure kg/cm ² 10 10 10 10 30 30 30 30 20 Press flower wheel temperature °C 100 130 100 130 100 130 100 130 120 Molecular weight of PVB (Mw) Dalton 186341 196523 195243 188543 202277 186303 203875 188399 189945 Thickness of polymer film mm 0.76 0.76 0.76 0.76 0.76 0.76 0.76 0.76 0.76 Tg of polymer film °C 12.53 12.48 17.33 17.35 12.67 12.47 17.52 17.55 14.53 Rz of polymer film μm 43.968 40.854 41.001 39.112 41.868 43.994 42.456 39.227 21.348 Vv of polymer film μm ³ /μm ² 9.052 20.61 3.068 19.036 27.27 34.267 25.072 30.248 22.259

Table 2-2: Composition and properties of PVB and polymer films of Comparative Examples 1-7 unit Comparative example 1 2 3 4 5 6 7 Press flower wheel pressure kg/cm ² Not applicable 2 40 20 20 20 20 Press flower wheel temperature °C Not applicable 120 120 120 120 80 140 Molecular weight of PVB (Mw) Dalton 183652 186301 190034 189752 190366 185254 185254 Thickness of polymer film mm 0.76 0.76 0.76 0.76 0.76 0.76 0.76 Tg of polymer film °C 14.38 15.34 15.87 3.54 20.36 14.93 14.58 Rz of polymer film μm 38.823 38.763 43.339 38.312 38.559 39.141 40.769 Vv of polymer film μm ³ /μm ² 1.686 1.791 35.344 1.585 1.641 1.773 36.296

3.4. Preparation and property evaluation of laminated glass

The polymer films of Examples 1 to 9 and Comparative Examples 1 to 7 were used to prepare laminated glass. First, prepare two clean transparent float glass sheets (length 300 mm, width 150 mm, thickness 2 to 4 mm), and then separate the polymer films of Examples 1 to 9 and Comparative Examples 1 to 7 It is sandwiched between two transparent float glass sheets to obtain a laminate, and the laminate is evacuated by a vacuum bag method for pre-compression bonding. The operation method of the vacuum bag type is as follows: Put the laminate into a vacuum bag and vacuum (vacuum degree>500 mmHg (mmHg)) at a temperature of 20°C to 30°C for at least 10 minutes, and then Put the vacuum bag containing the laminate into a heating furnace, first maintain it at a temperature of 20°C to 30°C for 10 to 20 minutes, and then increase the temperature to 60°C to 130°C and maintain it for 15 to 45 minutes, then Remove the vacuum bag from the heating furnace and cool down at room temperature. After cooling, release the vacuum and take out the laminate. Place the pre-compressed laminate in an autoclave at a pressure of 13 bar and a temperature of 135°C for 120 minutes, and then cool to room temperature to obtain a laminated glass.

According to the method described above, the laminated glasses of Examples 1 to 9 and Comparative Examples 1 to 7 were subjected to bubble residue test and edge degumming test, and the evaluation results were recorded in Tables 3-1 and 3-2.

Table 3-1: Properties of laminated glass of Examples 1-9 Example 1 2 3 4 5 6 7 8 9 Bubble residue test ○ ◎ ○ ◎ ◎ ◎ ○ ◎ ○ Edge degumming test ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎

Table 3-2: Properties of laminated glass of Comparative Examples 1-7 Comparative example 1 2 3 4 5 6 7 Bubble residue test X X ○ X X X ○ Edge degumming test X X X X X X X

As shown in Table 3-1, the laminated glass made from the polymer film of the present invention obtains excellent and good results in the bubble residue test without edge degumming defects, the bubble residue test results are excellent and can pass the edge degumming test. In particular, Examples 1 to 9 show that under different PVB molecular weight and Tg, and pressed flower conditions, as long as the void volume (Vv) value of the polymer film at 10% load area ratio is within the specified range, the laminated glass produced Both can meet the requirements of obtaining excellent and good results in the bubble residue test and no edge degumming.

In contrast, as shown in Table 3-2, the laminated glass made from the polymer film that does not belong to the present invention cannot meet the requirements of obtaining excellent and good results in the bubble residue test without edge degumming. In particular, Comparative Examples 1, 2 and 4 to 6 show that regardless of PVB molecular weight, Tg, and pressed flower conditions, when the void volume (Vv) value of the polymer film is lower than the specified range, the laminated glass cannot be achieved. Obtained excellent and good results in the bubble residue test and failed to pass the edge degumming test. Comparative Examples 3 and 7 show that when the void volume (Vv) value of the polymer film is higher than the specified range, although the bubble residue test can reach a good level, it still fails to pass the edge degumming test.

The above-mentioned embodiments are only illustrative to illustrate the principle and effects of the present invention, and to illustrate the technical features of the present invention, and are not intended to limit the protection scope of the present invention. Any changes or arrangements that can be easily made by a person familiar with the present invention without departing from the technical principles and spirit of the present invention fall within the scope of the present invention. Therefore, the scope of protection of the rights of the present invention is as listed in the appended patent scope.

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Claims (13)

A polymer film comprising polyvinylacetal (polyvinylacetal), wherein at least one surface of the polymer film has 3 cubic micrometers/square micrometer (μm ³ /μm) when the material ratio is 10% ² ) The void volume (Vv) value of 34.3 cubic micrometers/square micrometer, in which the definition of load area ratio and void volume is based on ISO 25178-2:2012. The polymer film according to claim 1, wherein the two surfaces of the polymer film independently have a void volume (Vv) of 3 cubic micrometers/square micrometer to 34.3 cubic micrometers/square micrometer when the load area ratio is 10% value. The polymer film according to claim 1, wherein the polyvinyl acetal is selected from the following group: poly(vinyl formal), poly(vinyl formal), poly(vinyl formal) (Vinyl butyral) (poly(vinyl butyral)), poly(vinyl valeral), poly(vinyl hexanal), and combinations thereof. The polymer film according to claim 1, wherein the at least one surface of the polymer film further has a surface roughness Rz value of 21 micrometers to 49 micrometers. The polymer film according to claim 2, wherein the two surfaces of the polymer film each independently have a surface roughness Rz value of 21 micrometers to 49 micrometers. The polymer film according to claim 1, wherein the glass transition temperature (Tg) of the polymer film is 12°C to 19°C. The polymer film according to claim 1, wherein the weight average molecular weight (Mw) of the polyvinyl acetal is 180,000 to 250,000. The polymer film according to any one of claims 1 to 7, further comprising a plasticizer. The polymer film according to claim 8, wherein the content of the plasticizer is 30 to 60 parts by weight based on 100 parts by weight of polyvinyl acetal. The polymer film according to any one of claims 1 to 7, which has a thickness of 0.69 mm to 0.83 mm. The polymer film according to any one of claims 1 to 7, which is a multilayer film. The polymer film according to any one of claims 1 to 7, further comprising additives selected from the following group: dyes, pigments, stabilizers, antioxidants, flame retardants, infrared absorbers, infrared blocking agents, ultraviolet rays Absorbents, ultraviolet stabilizers, lubricants, dispersants, surfactants, chelating agents, coupling agents, bonding agents, adhesion control agents, and combinations thereof. A laminated glass comprising a first glass sheet, a second glass sheet, and a polymer according to any one of claims 1 to 12 arranged between the first glass sheet and the second glass sheet membrane.