CN112876706B - Polymer film and use thereof - Google Patents
Polymer film and use thereof Download PDFInfo
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- CN112876706B CN112876706B CN201911201629.1A CN201911201629A CN112876706B CN 112876706 B CN112876706 B CN 112876706B CN 201911201629 A CN201911201629 A CN 201911201629A CN 112876706 B CN112876706 B CN 112876706B
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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
- B32B17/1055—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
- B32B17/10559—Shape of the cross-section
- B32B17/10577—Surface roughness
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
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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
- B32B17/1055—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
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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
- B32B17/1055—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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
- C03C27/06—Joining glass to glass by processes other than fusing
- C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping Of Tube Ends By Bending Or Straightening (AREA)
- Joining Of Glass To Other Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a polymer film containing polyvinyl acetal and laminated glass using the polymer film. At least one surface of the polymer film has a void volume (Vv) value of 2 cubic microns/square micron to 18 cubic microns/square micron at a load area rate of 10%, wherein the load area rate and void volume are defined according to ISO25178-2:2012. The polymer film of the invention is suitable for the preparation of laminated glass, and the prepared laminated glass can obtain excellent and good results in bubble residue test without edge degumming.
Description
Technical Field
The present invention relates to a polymer film, and more particularly, to a polymer film having a specific void volume (Vv) value at a specific load area ratio (material ratio) and suitable for use in the production of laminated glass (laminated glass) for construction.
Background
Laminated glass is a glass material with a composite structure, which is formed by sandwiching a polymer film between two glass sheets and tightly bonding the glass sheets to the polymer film by means of thermal compression. Laminated glass has been widely used in the automobile industry and the building industry because of its excellent impact resistance and sound insulation.
In general, laminated glass is produced by sandwiching a polymer film between two glass sheets to obtain a laminate, pre-pressing the laminate to exhaust air between the glass sheets and the polymer film, and then placing the pre-pressed laminate in an autoclave for a while under high temperature and high pressure conditions. When the laminated glass is a planar laminated glass, the pre-press is usually performed by pressing the laminate by a roller and then baking the laminate at a temperature higher than the roller.
Since the preparation of laminated glass involves thermal compression between the glass sheet and the polymer film, how to avoid air remaining between the glass sheet and the polymer film of laminated glass to improve the yield is an important issue. One known means of avoiding air entrapment between the glass sheet and the polymer film of laminated glass is by designing a relief structure in the surface of the polymer film to facilitate venting during pre-lamination, but existing polymer films are not sufficient to provide adequate venting performance and flaws such as edge delamination (delamination of edge) often occur (i.e., separation of the glass edges from the polymer film) such that the yield of laminated glass is still unsatisfactory.
Disclosure of Invention
The present invention is directed to a polymer film, and more particularly, to a polymer film having a specific void volume (Vv) value at a specific load area ratio, which exhibits excellent results in the production of laminated glass using roll-press pre-lamination, the polymer film can be closely and completely adhered to glass, and the produced laminated glass can obtain excellent and good results in a bubble remaining test without edge peeling. Thus, the polymer film of the present invention is particularly suitable for use in the production of laminated glass for construction.
It is therefore an object of the present invention to provide a polymer film comprising polyvinyl acetal (polyvinyl acetate), wherein at least one surface of the polymer film has a load area ratio of 10% of 2 cubic micrometers per square micrometer (μm) 3 /μm 2 ) To a void volume (Vv) value of 18 cubic microns/square micron, wherein the load area ratio and void volume are defined in accordance with ISO25178-2:2012.
In some embodiments of the invention, the two surfaces of the polymer film each independently have a void volume (Vv) value of 2 cubic microns/square micron to 18 cubic microns/square micron at a load area ratio of 10%.
In some embodiments of the invention, the polymer film comprises a polyvinyl acetal selected from the group consisting of: polyvinyl formal (poly (vinyl formal)), polyvinyl acetal (poly (vinyl butyral)), polyvinyl butyral (pva), polyvinyl valeraldehyde (pva), polyvinyl caproaldehyde (pva), and combinations thereof.
In some embodiments of the present invention, the at least one surface of the polymer film further has a surface roughness Rz value of 15 microns to 40 microns.
In some embodiments of the invention, the two surfaces of the polymer film also each independently have a surface roughness Rz value of 15 microns to 40 microns.
In some embodiments of the invention, the glass transition temperature (glass transition temperature, tg) of the polymer film is from 10 ℃ to 22 ℃.
In some embodiments of the invention, the polymer film comprises a polyvinyl acetal having a weight average molecular weight (Mw) of 150,000 daltons (dalton) to 250,000 daltons.
In some embodiments of the present invention, the polymer film further comprises a plasticizer, and the plasticizer is contained in an amount of 30 to 60 parts by weight based on 100 parts by weight of the polyvinyl acetal.
In some embodiments of the invention, the polymer film has a thickness of 0.2 millimeters to 2 millimeters.
In some embodiments of the invention, the polymer film is a multilayer film.
In some embodiments of the invention, the polymer film further comprises an additive selected from the group consisting of: dyes, pigments, stabilizers, antioxidants, flame retardants, infrared absorbers, infrared blockers, ultraviolet absorbers, ultraviolet stabilizers, lubricants, dispersants, surfactants, chelating agents, coupling agents, binders, 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 a polymer film as described above disposed between the first glass sheet and the second glass sheet.
In order to make the above objects, technical features and advantages of the present invention more comprehensible, a detailed description of some embodiments accompanied with figures is provided below.
Detailed Description
Some specific embodiments according to the present invention will be specifically described below; however, the invention may be embodied in many different forms without departing from the spirit thereof and should not be construed as limited to the specific embodiments set forth herein.
As used in this specification and the claims, the terms "a," "an," "the," and the like are to be construed to include both the singular and the plural, unless otherwise indicated.
Unless otherwise indicated, the terms "first," "second," and the like in the description and in the claims are used for distinguishing between elements or components described and not necessarily for describing a sequential or chronological order.
In the present description and claims, unless otherwise indicated, the term "load area ratio" is defined in accordance with ISO25178-2:2012. The load area graph is a graph of surface height as a function of the area covered by the graph, and the load area rate is the area of the area above a specified height.
In the present description and in the claims, unless otherwise indicated, the term "void volume (Vv)" is defined in accordance with ISO25178-2:2012. Void volume (Vv) refers to the volume of voids per unit area at a particular load area rate.
In the present specification and claims, unless otherwise specified, the term "surface roughness Rz value" means ten-point average roughness of a surface, and is measured in accordance with JIS B0601 (1994).
The present invention has an effect of providing a polymer film having a specific void volume (Vv) value at a specific load area ratio, and providing laminated glass, particularly laminated glass for construction, with excellent and good results in a bubble remaining test without edge peeling flaws, by using the polymer film, as compared with the prior art. A detailed description of the polymer films of the present invention and their related applications is provided below.
1. Polymer film
1.1. Construction 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 existing additives as needed. In some embodiments of the invention, the polymer film comprises or consists of a polyvinyl acetal and a plasticizer.
Examples of polyvinyl acetals include, but are not limited to, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, polyvinyl valeraldehyde, and polyvinyl caproaldehyde. The polyvinyl acetals may be used alone or in combination of two or more. In the latter embodiment of the invention, polyvinyl butyral is used.
Herein, a plasticizer refers to a chemical substance that can change the plasticity of a thermoplastic resin, and may also be referred to as a plasticizer. Examples of plasticizers include, but are not limited to, esters of polyacids or polyols, such as triethylene glycol bis (2-ethylhexanoate) (triethylene glycol bis (2-ethylenehexanoate)), tetraethylene glycol bis (2-ethylhexanoate), triethylene glycol bis (2-ethylbutyrate), tetraethylene glycol bis (2-ethylbutyrate), triethylene glycol diheptanoate, tetraethylene glycol diheptanoate, dihexyl adipate, dioctyl adipate, hexyl cyclohexyl adipate, diisononyl adipate, heptyl nonyl 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 oil, methyl ricinoleate, soybean oil, epoxidized soybean oil, and combinations thereof.
The existing additives may comprise any substance that adaptively improves the processability of the polymer film during manufacture or imparts a specific function to the polymer film. Examples of existing 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, coupling agents, binders, and adhesion control agents. The above additives may be used alone or in combination of two or more. For example, the polymer film may contain a dye or a pigment to form a colored polymer film, or contain an ultraviolet absorber or an infrared absorber to form a polymer film having an ultraviolet ray resistant function or to form a polymer film having an infrared ray resistant function.
The thickness of the polymer films of the present invention can be adjusted as desired, consistent with the indicated void volume (Vv) values. In general, the thickness of the polymer film may be from 0.2 mm to 2 mm, more particularly from 0.5 mm to 1.5 mm, for example 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, 0.62 mm, 0.63 mm, 0.64 mm, 0.65 mm, 0.66 mm, 0.67 mm, 0.68 mm, 0.69 mm, 0.7 mm, 0.71 mm, 0.72 mm, 0.73 mm, 0.74 mm, 0.75 mm, 0.76 mm, 0.77 mm, 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, 0.95 mm, 0.96 mm, 0.97 mm, 0.98 mm, 0.79 mm, 0.86 mm. 1.0 mm, 1.01 mm, 1.02 mm, 1.03 mm, 1.04 mm, 1.05 mm, 1.06 mm, 1.07 mm, 1.08 mm, 1.09 mm, 1.1 mm, 1.11 mm, 1.12 mm, 1.13 mm, 1.14 mm, 1.15 mm, 1.16 mm, 1.17 mm, 1.18 mm, 1.19 mm, 1.2 mm, 1.21 mm, 1.22 mm, 1.23 mm, 1.24 mm, 1.25 mm, 1.26 mm, 1.27 mm, 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 1.48 mm, but is not limited thereto.
The polymer film of the present invention may be a single-layer film composed of a single layer, or a multi-layer film composed of a plurality of layers, as long as the polymer film as a whole meets the conditions of the specified void volume (Vv) value. In the case where the polymer film is a multilayer film, the materials of the layers of the polymer film may be the same or different and each may play the same or different functional layers, for example, layers that may provide one or more of the following functions: sound insulation function, heat insulation function, reflection function, antireflection function, refraction function, antireflection function, light splitting function, and light reduction function.
1.2. Properties of Polymer film
The relief structure of the surface of the polymer film can be represented by measuring a three-dimensional image of the surface topography (surface morphology). ISO25178-2:2012 is a measurement specification for evaluating surface topography, in which a parameter relating to the surface topography, namely void volume (Vv), is described. Void volume (Vv) is defined as the void volume per unit area at a given load area ratio (material ratio) and is calculated from a regional load area graph, wherein the Y-axis of the regional load area graph represents surface height, the X-axis represents load area ratio, the surface height of the Y-axis is maximum when the load area ratio of the X-axis is 0%, and the surface height of the Y-axis is 0 when the load area ratio of the X-axis is 100%. For example, the void volume (Vv) at a load area ratio of 10% represents the void volume size covered below the horizontal cut plane (horizontal cutting plane) set at the Y-axis surface height for an X-axis load area ratio of 10%. Therefore, when the load area ratio is 0%, the void volume (Vv) value is the maximum value, and when the load area ratio is 100%, the void volume (Vv) value is 0. Related descriptions of void volume (Vv) parameters may be found in ISO25178-2:2012, which is incorporated herein by reference in its entirety.
The inventors have surprisingly found that by controlling the void volume (Vv) value of a polymer film at a specific load area ratio, laminated glass, in particular for construction, can be provided that gives excellent and good results in the bubble retention test without edge-degumping defects. In particular, the polymer films of the present invention have void volume (Vv) values of 2 cubic microns/square micron to 18 cubic microns/square micron at a load area ratio of 10% on at least one surface, for example, 2.5 cubic microns/square micron, 3 cubic microns/square micron, 3.5 cubic microns/square micron, 4 cubic microns/square micron, 4.5 cubic microns/square micron, 5.5 cubic microns/square micron, 6 cubic microns/square micron, 6.5 cubic microns/square micron, 7 cubic microns/square micron, 7.5 cubic microns/square micron, 8 cubic microns/square micron, 8.5 cubic microns/square micron, 9 cubic microns/square micron, 9.5 cubic microns/square micron, 10 cubic microns/square micron, 10.5 cubic microns/square micron, 11 cubic microns/square micron, 11.5 cubic microns/square micron, 12.5 cubic microns/square micron, 13 cubic microns/square micron, 13.5 cubic microns/square micron, 14 cubic microns/square micron, 14.5 cubic microns/square micron, 15 cubic microns/square micron, 15.5 cubic microns/square micron, 16 cubic microns/square micron, 16.5 cubic microns/square micron, 17 cubic microns/square micron, 17.5 cubic microns/square micron, and 17 cubic microns/square micron, wherein the void volume ratio is in accordance with the definition of the void volume of(s) of 2 to 2512. In a preferred embodiment of the invention, the polymer films of the invention each independently have void volume (Vv) values on both surfaces of from 2 cubic microns/square micron to 18 cubic microns/square micron at a load area ratio of 10%.
In some embodiments of the present invention, at least one surface of the polymer film of the present invention also has a surface roughness Rz value of 15 microns to 40 microns, preferably both surfaces of the polymer film each independently have a surface roughness Rz value of 15 microns to 40 microns, for example 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 or 39 microns. The Rz value is measured in accordance with JIS B0601 (1994).
The polymer film surface of the present invention can be provided with the desired void volume (Vv) value and surface roughness Rz value by any conventional means. For example, the relief structure can be formed on the surface of the polymer film by mechanically embossing the surface of the polymer film, and the composition of the polymer film or the mechanical embossing conditions can be adjusted to provide a specified void volume (Vv) value and surface roughness Rz value. In this context, mechanical embossing refers to the production of texture on the surface of the formed polymer film using rollers. The mechanical embossing method includes, but is not limited to, embossing wheel method and calender wheel method, among which embossing wheel method is preferred. The texture of the mechanical embossing is not particularly limited and includes, for example, diamond, line, zigzag, square, cone, circle, approximately circle, and irregular. The above-mentioned each line pattern may exist alone or in combination. For example, the relevant properties of the polymer film or the mechanical extrusion conditions may be adjusted to provide a specified void volume (Vv) value and surface roughness Rz value in accordance with one or more of the following conditions:
the weight average molecular weight (Mw) of the polyvinyl acetal (one) 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, 190,000 daltons, 195,000 daltons, 200,000 daltons, 205,000 daltons, 210,000 daltons, 215,000 daltons, 220,000 daltons, 225,000 daltons, 230,000 daltons, 235,000 daltons, 240,000 daltons, or 245,000 daltons. In some embodiments of the invention, the polyvinyl acetal has a weight average molecular weight (Mw) of 180,000 daltons to 205,000 daltons.
The glass transition temperature (Tg) of the (II) polymer film may be 10℃to 22℃such as 10.5 ℃, 11 ℃, 11.5 ℃, 12 ℃, 12.5 ℃, 13 ℃, 13.5 ℃, 14 ℃, 14.5 ℃, 15 ℃, 15.5 ℃, 16 ℃, 16.5 ℃, 17 ℃, 17.5 ℃, 18 ℃, 18.5 ℃, 19 ℃, 19.5 ℃, 20 ℃, 20.5 ℃, 21 ℃ or 21.5 ℃.
The plasticizer in the polymer film may be used in an amount of 30 to 60 parts by weight, for example, 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 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 the plasticizer based on 100 parts by weight of the polyvinyl acetal.
The pressure of the embossing wheel can be 1 kilogram per square centimeter (kg/cm) 2 ) To 15 kg/square cm, preferably 3 kg/square cm to 13 kg/square cm, more particularly 5 kg/square cm to 10 kg/square cm, for example 6 kg/square cm, 7 kg/square cm, 8 kg/square cm or 9 kg/square cm.
The temperature of the embossing wheel may be from 80 c to 130 c, preferably from 85 c to 125 c, more particularly from 90 c to 120 c, for example 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃, 110 ℃, 111 ℃, 112 ℃, 113 ℃, 114 ℃, 115 ℃, 116 ℃, 117 ℃, 118 ℃, or 119 ℃. When the temperature of the embossing wheel falls outside of a particular range, the polymer film may not achieve a desired void volume (Vv) value.
1.3. Preparation of polymeric films
The preparation method of the polymer film of the present invention is not particularly limited, and for example, a polymer composition can be obtained by kneading a polyvinyl acetal with optional components (e.g., plasticizers), and then forming a film of the polymer composition by the conventional film preparation method, and optionally mechanically embossing the film to provide a 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, a calendaring method, a casting method, an extrusion tentering method, a direct extrusion method, and an extrusion blow molding method.
In some embodiments of the invention, the polymer film is prepared as follows: the resinous polyvinyl acetal and the plasticizer are mixed and kneaded at a temperature of 100 to 150 ℃ and a rotation speed of 10 to 50rpm using a mixer for 5 to 30 minutes to obtain a polymer composition, and after the polymer composition is cooled to room temperature, the polymer composition is put into a hot press and hot-pressed at a temperature of 100 to 200 ℃ and a pressure of 2 to 5 kg for 1 to 10 minutes to form a film. Repeating the above film forming steps and adjusting the composition of the polymer composition as needed to provide films of different functions, and laminating the films to form a polymer film having a multilayer structure; finally, the polymer film is optionally mechanically embossed to provide a desired void volume (Vv) value and surface roughness Rz value, wherein the mechanical embossing parameters are as follows: the pressure of the embossing wheel is 5 kg/square cm to 8 kg/square cm, and the temperature of the embossing wheel is 90 ℃ to 120 ℃.
2. Laminated glass
The polymer film of the present invention can be used to prepare laminated glass. Accordingly, the present invention also provides a laminated glass comprising 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 currently used for manufacturing laminated glass, such as float glass (float glass), tempered glass, wired glass, or conventional flat glass, but the present invention is not limited thereto. In the latter embodiment, float glass is used as the first glass sheet and the second glass sheet.
The laminated glass of the present invention can be produced by a method for producing laminated glass existing in the related art. For example, the preparation of laminated glass can be performed as follows: the polymer film is sandwiched between two glass sheets to obtain a laminate, the conveying speed of a conveying belt of a roller press is set to be 2 m/min to 8 m/min, the temperature of an oven is set to be 150 ℃ to 200 ℃, the laminate is placed on the conveying belt to pass through the oven first and then between a pair of rollers, the distance between the rollers is set to be 5.5 mm to 6.5 mm, and then the rolled laminate is cooled to room temperature to complete pre-lamination. And then placing the laminated material after the pre-pressing in an autoclave, and hot-pressing for 100 to 150 minutes under the high-temperature and high-pressure condition to obtain the laminated glass. The high temperature and high pressure conditions are a pressure of 10 bar to 15 bar and a temperature of 100 ℃ to 150 ℃.
3. Examples
3.1. Description of measurement modes
The invention will now be further illustrated by the following specific embodiments, in which the measuring apparatus and method employed are each as follows:
[ measurement of molecular weight of polyvinyl acetal ]
The molecular weight distribution of the polyvinyl acetal was measured by gel permeation chromatography (gel permeation chromatography, GPC) in which the polyvinyl acetal was dissolved in Tetrahydrofuran (THF), GPC analysis was performed under the following conditions, and the molecular weight thereof was calculated in a ratio corresponding to the area of polystyrene standards (Waters PS STD).
The device comprises: waters 1515PUMP system
The detector comprises: waters 2414RI
The brewing conditions are as follows: 1.0 milliliter/minute (mL/min), THF
And (3) pipe column: waters Styragel HR5 THF, waters Styragel HR THF, waters Styragel HR THF, waters Styragel HR1 THF
[ measurement of void volume (Vv) ]
The void volume (Vv) value of the surface of the polymer film at 10% load area was measured using a laser confocal microscope (laser confocal microscope) (model: LEXT OLS5000-SAF, available from Olympus) at a temperature of 24±3 ℃ and a relative humidity of 63±3%, according to ISO25178-2:2012. The measurement conditions were as follows: the light source has a wavelength of 405 nm, the objective lens is 100 times (mplpon-100 xLEXT), the optical zoom is 50 times, the observation area is 1500 micrometers by 1500 micrometers, the resolution is 1024 pixels by 1024 pixels, the operating condition is set to auto tilt removal (auto tilt removal), and no optical filter is used. In the obtained load area graph, a core void volume (Vvc) value and a trough void volume (Vvv) value are obtained, the void volume (Vv) value being the sum of the trough void volume (Vvv) value and the core void volume (Vvc) value. Void volume (Vv) values are in units of cubic microns per square micron.
[ measurement of surface roughness Rz value ]
The surface roughness Rz value was measured by a roughness tester (model: SE 300, available from Session research Co., ltd.) (Kosaka Laboratory Ltd.) and according to JIS B0601 (1994). First, a polymer film was cut into a size of 8 cm×30 cm as a test sample. The measurement conditions were set as follows: the vertical magnification (vertical magnification) is set to be automatic, and the horizontal magnification (horizontal magnification) is set to 25 mm/lambda c The cut off distance was set to 2.5 mm (i.e., calculated every 2.5 mm), the evaluation length was seven times the cut off distance, and the reference length was set to 17.5 mm, the measurement direction was the mechanical direction (machine direction).
[ measurement of glass transition temperature (Tg) ]
The Tg of the polymer film was measured under nitrogen using a differential scanning calorimeter (model: TA DSC 25, available from TA Instruments). First, 7 mg of the polymer film was taken as a sample and placed on a sample stage of a differential scanning calorimeter, and the temperature was raised to 150℃at a heating rate of 10℃per minute and then kept at that temperature for 5 minutes. Next, the sample was equilibrated at-50 ℃ and held at temperature for 5 minutes, then heated to 100 ℃ at a heating rate of 10 ℃/minute to obtain a graph of temperature versus heat flow (heat flow) (X-axis is temperature, Y-axis is heat flow), and the temperature corresponding to the midpoint of glass transition (midpoint) was recorded as Tg.
[ test for residual bubble ]
The laminated glass was cut into test specimens having a width of 30 cm and a length of 30 cm. The test sample was placed in a vertically placed manner in an oven at 120 deg.c for 14 days to visually observe whether or not bubbles, which are bubbles existing between the glass and the polymer film and not in contact with the outside air, remained. The evaluation criteria were as follows: if the test sample has no bubble residue, recording as 'very good', and representing that the bubble test result is very good; if the test sample has bubbles with the diameter smaller than 0.5 mm and the number of the bubbles is one, recording as O, and indicating that the bubble test result is good; and if the test sample has bubble residues with the diameter of less than 0.5 mm and the number of the bubbles is more than two, or has bubble residues with the diameter of more than 0.5 mm, recording as X, and indicating that the bubble test result is poor.
[ edge degumming test ]
The laminated glass was cut into test specimens having a width of 30 cm and a length of 30 cm. The test specimens were placed in a vertical-placed manner in an oven at 50℃and a relative humidity of 95% for 14 days, and whether the test specimens had edge-degummed or not was visually observed. The evaluation criteria were as follows: if the test sample did not exhibit edge debonding (i.e., the glass was tightly adhered to the polymer film), recorded as "verygood" representing passing the edge debonding test; conversely, if edge debonding occurs for the test sample (i.e., the glass does not adhere tightly to the polymer film), a record of "X" indicates that the edge debonding test was not passed.
3.2. Raw material information list for examples and comparative examples
Table 1: raw material information list
| Raw material model or abbreviation | Description and purchase Source |
| PVB | Polyvinyl butyral, commercially available from vinca petrochemicals Co., ltd |
| 3GO | Plasticizer, triethylene glycol bis (2-ethylhexanoate) |
3.3. Preparation of Polymer film and measurement of Properties
The polymer films of examples 1 to 10 and comparative examples 1 to 5 were produced in the following manner. First, 100 parts by weight of PVB was mixed with 38.5 parts by weight of 3GO to obtain a mixture, which was kneaded at 120℃for 15 minutes using a mixer at a rotation speed of 35rpm, and then cooled to room temperature to obtain a polymer film composition. Next, the polymer film composition was placed in a hot press, and hot press was performed at 150 ℃ and a pressure of 3 kg for 3 minutes to obtain a polymer film.
Thereafter, the polymer film is mechanically embossed on both surfaces by an embossing machine as needed. The mechanical embossing was carried out under the conditions shown in tables 2-1 to 2-2, and the linear velocity of the polymer film passing between the embossing wheels was 10 m/min to 18 m/min.
The molecular weights of the PVBs of examples 1 to 10 and comparative examples 1 to 5, as well as the thickness, tg, surface roughness Rz, void volume at 10% load area (Vv) of the polymer films were measured according to the measurement methods carried out previously, and the results are recorded in tables 2-1 to 2-2.
Table 2-1: ingredients and Properties of PVB and Polymer films of examples 1 to 10
Table 2-2: ingredients and properties of PVB and Polymer films of comparative examples 1 to 5
3.4. Preparation and property evaluation of laminated glass
Laminated glasses were prepared using the polymer films of examples 1 to 10 and comparative examples 1 to 5, respectively. First, two clear transparent float glass sheets (300 mm in length, 150 mm in width, 2 to 4 mm in thickness) were prepared, and then, polymer films of examples 1 to 10 and comparative examples 1 to 5 were respectively sandwiched between the two transparent float glass sheets to obtain a laminate, which was pre-laminated by a roll press method. The roll-pressing operation is as follows: the conveying speed of the conveyor belt of the roll press was set to 3.5 m/min and the oven temperature was set to 180 c, the laminate was placed on the conveyor belt to pass through the oven first and then between a pair of rollers, the distance between the rollers was set to 6.3 mm, and the rolled laminate was cooled to room temperature. The pre-laminated laminate was placed in an autoclave, hot-pressed at a pressure of 13 bar and a temperature of 135 ℃ for 120 minutes, and then cooled to room temperature, to prepare a laminated glass.
The laminated glasses of examples 1 to 10 and comparative examples 1 to 5 were subjected to the bubble remaining test and the edge degumming test according to the methods described above, and the evaluation results were recorded in tables 3-1 and 3-2.
Table 3-1: properties of the laminated glasses of examples 1 to 10
Table 3-2: properties of the laminated glasses of comparative examples 1 to 5
As shown in table 3-1, laminated glass produced from the polymer film of the present invention gave excellent and good results in the bubble remaining test without edge peeling flaws, and the bubble remaining test results were excellent and passed the edge peeling test. In particular, examples 1 to 10 show that, at different PVB molecular weights and Tg and in the embossing conditions, the laminated glass obtained meets the requirements of obtaining excellent and good results in the bubble residual test and no edge-peeling, as long as the void volume (Vv) value of the polymer film at 10% load area ratio is within the specified range.
In contrast, as shown in Table 3-2, laminated glass produced from polymer films not belonging to the present invention did not meet the requirements of obtaining excellent and good results in the bubble remaining test without edge peeling. In particular, comparative examples 2 to 4 show that when the void volume (Vv) value of the polymer film is below the specified range, the resulting laminated glass cannot achieve excellent and good results in the bubble remaining test and fails the edge-peeling test, regardless of the PVB molecular weight and Tg, and the pressing condition. Comparative examples 1 and 5 show that when the void volume (Vv) value of the polymer film is above the specified range, the edge-degluing test cannot be passed although the bubble-remaining test can be rated well.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and illustrate the technical features of the present invention, not intended to limit the scope of the protection of the present invention. Any person skilled in the art can easily accomplish the changes or arrangements without departing from the technical principle and spirit of the present invention, and the present invention is claimed. Accordingly, the scope of the invention is set forth in the following claims.
Claims (12)
1. A polymeric film comprising a polyvinyl acetal, at least one surface of the polymeric film having a void volume value of from 2 cubic microns/square micron to 18 cubic microns/square micron at a load area rate of 10%, wherein the load area rate and the void volume are defined according to ISO25178-2:2012, wherein the polymeric film has a glass transition temperature of from 10 ℃ to 22 ℃.
2. The polymer film of claim 1, wherein each of the two surfaces of the polymer film independently has a void volume value of 2 cubic micrometers per square micrometer to 18 cubic micrometers per square micrometer at a load area ratio of 10%.
3. The polymer film of claim 1, wherein the polyvinyl acetal is selected from the group consisting of: polyvinyl formal, polyvinyl acetal, polyvinyl butyral, polyvinyl valeraldehyde, polyvinyl caproaldehyde, and combinations thereof.
4. The polymer film of claim 1, wherein the at least one surface of the polymer film further has a surface roughness Rz value of 15 microns to 40 microns.
5. The polymer film of claim 2, wherein the two surfaces of the polymer film further each independently have a surface roughness Rz value of 15 microns to 40 microns.
6. The polymer film of claim 1, wherein the polyvinyl acetal has a weight average molecular weight of 150,000 to 250,000.
7. The polymer film of any one of claims 1-6, further comprising a plasticizer.
8. The polymer film according to claim 7, wherein the plasticizer is contained in an amount of 30 to 60 parts by weight based on 100 parts by weight of the polyvinyl acetal.
9. The polymer film of any one of claims 1 to 6, having a thickness of 0.2 mm to 2 mm.
10. The polymer film of any one of claims 1 to 6, which is a multilayer film.
11. The polymer film of any one of claims 1 to 6, further comprising an additive selected from the group consisting of: dyes, pigments, stabilizers, antioxidants, flame retardants, infrared absorbers, infrared blockers, ultraviolet absorbers, ultraviolet stabilizers, lubricants, dispersants, surfactants, chelating agents, coupling agents, binders, adhesion control agents, and combinations thereof.
12. A laminated glass comprising a first glass sheet, a second glass sheet, and a polymer film according to any one of claims 1 to 11 disposed between the first glass sheet and the second glass sheet.
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| KR1020200041969A KR102399169B1 (en) | 2019-11-29 | 2020-04-07 | Polymer film and uses of the same |
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| CN115991919A (en) * | 2021-10-18 | 2023-04-21 | 长春石油化学股份有限公司 | Polymer film and use thereof |
| US11746198B2 (en) | 2021-10-18 | 2023-09-05 | Chang Chun Petrochemical Co., Ltd. | Polymer film and uses of the same |
| JP7185797B1 (en) | 2021-10-18 | 2022-12-07 | チャン チュン ペトロケミカル カンパニー リミテッド | Polymer film and its use |
| CN115489180B (en) * | 2021-10-18 | 2024-04-16 | 长春石油化学股份有限公司 | Polymer film and use thereof |
| CN116619855A (en) * | 2022-02-11 | 2023-08-22 | 长春石油化学股份有限公司 | Polymer film and use thereof |
| US20230415461A1 (en) | 2022-06-28 | 2023-12-28 | Chang Chun Petrochemical Co., Ltd. | Polymer film and uses of the same |
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| JP2004168646A (en) * | 2002-11-01 | 2004-06-17 | Sekisui Chem Co Ltd | Interlayer film for glass laminate, glass laminate, and method for manufacturing glass laminate |
| EP2548729A1 (en) * | 2011-07-22 | 2013-01-23 | Kuraray Europe GmbH | Film of polyvinyl(iso)acetal containing plasticizers |
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| KR102378647B1 (en) * | 2014-09-30 | 2022-03-24 | 세키스이가가쿠 고교가부시키가이샤 | Interlayer film for laminated glass, and laminated glass |
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| JP2018187929A (en) * | 2017-05-10 | 2018-11-29 | クラレイ ユーロップ ゲゼルシャフト ミット ベシュレンクテル ハフツングＫｕｒａｒａｙ Ｅｕｒｏｐｅ ＧｍｂＨ | Interlayer film with shade band |
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