TWI778832B - Polymer film and uses of the same - Google Patents
Polymer film and uses of the same Download PDFInfo
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Description
本發明係關於一種聚合物膜，特別是關於一種在特定之負荷面積率（material ratio）下具有特定之空隙體積（void volume，Vv）值標準差的聚合物膜。本發明亦關於使用該聚合物膜所製備之夾層玻璃（laminated glass）。The present invention relates to a polymer film, and more particularly, to a polymer film having a specified standard deviation of void volume (Vv) values at a specified material ratio. The present invention also relates to laminated glass produced using the polymer film.
夾層玻璃係一種將聚合物膜夾在二玻璃片中間，藉由熱壓合之方式，使玻璃片與聚合物膜緊密接合而形成之具有複合式結構的玻璃材料。夾層玻璃因具有較佳的耐衝擊性及隔音性，故被廣泛應用於汽車工業與建築工業。Laminated glass is a kind of glass material with a composite structure formed by sandwiching a polymer film between two glass sheets and bonding the glass sheet and the polymer film closely by means of thermocompression. Laminated glass is widely used in automobile industry and construction industry because of its better impact resistance and sound insulation.
由於夾層玻璃的製備過程涉及玻璃片與聚合物膜之間的熱壓合，為了避免空氣殘留於夾層玻璃之玻璃片與聚合物膜之間，通常係預先於聚合物膜表面上押花以形成紋路（即，設計凹凸結構），以利在預壓合期間空氣可順利排出，從而避免夾層玻璃中有氣泡產生。然而，既有夾層玻璃往往因上述紋路而產生存在在光照下肉眼可見的細絲狀條紋，引起光學變形的視覺缺陷，影響夾層玻璃的可視性，亦會影響夾層玻璃的透光度，或易發生折射現象而出現眩光，導致觀看者眼睛不適的問題。Since the production process of laminated glass involves thermal pressing between the glass sheet and the polymer film, in order to avoid air remaining between the glass sheet and the polymer film of the laminated glass, embossing is usually performed on the surface of the polymer film to form textures. (That is, the concave-convex structure is designed), so that the air can be discharged smoothly during the pre-pressing, so as to avoid the generation of air bubbles in the laminated glass. However, the existing laminated glass often produces filamentous stripes visible to the naked eye due to the above-mentioned lines, causing visual defects of optical deformation, affecting the visibility of the laminated glass, and also affecting the light transmittance of the laminated glass, or easy to Glare occurs due to refraction, which causes discomfort to the viewer's eyes.
本發明人研究發現，上述問題意外地與聚合物膜表面上所形成之紋路的均勻性有關。若聚合物膜表面上的紋路非常不均勻，則在壓合後夾層玻璃容易存在在光照下肉眼可見之細絲狀條紋，引起光學變形的視覺缺陷，從而影響夾層玻璃的可視性，亦會影響夾層玻璃的透光度。反之，若聚合物膜表面上的紋路過於均勻，則在壓合後夾層玻璃容易出現眩光問題，會導致觀看者眼睛不適。The present inventors have found that the above-mentioned problems are unexpectedly related to the uniformity of the textures formed on the surface of the polymer film. If the lines on the surface of the polymer film are very uneven, the laminated glass is likely to have filamentous stripes that are visible to the naked eye after lamination, causing visual defects of optical deformation, thereby affecting the visibility of the laminated glass and also affecting Transmittance of laminated glass. On the contrary, if the texture on the surface of the polymer film is too uniform, the laminated glass is prone to glare after lamination, which will cause discomfort to the viewer's eyes.
基於此，本發明旨在提供一種聚合物膜，具體言之，係關於一種在特定之負荷面積率下具有特定之空隙體積（Vv）值標準差的聚合物膜。本發明聚合物膜在與玻璃片進行熱壓合後，夾層玻璃不存在光學變形及眩光問題，且具有經提升之光穿透率，進一步可控制空隙體積值於較佳範圍內，以進一步改良夾層玻璃之敲擊黏附力值測試與氣泡殘留測試結果。因此，本發明聚合物膜特別適合應用於車用夾層玻璃之製備。Based on this, the present invention aims to provide a polymer film, in particular, a polymer film having a specific standard deviation of void volume (Vv) value at a specific loading area ratio. After the polymer film of the present invention is hot-pressed with the glass sheet, the laminated glass has no optical distortion and glare problems, and has an improved light transmittance, which can further control the void volume value within a preferred range, so as to further improve The test results of the tap adhesion value and the residual bubble test of the laminated glass. Therefore, the polymer film of the present invention is particularly suitable for the preparation of laminated glass for vehicles.
具體言之，本發明之一目的在於提供一種聚合物膜，其中該聚合物膜具有第一表面及第二表面，第一表面在負荷面積率為10%時之空隙體積（Vv）值的標準差為0.5立方微米／平方微米（μm 3/μm 2）至2.5立方微米／平方微米，且該負荷面積率及空隙體積之定義係依據ISO 25178-2:2012。 Specifically, an object of the present invention is to provide a polymer film, wherein the polymer film has a first surface and a second surface, and the standard of the void volume (Vv) value of the first surface when the loading area ratio is 10% The difference is from 0.5 micrometers cubic per micrometer (μm 3 /μm 2 ) to 2.5 micrometers cubic per square micrometer, and the definitions of the loaded area ratio and void volume are in accordance with ISO 25178-2:2012.
於本發明之部分實施態樣中，聚合物的第一表面在負荷面積率為10%時之Vv值為2立方微米／平方微米至35立方微米／平方微米。In some embodiments of the present invention, the Vv value of the first surface of the polymer at a loading area ratio of 10% is 2 to 35 cubic micrometers/micrometer.
於本發明之部分實施態樣中，聚合物的第一表面具有15微米至55微米的表面粗糙度Rz值，所述Rz值係依據JIS B 0601(1994)測量而得。In some embodiments of the present invention, the first surface of the polymer has a surface roughness Rz value of 15 to 55 microns, which is measured in accordance with JIS B 0601 (1994).
於本發明之部分實施態樣中，聚合物的第二表面在負荷面積率為10%時之Vv值的標準差為0.5立方微米／平方微米至2.5立方微米／平方微米。In some embodiments of the present invention, the standard deviation of the Vv value of the second surface of the polymer at a loading area ratio of 10% is 0.5 to 2.5 cubic micrometers per square micrometer.
於本發明之部分實施態樣中，聚合物的第二表面在負荷面積率為10%時之Vv值為2立方微米／平方微米至35立方微米／平方微米。In some embodiments of the present invention, the second surface of the polymer has a Vv value of 2 to 35 cubic micrometers/micrometer at a loading area ratio of 10%.
於本發明之部分實施態樣中，聚合物的第二表面具有15微米至55微米的Rz值，所述Rz值係依據JIS B 0601(1994)測量而得。In some embodiments of the present invention, the second surface of the polymer has an Rz value of 15 microns to 55 microns, which is measured in accordance with JIS B 0601 (1994).
於本發明之部分實施態樣中，該聚合物膜包含聚乙烯醇縮醛（polyvinylacetal），且聚乙烯醇縮醛可選自以下群組：聚（乙烯醇縮甲醛）（poly(vinyl formal)）、聚（乙烯醇縮乙醛）、聚（乙烯醇縮丁醛）（poly(vinyl butyral)）、聚（乙烯醇縮戊醛）、聚（乙烯醇縮己醛）、及其組合。於本發明之較佳實施態樣中，聚乙烯醇縮醛係聚（乙烯醇縮丁醛）。In some embodiments of the present invention, the polymer film comprises polyvinylacetal, and the polyvinylacetal may be selected from the group consisting of: poly(vinyl formal) ), poly(vinyl acetal), poly(vinyl butyral), poly(vinyl valeral), poly(vinyl acetal), and combinations thereof. In a preferred embodiment of the present invention, the polyvinyl acetal is poly(vinyl butyral).
於本發明之部分實施態樣中，聚合物膜具有0.1毫米至2.5毫米之厚度。In some embodiments of the invention, the polymer film has a thickness of 0.1 mm to 2.5 mm.
本發明之另一目的在於提供一種夾層玻璃，其包含一第一玻璃片、一第二玻璃片、以及位於該第一玻璃片與第二玻璃片之間之中間膜，該中間膜係由如上述之聚合物膜所提供。Another object of the present invention is to provide a laminated glass comprising a first glass sheet, a second glass sheet, and an intermediate film between the first glass sheet and the second glass sheet, the intermediate film is made of The polymer film described above is provided.
為使本發明之上述目的、技術特徵及優點能更明顯易懂，下文係以部分具體實施態樣進行詳細說明。In order to make the above objects, technical features and advantages of the present invention more clearly understood, the following is a detailed description of some specific embodiments.
以下將具體地描述根據本發明之部分具體實施態樣；惟，在不背離本發明之精神下，本發明尚可以多種不同形式之態樣來實踐，不應將本發明保護範圍限於所述具體實施態樣。The following will specifically describe some embodiments of 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 style.
除非另有說明，於本說明書及申請專利範圍中所使用之「一」、「該」及類似用語應理解為包含單數及複數形式。Unless stated otherwise, the terms "a", "the" and similar terms used in this specification and the claims should be construed to include both the singular and the plural.
除非另有說明，於本說明書及申請專利範圍中所使用之「第一」、「第二」及類似用語僅係用於區隔所描述之元件或成分，本身並無特殊涵義，且並非用於代表先後順序。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 meaning per se, and are not used for in the order of representation.
除非另有說明，於本說明書及申請專利範圍中，用語「負荷面積率」係依據ISO 25178-2:2012而定義。負荷面積曲線圖為表面高度對其涵蓋之區域面積的函數曲線圖，負荷面積率係指在一指定高度以上的區域面積。Unless otherwise specified, in this specification and the scope of the patent application, the term "loaded area ratio" is defined in accordance with ISO 25178-2:2012. The load area curve is a function curve of the surface height to the area covered by it, and the load area rate refers to the area above a specified height.
除非另有說明，於本說明書及申請專利範圍中，用語「空隙體積（Vv）」係依據ISO 25178-2:2012而定義。空隙體積（Vv）係指在一特定負荷面積率下的每單位面積之空隙的體積。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 specified area rate of loading.
於本說明書及申請專利範圍中，用語「空隙體積（Vv）值的標準差」係藉由以下方式所計算而得：如圖1所示，在30公分×30公分的聚合物膜上，於四個角距離二邊緣各1公分處及正中心處裁切3公分×3公分的測試樣品而得到五個測試樣品，對該五個測試樣品進行Vv值的測量，並基於該五個Vv值計算而得到空隙體積值的標準差。In this specification and the scope of the patent application, the term "standard deviation of void volume (Vv) value" is calculated by the following method: As shown in Figure 1, on a polymer film of 30 cm × 30 cm, The four corners are 1 cm away from the two edges and the center of the test sample is cut 3 cm × 3 cm to obtain five test samples, the Vv value of the five test samples is measured, and based on the five Vv values Calculated to obtain the standard deviation of void volume values.
除非另有說明，於本說明書及申請專利範圍中，用語「表面粗糙度Rz值」係指表面之十點平均粗糙度，且係根據JIS B 0601（1994）測量而得。Unless otherwise specified, 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).
本發明對照現有技術的功效在於，提供一種在特定之負荷面積率下具有特定之Vv值標準差的聚合物膜，以及利用該聚合物膜提供無光學變形及眩光問題且具有良好光穿透率的夾層玻璃。所述夾層玻璃特別適合應用於汽車工業。以下就本發明聚合物膜及其相關應用提供詳細說明。The effect of the present invention compared with the prior art is to provide a polymer film with a specific standard deviation of Vv value under a specific load area ratio, and to use the polymer film to provide no optical distortion and glare problems and have good light transmittance of laminated glass. The laminated glass is particularly suitable for use in the automotive industry. A detailed description of the polymer film of the present invention and its related applications is provided below.
1.1. 聚合物膜polymer film
1.1.1.1. 聚合物膜之構成The composition of the polymer film
本發明聚合物膜係包含聚乙烯醇縮醛作為必要成分，且視需要可進一步包含其他選用成分，如塑化劑或其他習知添加劑。於本發明之部分實施態樣中，聚合物膜係包含聚乙烯醇縮醛及塑化劑，或者聚合物膜實質上係由聚乙烯醇縮醛及塑化劑所構成，或者聚合物膜係由聚乙烯醇縮醛及塑化劑所構成。The polymer film system 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 system comprises polyvinyl acetal and a plasticizer, or the polymer film is substantially composed of polyvinyl acetal and a plasticizer, or the polymer film system It is composed of polyvinyl acetal and plasticizer.
本發明聚合物膜可為由單一層構成之單層膜，或由多個層所構成之多層膜，只要聚合物膜整體而言符合所指定之Vv值標準差之條件即可。於聚合物膜為多層膜之態樣中，聚合物膜之各層的材質可為相同或不同，而各自扮演相同或不同之功能層，所述功能層例如是可提供以下一或多種功能之層：隔音功能、隔熱功能、反射功能、抗反射功能、折射功能、抗折射功能、分光功能、及減光功能。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 multiple layers, as long as the polymer film as a whole complies with the specified standard deviation of the Vv value. In the state where the polymer film is a multilayer film, the materials of each layer of the polymer film can be the same or different, and each plays the same or different functional layer, such as 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-reflection function, spectroscopic function, and light reduction function.
1.1.1.1.1.1. 聚乙烯醇縮醛Polyvinyl Acetal
聚乙烯醇縮醛的實例包括但不限於聚（乙烯醇縮甲醛）、聚（乙烯醇縮乙醛）、聚（乙烯醇縮丁醛）、聚（乙烯醇縮戊醛）、及聚（乙烯醇縮己醛）。前述各聚乙烯醇縮醛可單獨使用，亦可混合多種使用。於本發明之較佳實施態樣中，聚乙烯醇縮醛為聚（乙烯醇縮丁醛）。於後附實施例中，聚合物膜係由聚（乙烯醇縮丁醛）與塑化劑所構成。Examples of polyvinyl acetals include, but are not limited to, poly(vinyl formal), poly(vinyl acetal), poly(vinyl butyral), poly(vinyl valeral), and poly(ethylene acetal) acetal). Each of the above-mentioned polyvinyl acetals may be used alone or in combination of two or more. In a preferred embodiment of the present invention, the polyvinyl acetal is poly(vinyl butyral). In the following examples, the polymer film is composed of poly(vinyl butyral) and a plasticizer.
聚乙烯醇縮醛的分子量並無特殊限制。於本發明之部分實施態樣中，聚乙烯醇縮醛的數量平均分子量（Mn）可為90,000至125,000，更特定言之為105,000至120,000，例如90,000、90,500、91,000、91,500、92,000、92,500、93,000、93,500、94,000、94,500、95,000、95,500、96,000、96,500、97,000、97,500、98,000、98,500、99,000、99,500、100,000、100,500、101,000、101,500、102,000、102,500、103,000、103,500、104,000、104,500、105,000、105,500、106,000、106,500、107,000、107,500、108,000、108,500、109,000、109,500、110,000、110,500、111,000、111,500、112,000、112,500、113,000、113,500、114,000、114,500、115,000、115,500、116,000、116,500、117,000、117,500、118,000、118,500、119,000、119,500、120,000、120,500、121,000、121,500、122,000、122,500、123,000、123,500、124,000、124,500、或125,000，或介於由上述任二數值所構成之範圍內，但本發明不以此為限。The molecular weight of the polyvinyl acetal is not particularly limited. In some embodiments of the present invention, the polyvinyl acetal may have a number average molecular weight (Mn) of 90,000 to 125,000, more specifically 105,000 to 120,000, such as 90,000, 90,500, 91,000, 91,500, 92,000, 92,500, 93,000、93,500、94,000、94,500、95,000、95,500、96,000、96,500、97,000、97,500、98,000、98,500、99,000、99,500、100,000、100,500、101,000、101,500、102,000、102,500、103,000、103,500、104,000、104,500、105,000、 105,500、106,000、106,500、107,000、107,500、108,000、108,500、109,000、109,500、110,000、110,500、111,000、111,500、112,000、112,500、113,000、113,500、114,000、114,500、115,000、115,500、116,000、116,500、117,000、117,500、 118,000, 118,500, 119,000, 119,500, 120,000, 120,500, 121,000, 121,500, 122,000, 122,500, 123,000, 123,500, 124,000, 124,500, or 125,000, but not within the scope of the present invention This is limited.
於本發明之部分實施態樣中，以聚乙烯醇縮醛之羥基、縮醛基、乙醯基的總重量計，聚乙烯醇縮醛可具有74重量%至84重量%的縮醛基含量（即，縮醛度），例如74重量%、74.5重量%、75重量%、75.5重量%、76重量%、76.5重量%、77重量%、77.5重量%、78重量%、78.5重量%、79重量%、79.5重量%、80重量%、80.5重量%、81重量%、81.5重量%、82重量%、82.5重量%、83重量%、83.5重量%、或84重量%，或介於由上述任二數值所構成之範圍內的縮醛度。以聚乙烯醇縮醛之羥基、縮醛基、乙醯基的總重量計，聚乙烯醇縮醛可具有0.1重量%至3.0重量%的乙醯基含量（即，乙醯度），例如0.1重量%、0.2重量%、0.3重量%、0.4重量%、0.5重量%、0.6重量%、0.7重量%、0.8重量%、0.9重量%、1.0重量%、1.1重量%、1.2重量%、1.3重量%、1.4重量%、1.5重量%、1.6重量%、1.7重量%、1.8重量%、1.9重量%、2.0重量%、2.1重量%、2.2重量%、2.3重量%、2.4重量%、2.5重量%、2.6重量%、2.7重量%、2.8重量%、2.9重量%、或3.0重量%，或介於由上述任二數值所構成之範圍內的乙醯度。In some embodiments of the present invention, the polyvinyl acetal may have an acetal group content of 74% to 84% by weight based on the total weight of the hydroxyl groups, acetal groups, and acetyl groups of the polyvinyl acetal. (ie, degree of acetalization), such as 74% by weight, 74.5% by weight, 75% by weight, 75.5% by weight, 76% by weight, 76.5% by weight, 77% by weight, 77.5% by weight, 78% by weight, 78.5% by weight, 79% by weight wt %, 79.5 wt %, 80 wt %, 80.5 wt %, 81 wt %, 81.5 wt %, 82 wt %, 82.5 wt %, 83 wt %, 83.5 wt %, or 84 wt %, or in between The degree of acetalization within the range formed by two numerical values. The polyvinyl acetal may have an acetyl group content (ie, degree of acetyl) of 0.1 wt% to 3.0 wt%, based on the total weight of the hydroxyl groups, acetal groups, and acetyl groups of the polyvinyl acetal, for example, 0.1 % by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1.0% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight , 1.4% by weight, 1.5% by weight, 1.6% by weight, 1.7% by weight, 1.8% by weight, 1.9% by weight, 2.0% by weight, 2.1% by weight, 2.2% by weight, 2.3% by weight, 2.4% by weight, 2.5% by weight, 2.6% by weight wt %, 2.7 wt %, 2.8 wt %, 2.9 wt %, or 3.0 wt %, or an acetyl level within a range consisting of any two of the foregoing values.
於本發明之較佳實施態樣中，以聚乙烯醇縮醛之羥基、縮醛基、乙醯基的總重量計，聚乙烯醇縮醛的羥基含量較佳為16重量%至23重量%，更佳為18重量%至21重量%，例如16重量%、16.5重量%、17重量%、17.5重量%、18重量%、18.5重量%、19重量%、19.5重量%、20重量%、20.5重量%、21重量%、21.5重量%、22重量%、22.5重量%、或23重量%，或介於由上述任二數值所構成之範圍內。當聚乙烯醇縮醛的羥基含量在指定範圍內時，聚乙烯醇縮醛與塑化劑具有較佳相容性。若聚乙烯醇縮醛的羥基含量高於指定範圍，則塑化劑易有滲出的情形。若聚乙烯醇縮醛的羥基含量低於指定範圍，則所製得夾層玻璃的敲擊黏附力（pummel adhesion）較差，不符合規格。In a preferred embodiment of the present invention, based on the total weight of the hydroxyl groups, acetal groups and acetyl groups of the polyvinyl acetal, the hydroxyl content of the polyvinyl acetal is preferably 16% to 23% by weight , more preferably 18% to 21% by weight, such as 16% by weight, 16.5% by weight, 17% by weight, 17.5% by weight, 18% by weight, 18.5% by weight, 19% by weight, 19.5% by weight, 20% by weight, 20.5% by weight wt %, 21 wt %, 21.5 wt %, 22 wt %, 22.5 wt %, or 23 wt %, or a range consisting of any two of the foregoing values. When the hydroxyl content of the polyvinyl acetal is within the specified range, the polyvinyl acetal has better compatibility with the plasticizer. If the hydroxyl content of the polyvinyl acetal is higher than the specified range, the plasticizer tends to ooze out. If the hydroxyl content of the polyvinyl acetal is lower than the specified range, the resulting laminated glass has poor pummel adhesion and does not meet the specification.
1.1.2.1.1.2. 塑化劑Plasticizer
本文中，塑化劑係指可改變熱塑性樹脂的可塑性之化學物質，也可被稱為可塑劑。塑化劑的實例包括但不限於多元酸或多元醇之酯，例如三乙二醇雙（2-乙基己酸酯）（triethylene glycol bis(2-ethylhexanoate)）、四乙二醇雙（2-乙基己酸酯）、三乙二醇雙（2-乙基丁酸酯）、四乙二醇雙（2-乙基丁酸酯）、三乙二醇二庚酸酯、四乙二醇二庚酸酯、己二酸二己酯、己二酸二辛酯、環己基己二酸己酯、己二酸二異壬酯、己二酸庚基壬酯、癸二酸二丁酯、己二酸雙[2-（2-丁氧基乙氧基）乙酯]、聚合己二酸酯（polymeric adipate）、二丙二醇二苯甲酸酯、三丙二醇二苯甲酸酯、聚丙二醇二苯甲酸酯、苯甲酸異癸酯、苯甲酸-2-乙基己酯、丙二醇二苯甲酸酯、鄰苯二甲酸二異壬酯、對苯二甲酸二丁氧基乙酯、蓖麻油、蓖麻油酸甲酯、大豆油、環氧化大豆油、及其組合。Herein, plasticizers refer to chemical substances that can change the plasticity of thermoplastic resins, and may also be referred to as plasticizers. Examples of plasticizers include, but are not limited to, esters of polyacids or polyols, such as triethylene glycol bis(2-ethylhexanoate), tetraethylene glycol bis(2-ethylhexanoate), - ethylhexanoate), triethylene glycol bis (2-ethyl butyrate), tetraethylene glycol bis (2-ethyl butyrate), triethylene glycol diheptanoate, tetraethylene glycol Alcohol diheptanoate, dihexyl adipate, dioctyl adipate, cyclohexyl hexyl adipate, diisononyl adipate, heptyl nonyl adipate, dibutyl sebacate , bis[2-(2-butoxyethoxy)ethyl 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.
塑化劑之用量並無特殊限制，只要可提供所預之塑化效果即可。一般而言，塑化劑的用量可控制在以100重量份之聚乙烯醇縮醛計為30重量份至60重量份，例如30重量份、31重量份、32重量份、33重量份、34重量份、35重量份、36重量份、37重量份、38重量份、39重量份、40重量份、41重量份、42重量份、43重量份、44重量份、45重量份、46重量份、47重量份、48重量份、49重量份、50重量份、51重量份、52重量份、53重量份、54重量份、55重量份、56重量份、57重量份、58重量份、59重量份、或60重量份，或介於由上述任二數值所構成之範圍內。The amount of the plasticizer is not particularly limited, as long as the intended plasticizing effect can be provided. Generally speaking, the amount of plasticizer can be controlled to be 30 to 60 parts by weight based on 100 parts by weight of polyvinyl acetal, such as 30 parts by weight, 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight 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, 59 parts by weight parts by weight, or 60 parts by weight, or within the range consisting of any two of the above-mentioned values.
1.1.3.1.1.3. 其他習知添加Additional knowledge added 劑agent
習知添加劑可包含任何可適應性改良聚合物膜在製造過程中的可加工性，或賦予聚合物膜特定功能的物質。習知添加劑的實例包括但不限於染料、顏料、穩定劑、抗氧化劑、阻燃劑、紅外線吸收劑、紅外線阻擋劑、紫外線吸收劑、紫外線穩定劑、潤滑劑、分散劑、表面活性劑、螯合劑、耦合劑、黏結劑、及黏著力控制劑。前述各添加劑可單獨使用，亦可混合多種使用。例如，聚合物膜可包含染料或顏料以形成有色聚合物膜，或包含紫外線吸收劑或紅外線吸收劑以形成具有抗紫外線功能之聚合物膜或形成具有抗紅外線功能之聚合物膜。Conventional additives may include any material that can be adapted to improve the processability of the polymer film during manufacture, or to 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, couplants, binders, and adhesion control agents. Each of the above-mentioned additives may be used alone or in combination of two or more. For example, the polymer film may contain dyes or pigments to form a colored polymer film, or an ultraviolet absorber or an infrared absorber to form a polymer film with anti-ultraviolet function or to form a polymer film with anti-infrared function.
1.2.1.2. 聚合物膜之性質Properties of Polymer Films
1.2.1.1.2.1. 空隙體積（void volume ( VvVv ）)
聚合物膜的表面的凹凸結構可透過測量表面形貌（surface morphology）的三維影像來呈現。ISO 25178-2:2012即為一種用於評估表面形貌的測量規範，其中揭示一種與表面形貌相關的參數，即，空隙體積（Vv）。Vv定義為在一指定負荷面積率下，單位面積內之空隙體積大小，且可自一區域負荷面積曲線圖計算得到，其中區域負荷面積曲線圖之Y軸表示表面高度，X軸表示負荷面積率，X軸之負荷面積率為0%時，Y軸之表面高度為最大值，X軸之負荷面積率為100%時，Y軸之表面高度為0。舉例而言，負荷面積率為10%時之Vv值係代表，在X軸之負荷面積率為10%所對應之Y軸表面高度處所設之水平割平面（horizontal cutting plane）以下所涵蓋的空隙體積大小。因此，當負荷面積率為0%時，Vv值為最大值，當負荷面積率為100%時，Vv值為0。有關Vv參數之相關說明可參照ISO 25178-2:2012，其全文併於此，以供參考。The concavo-convex structure on 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 discloses a parameter related to surface topography, namely, void volume (Vv). Vv is defined as the void volume per unit area at a specified load area rate, and can be calculated from a regional load area graph, where the Y-axis of the area load-area graph represents the surface height and the X-axis represents the load area rate , When the load area rate of the X axis is 0%, the surface height of the Y axis is the maximum value, and when the load area rate of the X axis is 100%, the surface height of the Y axis is 0. For example, the Vv value when the load area rate is 10% represents the gap covered below the horizontal cutting plane set at the Y-axis surface height corresponding to the X-axis load area rate of 10% size. Therefore, when the loaded area ratio is 0%, the Vv value is the maximum value, and when the loaded area ratio is 100%, the Vv value is 0. For the relevant description of the Vv parameter, please refer to ISO 25178-2:2012, the full text of which is incorporated herein for reference.
在夾層玻璃的製備過程中，為了使空氣順利排出而不殘留於聚合物膜與玻璃片之間，聚合物膜的表面需要形成有紋路（即，特定的凹凸結構）以利排氣。然而，研究發現，當聚合物膜表面的Vv值標準差過大，經過熱壓合製程後夾層玻璃中間存在在光照下肉眼可見的細絲狀條紋，對觀看者而言將產生光學變形的視覺缺陷，影響夾層玻璃的可視性，甚至影響夾層玻璃的透光度。另一方面，若聚合物膜表面的Vv值標準差過小，夾層玻璃則會有眩光問題，引起觀看者的眼睛不適。In the production process of laminated glass, in order to allow the air to be discharged smoothly without remaining between the polymer film and the glass sheet, the surface of the polymer film needs to be formed with textures (ie, specific concave-convex structures) to facilitate exhaust. However, the study found that when the standard deviation of the Vv value on the surface of the polymer film is too large, there are filamentous stripes visible to the naked eye in the middle of the laminated glass after the thermal lamination process, which will cause visual defects of optical deformation to the viewer. , affect the visibility of the laminated glass, and even affect the light transmittance of the laminated glass. On the other hand, if the standard deviation of the Vv value on the surface of the polymer film is too small, the laminated glass will have a glare problem, causing discomfort to the viewer's eyes.
有鑑於此，本發明之一技術特徵在於將聚合物膜之Vv值標準差控制在特定範圍內以避免夾層玻璃之光學變形問題及眩光問題。具體言之，本發明聚合物膜的第一表面在負荷面積率為10%時之Vv值標準差為0.5立方微米／平方微米至2.5立方微米／平方微米，例如0.5立方微米／平方微米、0.6立方微米／平方微米、0.7立方微米／平方微米、0.8立方微米／平方微米、0.9立方微米／平方微米、1.0立方微米／平方微米、1.1立方微米／平方微米、1.2立方微米／平方微米、1.3立方微米／平方微米、1.4立方微米／平方微米、1.5立方微米／平方微米、1.6立方微米／平方微米、1.7立方微米／平方微米、1.8立方微米／平方微米、1.9立方微米／平方微米、2.0立方微米／平方微米、2.1立方微米／平方微米、2.2立方微米／平方微米、2.3立方微米／平方微米、2.4立方微米／平方微米、或2.5立方微米／平方微米，或介於由上述任二數值所構成之範圍內。In view of this, one technical feature of the present invention is to control the standard deviation of the Vv value of the polymer film within a specific range to avoid the problem of optical distortion and glare of the laminated glass. Specifically, the standard deviation of the Vv value of the first surface of the polymer film of the present invention when the loading area ratio is 10% is 0.5 cubic micrometers/square micrometers to 2.5 cubic micrometers/square micrometers, such as 0.5 cubic micrometers/square micrometers, 0.6 Cubic microns/microns, 0.7 cubic microns/microns, 0.8 cubic microns/microns, 0.9 cubic microns/microns, 1.0 cubic microns/microns, 1.1 cubic microns/microns, 1.2 cubic microns/microns, 1.3 cubic Micron/micron, 1.4 micron/micron, 1.5 micron/micron, 1.6 micron/micron, 1.7 micron/micron, 1.8 micron/micron, 1.9 micron/micron, 2.0 micron /micrometer, 2.1 micrometers/micrometer, 2.2 micrometers/micrometer, 2.3 micrometers/micrometer, 2.4 micrometers/micrometer, or 2.5 micrometers/micrometer, or any two of the above within the range.
此外，Vv值越小表示聚合物膜表面的凹槽較淺，容易使得在聚合物膜與玻璃片之間的空氣不易被完全排出而不容易完整地接合。鑑於此，為了使夾層玻璃沒有氣泡殘留且沒有邊緣脫膠瑕疵，本發明聚合物膜的第一表面較佳具有在特定範圍內之Vv值。於本發明之部分實施態樣中，聚合物膜的第一表面在負荷面積率為10%時之Vv值為2立方微米／平方微米至35立方微米／平方微米，例如2立方微米／平方微米、2.5立方微米／平方微米、3立方微米／平方微米、3.5立方微米／平方微米、4立方微米／平方微米、4.5立方微米／平方微米、5立方微米／平方微米、5.5立方微米／平方微米、6立方微米／平方微米、6.5立方微米／平方微米、7立方微米／平方微米、7.5立方微米／平方微米、8立方微米／平方微米、8.5立方微米／平方微米、9立方微米／平方微米、9.5立方微米／平方微米、10立方微米／平方微米、10.5立方微米／平方微米、11立方微米／平方微米、11.5立方微米／平方微米、12立方微米／平方微米、12.5立方微米／平方微米、13立方微米／平方微米、13.5立方微米／平方微米、14立方微米／平方微米、14.5立方微米／平方微米、15立方微米／平方微米、15.5立方微米／平方微米、16立方微米／平方微米、16.5立方微米／平方微米、17立方微米／平方微米、17.5立方微米／平方微米、18立方微米／平方微米、18.5立方微米／平方微米、19立方微米／平方微米、19.5立方微米／平方微米、20立方微米／平方微米、20.5立方微米／平方微米、21立方微米／平方微米、21.5立方微米／平方微米、22立方微米／平方微米、22.5立方微米／平方微米、23立方微米／平方微米、23.5立方微米／平方微米、24立方微米／平方微米、24.5立方微米／平方微米、25立方微米／平方微米、25.5立方微米／平方微米、26立方微米／平方微米、26.5立方微米／平方微米、27立方微米／平方微米、27.5立方微米／平方微米、28立方微米／平方微米、28.5立方微米／平方微米、29立方微米／平方微米、29.5立方微米／平方微米、30立方微米／平方微米、30.5立方微米／平方微米、31立方微米／平方微米、31.5立方微米／平方微米、32立方微米／平方微米、32.5立方微米／平方微米、33立方微米／平方微米、33.5立方微米／平方微米、34立方微米／平方微米、34.5立方微米／平方微米、或35立方微米／平方微米，或介於由上述任二數值所構成之範圍內。In addition, the smaller the Vv value is, the shallower the grooves on the surface of the polymer film are, and it is easy to make the air between the polymer film and the glass sheet not easily exhausted completely and not easy to be fully bonded. In view of this, in order for the laminated glass to have no residual bubbles and no edge debonding defects, the first surface of the polymer film of the present invention preferably has a Vv value within a specific range. In some embodiments of the present invention, the Vv value of the first surface of the polymer film at a loading area ratio of 10% is 2 μm/μm to 35 μm/μm, such as 2 μm/μm , 2.5 cubic micrometers/square micrometer, 3 cubic micrometers/square micrometer, 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 microns/microns, 6.5 microns/microns, 7 microns/microns, 7.5 microns/microns, 8 microns/microns, 8.5 microns/microns, 9 microns/microns, 9.5 Cubic microns/micron square, 10 cubic microns/micron square, 10.5 microns/microns, 11 microns/microns, 11.5 microns/microns, 12 microns/microns, 12.5 microns/microns, 13 cubic microns/microns, 13.5 microns/microns, 14 microns/microns, 14.5 microns/microns, 15 microns/microns, 15.5 microns/microns, 16 microns/microns, 16.5 microns /square micrometer, 17 cubic micrometer/square micrometer, 17.5 cubic micrometer/square micrometer, 18 cubic micrometer/square micrometer, 18.5 cubic micrometer/square micrometer, 19 cubic micrometer/square micrometer, 19.5 cubic micrometer/square micrometer, 20 cubic micrometer/ square microns, 20.5 cubic microns/square microns, 21 cubic microns/square microns, 21.5 cubic microns/square microns, 22 cubic microns/square microns, 22.5 cubic microns/square microns, 23 cubic microns/square microns, 23.5 cubic microns/square microns microns, 24 microns/microns, 24.5 microns/microns, 25 microns/microns, 25.5 microns/microns, 26 microns/microns, 26.5 microns/microns, 27 microns/microns , 27.5 cubic micrometers/square micrometer, 28 cubic micrometers/square micrometer, 28.5 cubic micrometers/square micrometer, 29 cubic micrometers/square micrometer, 29.5 cubic micrometers/square micrometer, 30 cubic micrometers/square micrometer, 30.5 cubic micrometers/square micrometer, 31 microns/microns, 31.5 microns/microns, 32 microns/microns, 32.5 microns/microns, 33 microns/microns, 33.5 microns/microns, 34 microns/microns, 34.5 Cubic micrometers/square micrometers, or 35 cubic micrometers/square micrometers, or within the range formed by any two of the above-mentioned values.
於本發明之較佳實施態樣中，聚合物膜的第二表面在負荷面積率為10%時之Vv值標準差亦為0.5立方微米／平方微米至2.5立方微米／平方微米。此外，聚合物的第二表面在負荷面積率為10%時之Vv值可為2立方微米／平方微米至35立方微米／平方微米。有關第二表面的Vv值的具體數值例示可參照第一表面的相關敘述，於此不再贅述。In a preferred embodiment of the present invention, the standard deviation of the Vv value of the second surface of the polymer film when the loading area ratio is 10% is also 0.5 cubic micrometers/square micrometer to 2.5 cubic micrometers/square micrometer. In addition, the Vv value of the second surface of the polymer at a loading area ratio of 10% may be 2 to 35 cubic micrometers/square micrometer. For specific numerical examples of the Vv value of the second surface, reference may be made to the relevant description of the first surface, and details are not repeated here.
1.2.2. Rz1.2.2. Rz 值value
於本發明之部分實施態樣中，聚合物膜的第一表面具有15微米至55微米的Rz值，例如15微米、16微米、17微米、18微米、19微米、20微米、21微米、22微米、23微米、24微米、25微米、26微米、27微米、28微米、29微米、30微米、31微米、32微米、33微米、34微米、35微米、36微米、37微米、38微米、39微米、40微米、41微米、42微米、43微米、44微米、45微米、46微米、47微米、48微米、49微米、50微米、51微米、52微米、53微米、54微米、或55微米，或介於由上述任二數值所構成之範圍內。所述Rz值係依據JIS B 0601(1994)測量而得。In some embodiments of the present invention, the first surface of the polymer film has an Rz value of 15 microns to 55 microns, such as 15 microns, 16 microns, 17 microns, 18 microns, 19 microns, 20 microns, 21 microns, 22 microns 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, 54 microns, or 55 microns micrometers, or within the range formed by any two of the above-mentioned numerical values. The Rz value is measured according to JIS B 0601 (1994).
於本發明之較佳實施態樣中，聚合物膜的第二表面較佳亦具有15微米至55微米的Rz值。有關第二表面的Rz值的具體數值例示可參照第一表面的相關敘述。In a preferred embodiment of the present invention, the second surface of the polymer film preferably also has an Rz value of 15 to 55 microns. For specific numerical examples of the Rz value of the second surface, reference may be made to the relevant description of the first surface.
1.2.3.1.2.3. 玻璃轉移溫度（glass transition temperature ( TgTg ）)
於本發明之部分實施態樣中，聚合物膜的玻璃轉移溫度（Tg）可控制在10°C至22°C，例如10°C、11°C、12°C、13°C、14°C、15°C、16°C、17°C、18°C、19°C、20°C、21°C、或22°C，或介於由上述任二數值所構成之範圍內。若聚合物膜的Tg高於指定範圍，則聚合物膜相對較硬，實施機械押花時可能不易形成所欲紋路。若聚合物膜的Tg低於指定範圍，則聚合物膜相對較軟，實施機械押花時聚合物膜可能容易破裂。於本發明之較佳實施態樣中，聚合物膜的Tg為12°C至15°C。In some embodiments of the present invention, the glass transition temperature (Tg) of the polymer film can be controlled at 10°C to 22°C, such as 10°C, 11°C, 12°C, 13°C, 14°C C, 15°C, 16°C, 17°C, 18°C, 19°C, 20°C, 21°C, or 22°C, or within a range consisting of any two of the above values. If the Tg of the polymer film is higher than the specified range, the polymer film is relatively hard, and it may not be easy to form desired textures when performing mechanical embossing. If the Tg of the polymer film is lower than the specified range, the polymer film is relatively soft, and the polymer film may be easily broken when mechanical embossing is performed. In a preferred embodiment of the present invention, the Tg of the polymer film is 12°C to 15°C.
1.2.4.1.2.4. 厚度thickness
在符合所指定之Vv值標準差之條件下，本發明聚合物膜的厚度可視實際需要而調整。一般而言，聚合物膜的厚度可為0.1毫米至2.5毫米，例如0.1毫米、0.15毫米、0.2毫米、0.25毫米、0.3毫米、0.35毫米、0.4毫米、0.45毫米、0.5毫米、0.55毫米、0.6毫米、0.65毫米、0.7毫米、0.75毫米、0.8毫米、0.85毫米、0.9毫米、0.95毫米、1.0毫米、1.05毫米、1.1毫米、1.15毫米、1.2毫米、1.25毫米、1.3毫米、1.35毫米、1.4毫米、1.45毫米、1.5毫米、1.55毫米、1.6毫米、1.65毫米、1.7毫米、1.75毫米、1.8毫米、1.85毫米、1.9毫米、1.95毫米、2.0毫米、2.05毫米、2.1毫米、2.15毫米、2.2毫米、2.25毫米、2.3毫米、2.35毫米、2.4毫米、2.45毫米、或2.5毫米，或介於由上述任二數值所構成之範圍內。於後附實施例中，聚合物膜的厚度為0.38毫米、0.76毫米、或1.52毫米。The thickness of the polymer film of the present invention can be adjusted according to actual needs under the condition that the standard deviation of the specified Vv value is met. In general, the thickness of the polymer film may be from 0.1 mm to 2.5 mm, such as 0.1 mm, 0.15 mm, 0.2 mm, 0.25 mm, 0.3 mm, 0.35 mm, 0.4 mm, 0.45 mm, 0.5 mm, 0.55 mm, 0.6 mm , 0.65 mm, 0.7 mm, 0.75 mm, 0.8 mm, 0.85 mm, 0.9 mm, 0.95 mm, 1.0 mm, 1.05 mm, 1.1 mm, 1.15 mm, 1.2 mm, 1.25 mm, 1.3 mm, 1.35 mm, 1.4 mm, 1.45 mm mm, 1.5 mm, 1.55 mm, 1.6 mm, 1.65 mm, 1.7 mm, 1.75 mm, 1.8 mm, 1.85 mm, 1.9 mm, 1.95 mm, 2.0 mm, 2.05 mm, 2.1 mm, 2.15 mm, 2.2 mm, 2.25 mm, 2.3 mm, 2.35 mm, 2.4 mm, 2.45 mm, or 2.5 mm, or within the range of any two values above. In the accompanying examples, the thickness of the polymer film is 0.38 mm, 0.76 mm, or 1.52 mm.
本發明之聚合物膜並不限於如前所述之厚度均等的膜。本發明聚合物膜亦可為二端厚度不同的楔形膜，所述楔形膜通常用於製備車用抬頭顯示器（head-up display，HUD），因此，於本文中，二端厚度不同的楔形膜亦被稱為「HUD膜」。於本發明之部分實施態樣中，HUD膜的薄端的厚度可為0.5至1毫米，例如0.5毫米、0.55毫米、0.6毫米、0.65毫米、0.7毫米、0.75毫米、0.8毫米、0.85毫米、0.9毫米、0.95毫米、或1毫米，或介於由上述任二數值所構成之範圍內。於本發明之部分實施態樣中，HUD膜的厚端的厚度可為1.2毫米至1.7毫米，例如1.2毫米、1.25毫米、1.3毫米、1.35毫米、1.4毫米、1.45毫米、1.5毫米、1.55毫米、1.6毫米、1.65毫米、或1.7毫米，或介於由上述任二數值所構成之範圍內。於後附實施例中，HUD膜的薄端的厚度為0.76毫米且厚端的厚度為1.45毫米，且HUD膜的寬度為1210毫米。The polymer film of the present invention is not limited to the film of uniform thickness as described above. The polymer film of the present invention can also be a wedge-shaped film with different thicknesses at the two ends. The wedge-shaped film is usually used to prepare a head-up display (HUD) for vehicles. Therefore, in this paper, the wedge-shaped film with different thicknesses at the two ends is used. Also known as "HUD film". In some embodiments of the present invention, the thickness of the thin end of the HUD film may be 0.5 to 1 mm, such as 0.5 mm, 0.55 mm, 0.6 mm, 0.65 mm, 0.7 mm, 0.75 mm, 0.8 mm, 0.85 mm, 0.9 mm , 0.95 mm, or 1 mm, or within the range consisting of any two of the above values. In some embodiments of the present invention, the thickness of the thick end of the HUD film may be 1.2 mm to 1.7 mm, such as 1.2 mm, 1.25 mm, 1.3 mm, 1.35 mm, 1.4 mm, 1.45 mm, 1.5 mm, 1.55 mm, 1.6 mm mm, 1.65 mm, or 1.7 mm, or within the range of any two of the above. In the following examples, the thickness of the thin end of the HUD film is 0.76 mm and the thickness of the thick end is 1.45 mm, and the width of the HUD film is 1210 mm.
1.3.1.3. 聚合物膜之製備Preparation of polymer films
本發明聚合物膜之製備方式並無特殊限制，例如可將聚乙烯醇縮醛與選用成分（如塑化劑）混合捏揉而得到一聚合物膜組合物，再利用習知薄膜製備方法將聚合物膜組合物成膜，並進行機械押花，以利於聚合物膜表面提供所欲之Vv值標準差、Vv值、及Rz值。所述薄膜製備方法的實例包括但不限於壓延法、流延法、擠出拉幅法、直接擠出法、及擠出吹塑法。The preparation method of the polymer film of the present invention is not particularly limited. For example, polyvinyl acetal can be mixed and kneaded with selected components (such as plasticizers) to obtain a polymer film composition. The polymer film composition is formed into a film and subjected to mechanical embossing, so as to provide desired standard deviation of Vv value, Vv value, and Rz value on the surface of the polymer film. Examples of such film production methods include, but are not limited to, calendering, casting, extrusion tentering, direct extrusion, and extrusion blow molding.
於本發明之部分實施態樣中，係以如下方式製備聚合物膜，但本發明並不以此為限：使用混合機將樹脂態之聚乙烯醇縮醛與塑化劑在100°C至150°C之溫度及10 rpm至50 rpm之轉速下混合，並捏揉5分鐘至30分鐘而得到聚合物膜組合物。待聚合物膜組合物冷卻至室溫後，將聚合物膜組合物置於擠出機中擠出成膜。視需要重複上述成膜步驟並調整聚合物膜組合物之組成以提供不同功能之膜，並層合各膜可形成具多層結構之聚合物膜。In some embodiments of the present invention, the polymer film is prepared in the following manner, but the present invention is not limited thereto: use a mixer to mix the resinous polyvinyl acetal and plasticizer at a temperature of 100° C. to Mixing at a temperature of 150° C. and a rotational speed of 10 rpm to 50 rpm, and kneading for 5 minutes to 30 minutes to obtain a polymer film composition. After the polymer film composition is cooled to room temperature, the polymer film composition is placed in an extruder and extruded to form a film. The above-mentioned film forming steps are repeated as necessary and the composition of the polymer film composition is adjusted to provide films with different functions, and lamination of each film can form a polymer film with a multi-layer structure.
聚合物膜後續再透過預熱及機械押花即可提供所欲之Vv值標準差、Vv值、及Rz值，其中可藉由調整上下押花輪的角度以使得所押出的聚合物膜成楔形，以製作HUD膜。機械押花係指利用滾輪在成形後的聚合物膜的表面製造紋路。機械押花的方法包括但不限於押花輪法及壓延輪法，其中押花輪法係較佳的。機械押花的紋路樣式並無特殊限制，例如包括菱形、線形、鋸齒形、正方形、錐形、圓形、近似圓形、及不規則形。前述各紋路樣式係可單獨採用，亦可同時採用多種。The polymer film can then be preheated and mechanically pressed to provide the desired Vv value standard deviation, Vv value, and Rz value. The extruded polymer film can be wedge-shaped by adjusting the angle of the upper and lower pressing wheels. to make HUD film. Mechanical embossing refers to the use of rollers to create textures on the surface of the formed polymer film. The methods of mechanically pressing flowers include, but are not limited to, the pressing flower wheel method and the calendering round method, among which the pressing flower wheel method is preferred. The grain pattern of the mechanical embossing is not particularly limited, for example, it includes rhombus, linear, zigzag, square, cone, circle, approximate circle, and irregular shape. Each of the aforementioned texture patterns can be used individually, or a plurality of them can be used simultaneously.
預熱及機械押花條件依照所使用之聚合物膜的組成不同而適應性調整。一般而言，預熱輪溫度可為45°C至82°C，特定言之為58°C至75°C，更特定言之為60°C至75°C。押花輪溫度可為80°C至150°C，特定言之為90°C至140°C，更特定言之為110°C至130°C。押花輪扭力可為0.3 N·m（牛頓．公尺）至1.8 N·m，特定言之為0.75 N·m至1.55 N·m，更特定言之為0.8 N·m至1.5 N·m。押花輪壓力可為2 kg/cm 2（公斤／平方公分）至50 kg/cm 2，特定言之為10 kg/cm 2至40 kg/cm 2，更特定言之為15 kg/cm 2至25 kg/cm 2。 The preheating and mechanical embossing conditions are adapted according to the composition of the polymer film used. In general, the preheat wheel temperature may be 45°C to 82°C, specifically 58°C to 75°C, and more specifically 60°C to 75°C. The extrusion wheel temperature may be 80°C to 150°C, specifically 90°C to 140°C, and more specifically 110°C to 130°C. The torque of the pressing wheel can be 0.3 N·m (Newton·m) to 1.8 N·m, specifically 0.75 N·m to 1.55 N·m, and more specifically 0.8 N·m to 1.5 N·m. The pressing wheel pressure can be 2 kg/cm 2 (kg/cm 2 ) to 50 kg/cm 2 , specifically 10 kg/cm 2 to 40 kg/cm 2 , more specifically 15 kg/cm 2 to 25 kg/cm 2 .
針對聚合物膜之Vv性質，研究發現可透過押花輪扭力或預熱輪溫度來調整Vv值與Vv值標準差。押花輪扭力越大，聚合物膜的Vv值標準差越大，且Vv值越大。預熱輪溫度越高，聚合物膜的Vv值標準差越小。Regarding the Vv property of the polymer film, the research found that the Vv value and the standard deviation of the Vv value can be adjusted by the torque of the extrusion wheel or the temperature of the preheating wheel. The greater the torque of the extrusion wheel, the greater the standard deviation of the Vv value of the polymer film, and the greater the Vv value. The higher the preheat wheel temperature, the smaller the standard deviation of the Vv value of the polymer film.
2.2. 夾層玻璃Laminated glass
本發明之聚合物膜可用於製備夾層玻璃。因此，本發明亦提供一種夾層玻璃，其包含第一玻璃片、第二玻璃片、以及位於該第一玻璃片與第二玻璃片之間之中間膜，該中間膜係由如上所述之聚合物膜所提供。The polymer film of the present invention can be used to prepare laminated glass. Therefore, the present invention also provides a laminated glass comprising a first glass sheet, a second glass sheet, and an intermediate film between the first glass sheet and the second glass sheet, and the intermediate film is polymerized as described above provided by the film.
第一玻璃片與第二玻璃片可相同或不同，且可為任何習用於製備夾層玻璃的玻璃片，例如浮法玻璃（float glass）、強化玻璃、夾絲玻璃、或普通平板玻璃，但本發明並不限於此。於後附實施例中，係使用浮法玻璃作為第一玻璃片與第二玻璃片。The first glass sheet and the second glass sheet may be the same or different, and may be any glass sheet conventionally used to make laminated glass, such as float glass, tempered glass, wired glass, or ordinary flat glass, but this The invention is not limited to this. In the following examples, float glass is used as the first glass sheet and the second glass sheet.
本發明之夾層玻璃可藉由相關技術領域中習知的夾層玻璃製備方法而製得。舉例言之，可以如下方式進行夾層玻璃之製備：將聚合物膜夾置於二玻璃片之間以得到一積層物，將積層物放入真空袋中並在20°C至30°C之溫度下抽真空（真空度＞500毫米汞柱（mmHg））至少10分鐘，接著將裝有積層物之真空袋放入加熱爐中，從60°C緩慢升溫至130°C，至少歷時30分鐘之後，將真空袋從加熱爐中取出，完成預壓合。接著將預壓合後之積層物置於高壓釜中，於高溫高壓條件下熱壓100分鐘至150分鐘，製得夾層玻璃。一般而言，所述高溫高壓條件可為10巴至15巴之壓力及100°C至150°C之溫度。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 production of laminated glass can be carried out by sandwiching a polymer film between two glass sheets to obtain a laminate, placing the laminate in a vacuum bag and placing the laminate at a temperature of 20°C to 30°C Under vacuum (vacuum degree > 500 millimeters of mercury (mmHg)) for at least 10 minutes, then put the vacuum bag containing the laminate into the heating furnace, and slowly raise the temperature from 60°C to 130°C for at least 30 minutes , take out the vacuum bag from the heating furnace to complete the pre-pressing. Then, the pre-pressed 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. In general, the high temperature and high pressure conditions may be a pressure of 10 bar to 15 bar and a temperature of 100°C to 150°C.
3.3. 實施例Example
3.1.3.1. 測量方式說明Description of measurement method
茲以下列具體實施態樣進一步例示說明本發明，其中，所採用之測量儀器及方法分別如下：The present invention is further illustrated and described by the following specific implementation aspects, wherein the measuring instruments and methods adopted are as follows:
[聚乙烯醇縮醛之分子量的測量][Measurement of molecular weight of polyvinyl acetal]
利用膠體滲透層析法（gel permeation chromatography，GPC）來測量聚乙烯醇縮醛之分子量分布，其中係將聚乙烯醇縮醛溶解於四氫呋喃（tetrahydrofuran，THF）中，在以下條件下進行GPC分析，並以對應聚苯乙烯標準品（Waters PS STD）面積的比率計算其分子量。 裝置：Waters 1515 PUMP system 探測器：Waters 2414 RI 沖提條件：1.0毫升／分鐘（mL/min），THF 管柱：Waters Styragel HR5 THF、Waters Styragel HR4 THF、Waters Styragel HR3 THF、Waters Styragel HR1 THF The molecular weight distribution of polyvinyl acetal was measured by gel permeation chromatography (GPC), wherein polyvinyl acetal was dissolved in tetrahydrofuran (THF), and GPC analysis was performed under the following conditions: The molecular weight was calculated as the ratio of the area corresponding to the polystyrene standard (Waters PS STD). Device: Waters 1515 PUMP system Detector: Waters 2414 RI Elution conditions: 1.0 milliliters per minute (mL/min), THF Columns: Waters Styragel HR5 THF, Waters Styragel HR4 THF, Waters Styragel HR3 THF, Waters Styragel HR1 THF
[聚乙烯醇縮醛之縮醛度的測量][Measurement of acetal degree of polyvinyl acetal]
聚乙烯醇縮醛的縮醛度係依據JIS K6728所測得。The acetal degree of polyvinyl acetal is measured according to JIS K6728.
[聚乙烯醇縮醛之乙醯度的測量][Measurement of Acetyl Degree of Polyvinyl Acetal]
聚乙烯醇縮醛的乙醯度係依據JIS K6728所測得。The acetal degree of polyvinyl acetal is measured according to JIS K6728.
[聚乙烯醇縮醛之羥基含量的測量][Measurement of hydroxyl content of polyvinyl acetal]
聚乙烯醇縮醛的羥基含量係依據JIS K6728所測得。The hydroxyl content of polyvinyl acetal is measured according to JIS K6728.
[玻璃轉移溫度（Tg）之測量][Measurement of glass transition temperature (Tg)]
利用差示掃描量熱儀（型號：TA DSC 25，購自TA儀器（TA Instruments））在氮氣氛圍下測量聚合物膜之Tg。首先，取7毫克之聚合物膜作為樣品放入差示掃描量熱儀的樣品載台上，以10°C／分鐘之升溫速率升溫至150°C後在該溫度下保持5分鐘。接著，使樣品在-50°C平衡並在該溫度下保持5分鐘，接著，以10°C／分鐘之升溫速率升溫至100°C而得到溫度對熱流（heat flow）之曲線圖（X軸為溫度，Y軸為熱流），並將玻璃轉化中點（midpoint）所對應的溫度記錄為Tg。The Tg of the polymer film was measured using a differential scanning calorimeter (model: TA DSC 25, available from TA Instruments) under a nitrogen atmosphere. First, 7 mg of the polymer film was taken as a sample and placed on the sample stage of the differential scanning calorimeter, heated to 150°C at a heating rate of 10°C/min, and then kept at this temperature for 5 minutes. Next, the sample was equilibrated at -50°C and held at this temperature for 5 minutes, then heated to 100°C at a ramp 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.
[氣泡殘留測試][Bubble Residue Test]
將夾層玻璃裁切成30公分×30公分的測試樣品。將測試樣品以垂直置放之方式放入120°C之烘箱中14天，以肉眼觀察測試樣品是否有氣泡殘留，其中所述氣泡係指在夾層玻璃邊緣部存在於玻璃與聚合物膜之間且未與外部空氣接觸之氣泡。評估標準如下：若測試樣品無氣泡殘留，紀錄為「◎」，代表氣泡測試結果極佳；若測試樣品中有直徑小於0.5毫米的氣泡殘留且氣泡數量為一顆，紀錄為「○」，代表氣泡測試結果良好；以及若測試樣品中有直徑小於0.5毫米的氣泡殘留且氣泡數量為二顆以上，或者有直徑0.5毫米以上的氣泡殘留，紀錄為「×」，代表氣泡測試結果不佳。Cut the laminated glass into 30cm x 30cm test samples. Put the test sample in an oven at 120°C in a vertical position for 14 days, and visually observe whether the test sample has air bubbles remaining, wherein the air bubbles refer to the existence of bubbles between the glass and the polymer film at the edge of the laminated glass Air bubbles that are not in contact with the outside air. The evaluation criteria are as follows: if the test sample has no residual bubbles, it is recorded as "◎", which means that the bubble test results are excellent; if the test sample has residual bubbles with a diameter of less than 0.5 mm and the number of bubbles is one, it is recorded as "○", which means The result of the bubble test is good; and if the test sample has residual bubbles with a diameter of less than 0.5 mm and the number of bubbles is two or more, or if there are residual bubbles with a diameter of more than 0.5 mm, the record is “×”, which means that the bubble test result is not good.
[空隙體積（Vv）之測量及Vv值標準差之計算][Measurement of void volume (Vv) and calculation of standard deviation of Vv value]
首先，將聚合物膜裁切成3公分×3公分的測試樣品。在24±3°C之溫度與63±3%之相對溼度下，根據ISO 25178-2:2012之規範，利用雷射掃描共軛焦顯微鏡（laser scanning confocal microscope）（型號：LEXT OLS5000-SAF，購自奧林巴斯（Olympus））來測量聚合物膜在10%負荷面積率時之空隙體積（Vv）值。Vv值的測量條件如下：光源具有405奈米之波長，接物鏡倍率為100倍（MPLAPON-100xLEXT），光學變焦（optical zoom）為50倍，圖像面積為1500微米×1500微米，解析度為1024像素×1024像素，操作條件設定為自動傾斜去除（auto tilt removal），不使用濾光片。於所得到之負荷面積曲線圖中，可獲得在10%至80%負荷面積率時的核心部空隙體積（Vvc）值以及在80%負荷面積率時的波谷部空隙體積（Vvv）值，空隙體積（Vv）值即為波谷部空隙體積（Vvv）的值與核心部空隙體積（Vvc）的值之總和。空隙體積（Vv）值的單位為立方微米／平方微米。於後附實施例中，是基於五個Vv值進行平均計算而得到Vv值。取樣方式如圖1所示，取一片30公分×30公分的聚合物膜，在聚合物膜的四個角距離邊緣各1公分處裁切3公分×3公分的測試樣品，以及在聚合物膜的中心處裁切3公分×3公分的測試樣品，獲得共五個測試樣品。First, the polymer film was cut into 3 cm x 3 cm test samples. Under the temperature of 24±3°C and the relative humidity of 63±3%, according to the specification of ISO 25178-2:2012, using a laser scanning confocal microscope (model: LEXT OLS5000-SAF, Available from Olympus) to measure the void volume (Vv) value of the polymer film at 10% area loading. The measurement conditions for the Vv value are as follows: the light source has a wavelength of 405 nm, the objective lens magnification is 100 times (MPLAPON-100xLEXT), the optical zoom is 50 times, the image area is 1500 μm × 1500 μm, and the resolution is 1024 pixels x 1024 pixels, the operating conditions are set to auto tilt removal, and no filter is used. From the obtained load area curve graph, the core void volume (Vvc) value at 10% to 80% load area rate and the valley void volume (Vvv) value at 80% load area rate can be obtained. The volume (Vv) value is the sum of the value of the void volume (Vvv) at the trough and the value of the void volume at the core (Vvc). The void volume (Vv) values are in cubic micrometers per square micrometer. In the following examples, the Vv value is obtained by performing an average calculation based on five Vv values. The sampling method is shown in Figure 1. Take a piece of polymer film of 30 cm × 30 cm, cut a test sample of 3 cm × 3 cm at the four corners of the polymer film and 1 cm from the edge, and cut a test sample of 3 cm × 3 cm on the polymer film. Cut a test sample of 3 cm × 3 cm at the center of the tester to obtain a total of five test samples.
此外，對五個Vv值進行標準差計算，得到Vv值標準差。In addition, the standard deviation calculation was performed on the five Vv values to obtain the standard deviation of the Vv values.
[表面粗糙度Rz值之測量][Measurement of surface roughness Rz value]
聚合物膜的表面粗糙度Rz值係利用粗糙度測試儀（型號：SE 300，購自小坂研究所（Kosaka Laboratory Ltd.））並根據JIS B 0601（1994）測量而得。首先，將聚合物膜裁切為8公分×30公分之大小作為測試樣品。測量條件係設定如下：垂直放大率（vertical magnification）設定為自動，水平放大率（horizontal magnification）設定為25毫米／λc，截止（cut off）距離設定為2.5毫米（即，每2.5毫米計算一次），評估長度為截止距離之七倍，且基準長度係設定為17.5毫米，測量方向為機械方向（machine direction）。The surface roughness Rz value of the polymer film was measured according to JIS B 0601 (1994) using a roughness tester (model: SE 300, available from Kosaka Laboratory Ltd.). First, the polymer film was cut into a size of 8 cm×30 cm as a test sample. The measurement conditions are set as follows: vertical magnification is set to auto, horizontal magnification is set to 25 mm/λc, and cut off distance is set to 2.5 mm (ie, calculated every 2.5 mm) , 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.
[光學變形的評價][Evaluation of Optical Distortion]
首先，準備30公分×30公分的夾層玻璃作為測試樣品，並準備投影機、樣品支架、及白色屏幕。將投影機、樣品支架及白色屏幕放到暗室中，其中樣品支架係置於投影機與白色屏幕之間，投影機與樣品支架之間的距離以及樣品支架與白色屏幕之間的距離均為1.5 公尺。將測試樣品安置到樣品支架上，並調整角度使得測試樣品相對於垂直地面之軸朝投影機傾斜15度。開啟投影機光源，使光線通過測試樣品而投射到白色屏幕上。觀察白色屏幕是否有顯著的明暗度區別（即，連續的明暗條紋），若無，表示夾層玻璃中不存在細絲狀條紋（光波紋），紀錄為「無」；若有，表示夾層玻璃中存在有細絲狀條紋（光波紋），紀錄為「有」。First, prepare a 30cm x 30cm laminated glass as a test sample, and prepare a projector, a sample holder, and a white screen. Place the projector, sample holder and white screen in the dark room, where the sample holder is placed between the projector and the white screen, and the distance between the projector and the sample holder and the distance between the sample holder and the white screen are both 1.5 meter. Place the test sample on the sample holder and adjust the angle so that the test sample is inclined 15 degrees toward the projector relative to the axis vertical to the ground. Turn on the projector light source so that light passes through the test sample and onto the white screen. Observe whether there is a significant difference between light and dark (ie, continuous light and dark stripes) on the white screen. If not, it means that there are no filamentous stripes (light ripples) in the laminated glass, and the record is "None"; The presence of filamentous streaks (light ripples) is recorded as "yes".
[光穿透率測量][Light transmittance measurement]
夾層玻璃之光穿透率的分析係根據ASTM D1003來進行。首先，取二片長度6公分×寬度6公分×厚度3毫米的平板玻璃片，以水清洗並吹乾。將二片玻璃片對貼，利用霧度計（型號：NDH2000 Haze meter，購自日本電色（Nippon Denshoku））來測定二片玻璃片的光穿透率。接著，將聚合物膜置於二片玻璃片之間，以熱壓機在150°C及2 kg/cm 2至3 kg/cm 2的壓力下熱壓2至3分鐘而得到夾層玻璃，再以酒精清潔玻璃的表面。之後，利用霧度計來測定夾層玻璃的光穿透率。 The analysis of the light transmittance of the laminated glass was carried out according to ASTM D1003. First, take two pieces of flat glass with a length of 6 cm x a width of 6 cm x a thickness of 3 mm, rinse with water and blow dry. Two pieces of glass sheets were put together, and a haze meter (model: NDH2000 Haze meter, purchased from Nippon Denshoku) was used to measure the light transmittance of the two pieces of glass sheets. Next, the polymer film is placed between two glass sheets, and the laminated glass is obtained by hot pressing for 2 to 3 minutes at 150° C. and a pressure of 2 kg/cm 2 to 3 kg/cm 2 with a hot press. Clean the surface of the glass with alcohol. After that, the light transmittance of the laminated glass was measured with a haze meter.
[眩光評價][Glare Evaluation]
將聚合物膜裁切成50公分×50公分的測試樣品後，將測試樣品放置在60公分×60公分×厚度2毫米的玻璃片上。於玻璃片下方30公分處放置白熾燈。讓10位測試人員在測試樣品上方100公分處以肉眼直視膜片，並紀錄測試人員的眼睛是否感到不適。評價標準如下：若眼睛感到不適的測試人員人數為0至3人，表示眩光評價良好，紀錄為「A」；若眼睛感到不適的測試人員人數為4至6人，表示眩光評價普通，紀錄為「B」；若眼睛感到不適的測試人員人數為7至10人，表示眩光評價不良，紀錄為「C」。After cutting the polymer film into test samples of 50 cm x 50 cm, the test samples were placed on a glass sheet of 60 cm x 60 cm x thickness of 2 mm. Place an incandescent lamp 30 cm below the glass sheet. Let 10 testers look directly at the diaphragm 100 cm above the test sample, and record whether the tester's eyes feel discomfort. The evaluation criteria are as follows: if the number of testers with eye discomfort is 0 to 3, the glare evaluation is good, and the record is "A"; if the number of testers with eye discomfort is 4 to 6, the glare evaluation is average, and the record is "B"; if the number of testers with eye discomfort is 7 to 10, it indicates that the glare evaluation is poor, and the record is "C".
[敲擊黏附力值的測試（pummel adhesion test）][Pummel adhesion test]
準備三片30公分×15公分的夾層玻璃，並將夾層玻璃在-20°C下放置2小時。接著，在20°C至25°C的溫度下將夾層玻璃放在用於敲擊黏附力測試的自動敲擊機上，以一磅重的鐵鎚從夾層玻璃的端部開始敲打，並以約12.7毫米之間隔在橫向上連續敲打至夾層玻璃的中央處。將敲擊過的夾層玻璃在室溫下放置30分鐘，之後與標準試片進行比較，依據敲擊過的夾層玻璃的聚合物膜的暴露程度來評價夾層玻璃，且評價結果以0至9之數值表示，數值為0表示聚合物膜的暴露程度為大於90%，數值為1表示聚合物膜的暴露程度為90%以下且大於80%，數值為2表示聚合物膜的暴露程度為80%以下且大於70%，數值為3表示聚合物膜的暴露程度為70%以下且大於60%，數值為4表示聚合物膜的暴露程度為60%以下且大於50%，數值為5表示聚合物膜的暴露程度為50%以下且大於40%，數值為6表示聚合物膜的暴露程度為40%以下且大於30%，數值為7表示聚合物膜的暴露程度為30%以下且大於20%，數值為8表示聚合物膜的暴露程度為20%以下且大於10%，數值為9表示聚合物膜的暴露程度為10%以下。若數值大於6，表示接著性過高，玻璃不易碎裂容易使人撞擊受傷，不適合作為車用夾層玻璃。若數值小於4，表示接著性過差，玻璃容易碎裂噴出，亦不適合作為車用夾層玻璃。若數值介於4至6之間，表示接著性適中，適合作為車用夾層玻璃。Prepare three pieces of 30 cm × 15 cm laminated glass, and place the laminated glass at -20°C for 2 hours. Next, place the laminated glass on an automatic tapping machine for tapping adhesion testing at a temperature of 20°C to 25°C, start tapping with a one-pound hammer from the end of the laminated glass, and tap The intervals of about 12.7 mm are continuously tapped to the center of the laminated glass in the transverse direction. The tapped laminated glass was placed at room temperature for 30 minutes, and then compared with the standard test piece, the laminated glass was evaluated according to the degree of exposure of the polymer film of the tapped laminated glass, and the evaluation result was based on a scale of 0 to 9. Numerical representation, a value of 0 indicates that the exposure degree of the polymer film is greater than 90%, a value of 1 indicates that the exposure degree of the polymer film is less than 90% and greater than 80%, and a value of 2 indicates that the exposure degree of the polymer film is 80% Below and greater than 70%, a value of 3 means the exposure of the polymer film is below 70% and greater than 60%, a value of 4 means the exposure of the polymer film is below 60% and greater than 50%, and a value of 5 means the polymer The exposure of the film is less than 50% and greater than 40%, a value of 6 indicates that the exposure of the polymer film is less than 40% and greater than 30%, and a value of 7 indicates that the exposure of the polymer film is less than 30% and greater than 20% , a value of 8 indicates that the exposure degree of the polymer film is less than 20% and greater than 10%, and a value of 9 indicates that the exposure degree of the polymer film is less than 10%. If the value is greater than 6, it means that the adhesiveness is too high, the glass is not easy to be broken, and it is easy to cause people to be injured. It is not suitable for laminated glass for vehicles. If the value is less than 4, it means that the adhesiveness is too poor, the glass is easily broken and sprayed, and it is not suitable for automotive laminated glass. If the value is between 4 and 6, it means that the adhesiveness is moderate, and it is suitable for automotive laminated glass.
3.2.3.2. 聚合物膜之製備及性質量測Preparation and quality measurement of polymer films
首先，將100重量份的聚（乙烯醇縮丁醛）（PVB，購自長春石油化學股份有限公司）與40重量份的塑化劑（三乙二醇雙（2-乙基己酸酯））混合而得到一混合物，使用混合機在120°C下以35 rpm之旋轉速度捏揉該混合物15分鐘之後，冷卻至室溫而得到一聚合物膜組合物。接著，將聚合物膜組合物置於擠出機中，擠出成聚合物膜。First, 100 parts by weight of poly(vinyl butyral) (PVB, purchased from Changchun Petrochemical Co., Ltd.) and 40 parts by weight of a plasticizer (triethylene glycol bis(2-ethylhexanoate) ) was mixed to obtain a mixture, and after kneading the mixture at a rotational speed of 35 rpm using a mixer for 15 minutes, it was cooled to room temperature to obtain a polymer film composition. Next, the polymer film composition is placed in an extruder and extruded into a polymer film.
根據表1-1及表1-2所示參數條件對聚合物膜的二表面進行預熱及機械押花，得到實施例1至11及比較實施例1至9之聚合物膜。除了表1-1及表1-2所示參數條件之外，聚合物膜通過押花輪之間的線速度為18 m/min。依照前文所載方法測量實施例1至11及比較實施例1至9所使用之PVB的分子量、縮醛度、乙醯度與羥基含量比，並將結果紀錄於表2-1至表2-2中。另外，依照前文測量方法測量實施例1至11及比較實施例1至9之聚合物膜的厚度、Tg、Vv、Vv標準差、與Rz，並將結果紀錄於表2-3至表2-4中。The two surfaces of the polymer film were preheated and mechanically embossed according to the parameter conditions shown in Table 1-1 and Table 1-2 to obtain the polymer films of Examples 1 to 11 and Comparative Examples 1 to 9. In addition to the parameter conditions shown in Table 1-1 and Table 1-2, the linear speed of the polymer film passing between the extrusion wheels was 18 m/min. The molecular weight, acetal degree, acetyl degree and hydroxyl content ratio of PVB used in Examples 1 to 11 and Comparative Examples 1 to 9 were measured according to the methods described above, and the results were recorded in Table 2-1 to Table 2- 2 in. In addition, the thickness, Tg, Vv, Vv standard deviation, and Rz of the polymer films of Examples 1 to 11 and Comparative Examples 1 to 9 were measured according to the aforementioned measurement methods, and the results were recorded in Tables 2-3 to 2- 4 in.
表1-1：實施例1至11的聚合物膜的機械押花參數條件
表1-2：比較實施例1至9的聚合物膜的機械押花參數條件
表2-1：實施例1至11的PVB的性質
表2-2：比較實施例1至9的PVB的性質
表2-3：實施例1至11的聚合物膜的性質
表2-4：比較實施例1至9的聚合物膜的性質
3.3.3.3. 夾層玻璃之製備及性質評估Preparation and property evaluation of laminated glass
分別使用實施例1至11及比較實施例1至9之聚合物膜來製備夾層玻璃。首先，準備二片潔淨的透明浮法玻璃片（長度為300毫米、寬度為300毫米、厚度為2至2.2毫米），接著，將實施例1至11及比較實施例1至9之聚合物膜分別夾在二片透明浮法玻璃片之間而得到一積層物，利用真空袋式方法對積層物進行抽真空，以進行預壓合。真空袋式的操作方式係如下所述：將積層物放入真空袋中並在20°C至30°C之溫度下抽真空（真空度＞500毫米汞柱（mmHg））至少10分鐘，接著將裝有積層物之真空袋放入加熱爐中，首先在20°C至30°C之溫度下維持10至20分鐘，再升溫至60°C至130°C並維持15至45分鐘，之後將真空袋從加熱爐中取出並在室溫下冷卻。冷卻後解開真空並取出積層物。將經預壓合之積層物置於高壓釜中以13巴之壓力及135°C之溫度熱壓120分鐘，接著冷卻至室溫，製得夾層玻璃。Laminated glasses were prepared using the polymer films of Examples 1 to 11 and Comparative Examples 1 to 9, respectively. First, prepare two clean transparent float glass sheets (300 mm in length, 300 mm in width, 2 to 2.2 mm in thickness), then, the polymer films of Examples 1 to 11 and Comparative Examples 1 to 9 were prepared A laminate is obtained by sandwiching two transparent float glass sheets respectively, and the laminate is evacuated by a vacuum bag method for pre-pressing. The vacuum bag operation method is as follows: The laminate is placed in a vacuum bag and evacuated (vacuum degree > 500 mmHg) at a temperature of 20°C to 30°C for at least 10 minutes, 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, then heat it up to 60°C to 130°C and maintain it for 15 to 45 minutes, then Remove the vacuum bag from the oven and cool at room temperature. After cooling, the vacuum was released and the stack was removed. The pre-pressed laminate was placed in an autoclave with a pressure of 13 bar and a temperature of 135° C. for hot pressing for 120 minutes, followed by cooling to room temperature to prepare a laminated glass.
依照前文所載方法，對實施例1至11及比較實施例1至9之夾層玻璃進行光學變形評價、光穿透率測量、眩光評價、敲擊黏附力值測試、與氣泡殘留測試，並將結果紀錄於表3-1及表3-2中。According to the methods set forth above, optical deformation evaluation, light transmittance measurement, glare evaluation, tap adhesion value test, and bubble residual test were performed on the laminated glass of Examples 1 to 11 and Comparative Examples 1 to 9, and the The results are recorded in Table 3-1 and Table 3-2.
表3-1：實施例1至11的夾層玻璃的性質
表3-2：比較實施例1至9的夾層玻璃的性質
如表3-1所示，由本發明聚合物膜所製得之夾層玻璃在光學變形評價、眩光評價、敲擊黏附力值測試與氣泡殘留測試中均獲得令人滿意的結果且同時具有至少87%的光穿透率。實施例1至11顯示，當聚合物膜表面的Vv值標準差在指定範圍內，所製得夾層玻璃均具備光學變形、無眩光、良好穿透率的優點。尤其，實施例1至10進一步顯示，當聚合物膜表面的Vv值標準差在指定範圍內，且Vv值及Rz值均在較佳範圍內時，所製得夾層玻璃在具備無光學變形、無眩光、良好穿透率的優點的情況下，更具有合宜的敲擊黏附力值，也無氣泡殘留。As shown in Table 3-1, the laminated glass made from the polymer film of the present invention all obtained satisfactory results in optical distortion evaluation, glare evaluation, tap adhesion value test and bubble residual test, and at the same time had at least 87 % light transmittance. Examples 1 to 11 show that when the standard deviation of the Vv value on the surface of the polymer film is within the specified range, the prepared laminated glass has the advantages of optical distortion, no glare, and good transmittance. In particular, Examples 1 to 10 further show that when the standard deviation of the Vv value on the surface of the polymer film is within the specified range, and both the Vv value and the Rz value are within the preferred range, the prepared laminated glass has no optical distortion, Under the advantages of no glare and good penetration, it has a more suitable tap adhesion value, and no bubbles remain.
相較於此，如表3-2所示，由不屬於本發明之聚合物膜所製得之夾層玻璃則無法同時具備無光學變形、無眩光、良好穿透率的優點。具體言之，比較實施例1至9顯示，若聚合物膜表面的Vv值標準差不在指定範圍內，即使Vv值及Rz值均在較佳範圍內，所製得夾層玻璃也無法同時具備無光學變形、無眩光、良好穿透率的優點。In contrast, as shown in Table 3-2, the laminated glass made from the polymer film not belonging to the present invention cannot simultaneously have the advantages of no optical distortion, no glare, and good transmittance. Specifically, Comparative Examples 1 to 9 show that if the standard deviation of the Vv value on the surface of the polymer film is not within the specified range, even if the Vv value and the Rz value are both within the preferred range, the obtained laminated glass cannot have both The advantages of optical distortion, no glare, good transmittance.
上述實施例僅為例示性說明本發明之原理及其功效，並闡述本發明之技術特徵，而非用於限制本發明之保護範疇。任何熟悉本技術者在不違背本發明之技術原理及精神下，可輕易完成之改變或安排，均屬本發明所主張之範圍。因此，本發明之權利保護範圍係如後附申請專利範圍所列。The above-mentioned embodiments are only used to illustrate the principles and effects of the present invention, and to illustrate the technical characteristics of the present invention, but are not intended to limit the protection scope of the present invention. Any changes or arrangements that can be easily accomplished by those skilled in the art without departing from the technical principles and spirit of the present invention are within the scope of the present invention. Therefore, the protection scope of the present invention is as listed in the appended patent application scope.
無none
圖1係本發明之「空隙體積（Vv）值的標準差」之測試取樣示意圖。Fig. 1 is a schematic diagram of the test sampling of "standard deviation of void volume (Vv) value" of the present invention.
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| TW202120604A (en) * | 2019-11-29 | 2021-06-01 | 長春石油化學股份有限公司 | Polymer film and uses of the same |
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| US20200255628A1 (en) * | 2015-04-22 | 2020-08-13 | Ineos Styrolution Group Gmbh | Translucent fibre composite materials comprising chemically modified polymers |
| TW201934697A (en) * | 2018-02-20 | 2019-09-01 | 日商拓自達電線股份有限公司 | Electromagnetic wave shielding film capable of easily peeling off a transfer film without damaging the insulating protective layer |
| JP2019144475A (en) * | 2018-02-22 | 2019-08-29 | Ａｇｃ株式会社 | Light transmissive structure |
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