TWI531467B - Optical film - Google Patents
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- TWI531467B TWI531467B TW103133738A TW103133738A TWI531467B TW I531467 B TWI531467 B TW I531467B TW 103133738 A TW103133738 A TW 103133738A TW 103133738 A TW103133738 A TW 103133738A TW I531467 B TWI531467 B TW I531467B
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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Description
本發明係有關於一種光學膜，更具體地，係有關於一種聚酯基(polyester base)光學膜，其藉由在聚酯基薄膜的一個表面或兩個表面上塗覆聚氨基甲酸酯(polyurethane)塗料組合物以形成底層塗料層(primer layer)而在高溫與高濕度下具有極佳的黏著性。 The present invention relates to an optical film, and more particularly to a polyester base optical film which is coated with polyurethane on one surface or both surfaces of a polyester-based film ( The polyurethane coating composition forms an primer layer and has excellent adhesion at high temperatures and high humidity.
通常，雙軸向拉伸的聚酯薄膜具有極佳的尺寸穩定性、厚度均勻性以及光學透明度，以致不僅顯著廣泛地用於顯示裝置而且用於各種產業的材料。 In general, the biaxially stretched polyester film has excellent dimensional stability, thickness uniformity, and optical transparency, so that it is not only widely used for display devices but also materials for various industries.
在將雙軸向拉伸的聚酯多層膜用於光學器件的情況下，底層塗料層通常係由聚酯薄膜以及具有優異黏著性的共聚聚酯基樹脂形成。在單獨使用該共聚聚酯基樹脂時，與聚酯基基膜的黏著性是充分的；然而，在進行各種後處理以作為稜鏡鏡片、抗反射層、硬塗層等使用的情況下，該共聚聚酯基樹脂不足。為了補充該些問題，已經研究在製備聚酯以將其用於許多需要黏著性的領域中時藉由利用聚氨基甲酸酯基樹脂塗覆底層塗料層來改善黏著力的方法，該聚氨基甲酸酯基樹脂具有極佳的易黏著性、柔韌性與耐磨性以及強黏著性等。然而，在藉由聚氨基甲酸酯樹脂形成底層塗料層的情況下，與外層例如硬塗層等的黏著力得到改善；然而，與作為基材的聚酯薄膜的黏著力不足，結果，存在無法獲得足夠的外層黏著性的問題。 In the case where a biaxially stretched polyester multilayer film is used for an optical device, the primer layer is usually formed of a polyester film and a copolyester-based resin having excellent adhesion. When the copolyester-based resin is used alone, the adhesion to the polyester-based film is sufficient; however, in the case where various post-treatments are carried out as a ruthenium lens, an antireflection layer, a hard coat layer, or the like, The copolyester-based resin is insufficient. In order to supplement these problems, a method of improving adhesion by coating a primer layer with a polyurethane-based resin in the preparation of a polyester for use in many fields requiring adhesion has been studied. The formate-based resin has excellent adhesion, flexibility and abrasion resistance, and strong adhesion. However, in the case where the primer layer is formed by the polyurethane resin, the adhesion to the outer layer such as the hard coat layer or the like is improved; however, the adhesion to the polyester film as the substrate is insufficient, and as a result, there is There is no way to get enough adhesion to the outer layer.
另外，作為在進行後處理之後評估黏著性的其中一種方法，在高溫與高濕度例如65℃與90%濕度的條件下評估抗濕性時，因水滲透到經後處理的表面中而產生黏著力缺陷，因此，為了克服該問題，已試圖藉由將硬化劑塗覆到該聚氨基甲酸酯基樹脂以形成聚合物網絡來改善耐久性。 然而，該底層塗料層的該聚氨基甲酸酯樹脂不能藉由常用的三聚氰胺基或環氧基硬化劑充分交聯，並且會降低光學物理性質。 In addition, as one of methods for evaluating adhesion after post-treatment, when moisture resistance is evaluated under conditions of high temperature and high humidity such as 65 ° C and 90% humidity, adhesion occurs due to penetration of water into the post-treated surface. Force defects, therefore, in order to overcome this problem, attempts have been made to improve durability by applying a hardener to the polyurethane-based resin to form a polymer network. However, the polyurethane resin of the primer layer cannot be sufficiently crosslinked by a conventional melamine-based or epoxy-based hardener, and the optical physical properties are lowered.
韓國專利第10-1050216號(專利文獻1)公開了一種聚合物基材料，在該聚合物基材料中，利用水分散型聚碳化二亞胺作為水性的聚異氰酸酯(isocyanate)樹脂中的硬化劑。在這種情況下，與該聚合物基材料的黏著力在高溫與高濕度下得到改善；然而，問題仍然存在，因為光學性質例如透射比、霧度、黃色指數等已經降低，導致難以作為光學膜使用。 Korean Patent No. 10-1050216 (Patent Document 1) discloses a polymer-based material in which a water-dispersible polycarbodiimide is used as a hardener in an aqueous polyisocyanate resin. . In this case, the adhesion to the polymer-based material is improved at high temperature and high humidity; however, the problem still exists because optical properties such as transmittance, haze, yellowness index, etc. have been lowered, resulting in difficulty in being optical. Membrane use.
韓國專利第10-1050216號 Korean Patent No. 10-1050216
本發明的一實施例旨在提供一種聚酯光學膜，該聚酯光學膜具有一底層塗料層，該底層塗料層在高溫與高濕度下與一聚酯基薄膜具有極佳的黏著性。 An embodiment of the present invention is directed to a polyester optical film having a primer layer which has excellent adhesion to a polyester-based film under high temperature and high humidity.
更具體地，本發明的目的為提供一種聚酯光學膜，該聚酯光學膜不僅在高溫與高濕度下與該聚酯基薄膜具有黏著性，而且藉由以聚氨基甲酸酯塗料組合物形成底層塗料層而與例如硬塗層等外層具有顯著改善的的黏著性，該外層係在後處理過程中形成，該聚氨基甲酸酯塗料組合物含有可水分散的(water-dispersible)聚氨基甲酸酯樹脂以及可水分散的聚氨基甲酸酯硬化劑，其中所述可水分散的聚氨基甲酸酯樹脂由10wt%至75wt%之具有兩個端基的線性聚合物以及25wt%至90wt%之具有三個以上端基的支鏈聚合物組成，所述可水分散的聚氨基甲酸酯硬化劑具有4至6個官能基。 More specifically, it is an object of the present invention to provide a polyester optical film which has adhesion to the polyester-based film not only at high temperature and high humidity, but also by a polyurethane coating composition. The primer layer is formed to have a significantly improved adhesion to an outer layer such as a hard coat layer which is formed during post-treatment, the polyurethane coating composition containing water-dispersible poly a urethane resin and a water-dispersible polyurethane hardener, wherein the water-dispersible polyurethane resin is from 10% by weight to 75% by weight of a linear polymer having two terminal groups and 25% by weight Up to 90% by weight of a branched polymer having three or more terminal groups, the water-dispersible polyurethane hardener having 4 to 6 functional groups.
本發明的另一實施例旨在提供一種聚酯光學膜，該聚酯光學膜含有一可水分散的聚氨基甲酸酯硬化劑，以便即使在加濕條件處理後仍具有極佳的黏著力。 Another embodiment of the present invention is directed to a polyester optical film comprising a water-dispersible polyurethane hardener for excellent adhesion even after being subjected to humidification conditions. .
在一般形態中，提供一種光學膜，該光學膜包括：一底層塗料層，該底層塗料層係藉由在一聚酯基薄膜的一個表面或兩個表面上塗覆一可水分散的聚氨基甲酸酯塗料組合物而形成，其中該聚氨基甲酸酯塗料組合物含有一可水分散的聚氨基甲酸酯樹脂以及一可水分散的聚氨基甲酸酯硬化劑，所述可水分散的聚氨基甲酸酯樹脂由10wt%至75wt%之具有兩個端基的線性聚合物以及25wt%至90wt%之具有三個以上端基的支鏈聚合物組成，所述可水分散的聚氨基甲酸酯硬化劑具有4至6個官能基。 In a general aspect, an optical film is provided, the optical film comprising: a primer layer coated with a water-dispersible polyurethane on one or both surfaces of a polyester-based film Formed from an acid ester coating composition, wherein the polyurethane coating composition comprises a water-dispersible polyurethane resin and a water-dispersible polyurethane hardener, the water-dispersible The polyurethane resin is composed of 10% by weight to 755% by weight of a linear polymer having two terminal groups and 255% by weight to 90% by weight of a branched polymer having three or more terminal groups, the water-dispersible polyamino group The formate hardener has 4 to 6 functional groups.
所述可水分散的聚氨基甲酸酯樹脂的所述端基可為異氰酸酯基，所述異氰酸酯基部分地或全部地與無機酸鹽基黏連(block)。 The end group of the water-dispersible polyurethane resin may be an isocyanate group, and the isocyanate group partially or wholly blocks with a mineral acid salt group.
所述可水分散的聚氨基甲酸酯樹脂可藉由將39wt%至45wt%的多元醇(polyol)、0.3wt%至1.2wt%的三羥甲基丙烷(trimethylol propane)以及50wt%至57wt%的異氰酸酯化合物反應以製備具有異氰酸酯作為端基的預聚物，並將該製備的預聚物與3wt%至4wt%的無機酸鹽進行反應以使離子基黏連在該異氰酸酯的一端來製備。 The water-dispersible polyurethane resin can be obtained by using 39 wt% to 45 wt% of polyol, 0.3 wt% to 1.2 wt% of trimethylol propane, and 50 wt% to 57 wt. % of an isocyanate compound is reacted to prepare a prepolymer having an isocyanate as a terminal group, and the prepared prepolymer is reacted with 3 to 4% by weight of a mineral acid salt to adhere an ionic group to one end of the isocyanate to prepare .
該聚氨基甲酸酯塗料組合物可含有5wt%至10wt%的可水分散的聚氨基甲酸酯黏合劑、0.1wt%至1.5wt%的所述可水分散的聚氨基甲酸酯硬化劑、0.1wt%至0.5wt%的矽樹脂基(silicone-based)潤濕劑、0.1wt%至0.5wt%的膠體二氧化矽顆粒、以及剩餘含量的水，其中所述可水分散的聚氨基甲酸酯黏合劑具有10wt%至30wt%的所述可水分散的聚氨基甲酸酯樹脂的固體成分。 The polyurethane coating composition may contain from 5 wt% to 10 wt% of a water-dispersible polyurethane binder, and from 0.1 wt% to 1.5 wt% of the water-dispersible polyurethane hardener. a 0.1% to 0.5% by weight of a silicone-based wetting agent, 0.1% to 0.5% by weight of colloidal cerium oxide particles, and a remaining amount of water, wherein the water-dispersible polyamino group The formate adhesive has a solid content of the water-dispersible polyurethane resin of 10% by weight to 30% by weight.
所述可水分散的聚氨基甲酸酯硬化劑可具有50wt%至80wt%含聚異氰酸酯、有機溶劑及水的固體成分、4.0wt%至5.5wt%的異氰酸酯基成分，並且具有在25℃下以布氏黏度計(MODEL DV-II VISCOMETER,spindle No.#5)測出的2500cps以下的黏度。 The water-dispersible polyurethane hardener may have a solid content of 50% by weight to 80% by weight of a polyisocyanate, an organic solvent and water, an isocyanate group component of 4.0% by weight to 5.5% by weight, and has a composition at 25 ° C The viscosity below 2500 cps measured by a Brookfield viscometer (MODEL DV-II VISCOMETER, spindle No. #5).
該有機溶劑可為選自由二乙二醇單甲醚(diethylene glycol monomethyl ether)、二乙二醇二甲醚(diethylene glycol dimethyl ether)、二丙二醇單甲醚(dipropylene glycol monomethyl ether)、二丙二醇二甲醚(dipropylene glycol dimethyl ether)、二丁二醇單甲醚(dibutylene glycol monomethyl ether)以及二丁二醇二甲醚(dibutylene glycol dimethyl ether)所組成的群組中的一種或兩種以上。 The organic solvent may be selected from the group consisting of diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol. One or more of the group consisting of dipropylene glycol dimethyl ether, dibutylene glycol monomethyl ether, and dibutylene glycol dimethyl ether.
該聚異氰酸酯可為脂肪族聚異氰酸酯。 The polyisocyanate can be an aliphatic polyisocyanate.
依據以下等式2測出的膠體部分可為50%至95%，且玻璃轉換溫度(Tg)可為40℃以上：[等式2]膠體部分(%)=(塗覆薄膜乾燥後的重量-初始重量)/初始重量×100 The colloidal portion measured according to the following Equation 2 may be 50% to 95%, and the glass transition temperature (Tg) may be 40 ° C or more: [Equation 2] Colloidal portion (%) = (weight of the coated film after drying) - initial weight) / initial weight × 100
(在上述等式2中，塗覆薄膜乾燥後的重量指的是將約1g乾燥的塗覆薄膜浸入50g蒸餾水中，在70℃下擱置該塗覆薄膜24小時，並將擱置的該塗覆薄膜在120℃下乾燥3小時之後測出的重量)。 (In the above Equation 2, the weight after drying of the coated film means that about 1 g of the dried coated film is immersed in 50 g of distilled water, the coated film is left at 70 ° C for 24 hours, and the coating is left to stand. The weight of the film measured after drying at 120 ° C for 3 hours).
依據以下等式2測出的膠體部分可為80%至95%，且玻璃轉換溫度(Tg)可為60℃至80℃。 The colloidal portion measured according to the following Equation 2 may be 80% to 95%, and the glass transition temperature (Tg) may be 60 ° C to 80 ° C.
表面能可為30dyne/cm至60dyne/cm。 The surface energy can range from 30 dyne/cm to 60 dyne/cm.
依據本發明的光學膜可在室溫以及高溫、高濕度下具有極佳的抗濕性。 The optical film according to the present invention has excellent moisture resistance at room temperature as well as high temperature and high humidity.
另外，在依據本發明的光學膜中，將可水分散的聚氨基甲酸酯硬化劑引入到可水分散的聚氨基甲酸酯黏合劑中，以增加交聯密度，以使得塗覆薄膜具有提高的強度，以提供極佳的耐久性與極佳的抗濕性，藉此可提高抗黏連性(anti-blocking property)，以提高該光學膜的性能，並增強與稜鏡塗覆層的黏著力，其適合作為光學膜，例如具有極佳UV易黏著性的稜鏡片等。 Further, in the optical film according to the present invention, a water-dispersible polyurethane hardener is introduced into the water-dispersible polyurethane adhesive to increase the crosslinking density so that the coated film has Increased strength to provide excellent durability and excellent moisture resistance, thereby improving anti-blocking properties, improving the performance of the optical film, and enhancing the coating with ruthenium The adhesion is suitable as an optical film, for example, a ruthenium having excellent UV adhesion.
第1圖為顯示根據本發明的黏連評估方法的評估標準的照片。 Fig. 1 is a photograph showing evaluation criteria of the adhesion evaluation method according to the present invention.
下文中，詳細說明本發明光學膜的較佳示例性實施例以及物理性質的測量方法。藉由以下示例將更加領會本發明，所述示例以舉例說明的方式給出，而並非意圖限制本發明的保護範圍，本發明的保護範圍由所附的申請專利範圍所界定。 Hereinafter, preferred exemplary embodiments of the optical film of the present invention and methods of measuring physical properties will be described in detail. The invention will be further appreciated by the following examples, which are given by way of illustration and not by way of limitation.
作為達成本發明的目的而進行的研究的結果，本發明人發現，在利用含有具三個以上作為端基的異氰酸酯官能基及與無機酸鹽黏連的一末端的可水分散的聚氨基甲酸酯樹脂以及具4至6個官能基的可水分散的聚氨基甲酸酯硬化劑的聚氨基甲酸酯塗料組合物，形成底層塗料層的情況下，在高溫與高濕度的嚴酷條件下抗濕性得到改善，以在後處理時提供與聚合物基薄膜的優異黏著性，該聚合物基薄膜用於光學器件，例如稜鏡片等，從而完成了本發明。 As a result of a study conducted to achieve the object of the present invention, the inventors have found that a water-dispersible polyaminocarb having a terminal having an isocyanate functional group having three or more terminal groups and a binder with a mineral acid salt is used. A polyurethane resin coating composition of an acid ester resin and a water-dispersible polyurethane hardener having 4 to 6 functional groups, in the case of forming a primer layer, under severe conditions of high temperature and high humidity The moisture resistance is improved to provide excellent adhesion to a polymer-based film which is used for an optical device such as a ruthenium sheet or the like at the time of post-treatment, thereby completing the present invention.
下文中，詳細說明本發明。 Hereinafter, the present invention will be described in detail.
本發明中所使用的基膜沒有特別限制，只要其為通常用作光學膜的透明聚合物薄膜即可，例如，聚酯薄膜。 The base film used in the present invention is not particularly limited as long as it is a transparent polymer film which is generally used as an optical film, for example, a polyester film.
更具體地，因為極佳的透光率，較佳使用所述聚酯薄膜中的聚對苯二甲酸乙二醇酯(PET)薄膜或者聚萘二甲酸乙二醇酯(PEN)薄膜。考慮到該基膜的用途與物理性質，可進一步包括添加劑或者粒子。作為該基膜，較佳使用拉伸薄膜，並且可使用單軸向拉伸薄膜或者雙軸向拉伸薄膜。該基膜可具有50μm至250μm的厚度，但本發明不限於此。 More specifically, a polyethylene terephthalate (PET) film or a polyethylene naphthalate (PEN) film in the polyester film is preferably used because of excellent light transmittance. Additives or particles may be further included in view of the use and physical properties of the base film. As the base film, a stretched film is preferably used, and a uniaxially stretched film or a biaxially stretched film can be used. The base film may have a thickness of 50 μm to 250 μm, but the invention is not limited thereto.
本發明中的底層塗料層形成在基膜的一個表面或兩個表面上，具有極佳的黏著性，以展現出有助於與其他基材黏著的易黏著性。 The primer layer in the present invention is formed on one surface or both surfaces of the base film, and has excellent adhesion to exhibit adhesion which contributes to adhesion to other substrates.
該底層塗料層的特點在於使用含有所述可水分散的聚氨基甲酸酯樹脂以及所述可水分散的聚氨基甲酸酯硬化劑的該聚氨基甲酸酯塗料組合物。所述可水分散的聚氨基甲酸酯樹脂可包括：具有三個以上作為端基的異氰酸酯官能基的支鏈聚合物，其中異氰酸酯基部分地或全部地與無機酸鹽基黏連；以及具有部分地或全部地與無機酸鹽基黏連的兩個異氰酸酯官能基的線性聚合物。 The primer layer is characterized by using the polyurethane coating composition containing the water-dispersible polyurethane resin and the water-dispersible polyurethane hardener. The water-dispersible polyurethane resin may include: a branched polymer having three or more isocyanate functional groups as a terminal group, wherein the isocyanate group partially or wholly adheres to the inorganic acid salt group; A linear polymer of two isocyanate functional groups that are partially or wholly bonded to a mineral acid salt group.
在本發明中，「線性聚合物」指的是具有兩個異氰酸酯官能基的樹脂，「支鏈聚合物」指的是具有三個或三個以上異氰酸酯官能基的樹脂。 In the present invention, "linear polymer" refers to a resin having two isocyanate functional groups, and "branched polymer" refers to a resin having three or more isocyanate functional groups.
該無機酸鹽基不受限制，但更具體地，可為無機鹽，例如硫酸鹽。尤其是，較佳使用硫酸氫鈉(Sodium Hydrogen Sulfate)，並且具有3wt%至4wt%的含量是有效的。 The inorganic acid salt group is not limited, but more specifically, may be an inorganic salt such as a sulfate. In particular, sodium hydrogen sulfate (Sodium Hydrogen Sulfate) is preferably used, and it is effective to have a content of from 3 wt% to 4 wt%.
較佳的是，所述可水分散的聚氨基甲酸酯樹脂由10wt%至75wt%的線性聚合物以及25wt%至90wt%的支鏈聚合物組成。當該支鏈聚 合物具有小於25wt%的含量時，不能滿足本發明中期望的膨脹比與膠體部分，且難以獲得在高溫與高濕度條件下具有極佳易黏著性的塗覆薄膜。在製備所述可水分散的聚氨基甲酸酯樹脂時，可藉由調整三羥甲基丙烷的含量來調整該支鏈聚合物的含量。 Preferably, the water-dispersible polyurethane resin is composed of 10% by weight to 75% by weight of a linear polymer and 25% by weight to 90% by weight of a branched polymer. When the branch gathers When the composition has a content of less than 25% by weight, the desired expansion ratio and the colloidal portion in the present invention are not satisfied, and it is difficult to obtain a coated film which has excellent adhesion under high temperature and high humidity conditions. In the preparation of the water-dispersible polyurethane resin, the content of the branched polymer can be adjusted by adjusting the content of trimethylolpropane.
另外，當該支鏈聚合物具有大於90wt%的含量時，因過度膠體化使黏度迅速增加，以至於難以製備可水分散的組合物，並且在對薄膜表面進行塗覆處理時，外表會出現缺陷，例如，表面出現破裂等。 In addition, when the branched polymer has a content of more than 90% by weight, the viscosity is rapidly increased due to excessive colloidation, so that it is difficult to prepare a water-dispersible composition, and when the surface of the film is coated, the appearance appears. Defects, for example, cracks on the surface.
在所述可水分散的聚氨基甲酸酯樹脂的製備方法中，較佳地，藉由將39wt%至45wt%的多元醇、0.3wt%至1.2wt%的三羥甲基丙烷以及50wt%至57wt%的異氰酸酯化合物反應以製備具有異氰酸酯作為端基的預聚物，並將製備的預聚物與3wt%至4wt%的無機酸鹽進行反應以使該無機酸鹽的離子基黏連在該異氰酸酯的一端，來製備所述可水分散的聚氨基甲酸酯樹脂，但其方法不限於此。 In the preparation method of the water-dispersible polyurethane resin, preferably, by using 39 wt% to 45 wt% of a polyol, 0.3 wt% to 1.2 wt% of trimethylolpropane, and 50 wt% Up to 57% by weight of the isocyanate compound is reacted to prepare a prepolymer having an isocyanate as a terminal group, and the prepared prepolymer is reacted with 3 to 4% by weight of a mineral acid salt to adhere the ionic group of the inorganic acid salt to The water-dispersible polyurethane resin is prepared at one end of the isocyanate, but the method is not limited thereto.
另外，當所述可水分散的聚氨基甲酸酯樹脂具有10,000g/mol至20,000g/mol的重均分子量時，樹脂沒有變成膠體，實現了均勻的水分散，並且能夠得到在高溫與高濕度條件下具有極佳物理性質的塗覆薄膜。 Further, when the water-dispersible polyurethane resin has a weight average molecular weight of 10,000 g/mol to 20,000 g/mol, the resin does not become a colloid, uniform water dispersion is achieved, and high temperature and high temperature can be obtained. A coated film having excellent physical properties under humidity conditions.
所述可水分散的聚氨基甲酸酯樹脂的重均分子量可利用GPC-MALS(多角度光散射，Multi Angle Light Scattering)系統(懷雅特技術公司，Wyatt Technology Corporation)測量，MALS系統的配置如下。 The weight average molecular weight of the water-dispersible polyurethane resin can be measured by a GPC-MALS (Multi Angle Light Scattering) system (Wyatt Technology Corporation, Wyatt Technology Corporation), and the configuration of the MALS system as follows.
MALS系統配置 MALS system configuration
GPC：Water 1525 Binary HPLC Pump GPC: Water 1525 Binary HPLC Pump
折射率檢測器：Optilab rex Refractive Index Detector: Optilab rex
MALS：Wyatt Dawn 8+ MALS: Wyatt Dawn 8+
色譜柱：PLgel 5μm Mixed-C(7.5mmΦ×300mm)×2(聚合物實驗室) Column: PLgel 5 μ m Mixed-C (7.5 mm Φ × 300 mm) × 2 (Polymer Laboratory)
流動相：DMF(50mM LiCl) Mobile phase: DMF (50 mM LiCl)
流率：0.5mL/min Flow rate: 0.5mL/min
溫度：50℃ Temperature: 50 ° C
注入體積：0.5%,500μl Injection volume: 0.5%, 500 μl
該多元醇可為聚酯基多元醇或者聚醚基多元醇，較佳為聚酯基多元醇。該多元醇可包括具有兩個官能基的多元醇二醇、具有三個官能基的多元醇三醇以及具有四個以上官能基的多元醇，更佳為聚酯基二醇。 The polyol may be a polyester-based polyol or a polyether-based polyol, preferably a polyester-based polyol. The polyol may include a polyol diol having two functional groups, a polyol triol having three functional groups, and a polyol having four or more functional groups, more preferably a polyester diol.
該聚酯基多元醇可為從己二酸、碳酸、癸二酸或酸酐與多元醇的反應中製備的多元醇。可使用該聚酯基多元醇，而並不受限制，只要其明顯為本領域中已知的聚酯基多元醇即可，尤其是，較佳使用具有600g/mol至3000g/mol重均分子量的聚酯多元醇。 The polyester-based polyol may be a polyol prepared from the reaction of adipic acid, carbonic acid, sebacic acid or an acid anhydride with a polyol. The polyester-based polyol may be used without limitation as long as it is clearly a polyester-based polyol known in the art, and in particular, it is preferred to use a weight average molecular weight of from 600 g/mol to 3000 g/mol. Polyester polyol.
依據本發明示例性實施例之用來製備聚氨基甲酸酯樹脂的多元醇的含量較佳為39wt%至45wt%。當該多元醇的含量小於39wt%時，該聚氨基甲酸酯樹脂具有減小的分子量，以至於該底層塗料層會非常硬。另外，難以拉伸該光學膜，以至於塗覆外貌會被降解。進一步地，當該多元醇的含量大於45wt%時，該底層塗料層太軟，黏連性會降低。 The content of the polyol used to prepare the polyurethane resin according to an exemplary embodiment of the present invention is preferably from 39% by weight to 45% by weight. When the content of the polyol is less than 39% by weight, the polyurethane resin has a reduced molecular weight, so that the primer layer may be very hard. In addition, it is difficult to stretch the optical film so that the coating appearance is degraded. Further, when the content of the polyol is more than 45 wt%, the primer layer is too soft and the adhesion is lowered.
另外，利用該三羥甲基丙烷來製備具有三個官能基以形成支鏈聚合物的預聚物，較佳具有0.3wt%至1.2wt%的含量。理論上，當該三羥甲基丙烷的含量為0.3wt%時，該支鏈聚合物可形成為含量為25wt%，而當該三羥甲基丙烷的含量為1.2wt%時，該支鏈聚合物可形成為含量為90wt%。 Further, the trimethylolpropane is used to prepare a prepolymer having three functional groups to form a branched polymer, preferably having a content of from 0.3% by weight to 1.2% by weight. Theoretically, when the content of the trimethylolpropane is 0.3% by weight, the branched polymer can be formed to have a content of 25% by weight, and when the content of the trimethylolpropane is 1.2% by weight, the branch is obtained. The polymer can be formed to a content of 90% by weight.
當該三羥甲基丙烷的含量小於0.3wt%時，因減小的交聯密度而導致抗黏連性會降低，當該三羥甲基丙烷的含量大於1.2wt%時，因過度增加的交聯密度而導致拉伸性會降低，以至於不能提供極佳的塗覆外貌，並且黏著力會減小。 When the content of the trimethylolpropane is less than 0.3% by weight, the blocking resistance is lowered due to the reduced crosslinking density, and when the content of the trimethylolpropane is more than 1.2% by weight, the excessive increase is caused. The crosslink density causes the stretchability to be lowered, so that an excellent coating appearance cannot be provided, and the adhesive force is reduced.
依據本發明示例性實施例用來製備聚氨基甲酸酯樹脂的異氰酸酯化合物不受限制，但可為脂肪族異氰酸酯。 The isocyanate compound used to prepare the polyurethane resin according to an exemplary embodiment of the present invention is not limited, but may be an aliphatic isocyanate.
本發明的脂肪族異氰酸酯可包括在主鏈中具有3至20個碳原子的脂肪族或脂環族異氰酸酯。例如，可使用環己烷二異氰酸酯(hexamethylene diisocyanate)、二環己基甲烷二異氰酸酯(dicyclohexyl methan diisocyanate)、異佛爾酮二異氰酸酯(isophorone methan diisocyanate)及其混合物。更佳地，可使用環己烷二異氰酸酯。含量為50wt%至57wt%之本發明的異氰酸酯化合物足以製備具有三個官能基的預聚物。 The aliphatic isocyanate of the present invention may include an aliphatic or alicyclic isocyanate having 3 to 20 carbon atoms in the main chain. For example, hexamethylene diisocyanate, dicyclohexyl methan diisocyanate, isophorone methan diisocyanate, and mixtures thereof can be used. More preferably, cyclohexane diisocyanate can be used. The isocyanate compound of the present invention in an amount of from 50% by weight to 57% by weight is sufficient to prepare a prepolymer having three functional groups.
在本發明中，含有聚氨基甲酸酯樹脂與水的可水分散的聚氨基甲酸酯黏合劑較佳用於提高可分散性以及製程的容易性。所述可水分散的 聚氨基甲酸酯黏合劑有效地具有10wt%至30wt%的固體成分，並且由於該底層塗料層的厚度可輕易調整，因此該含量範圍是可取的。 In the present invention, a water-dispersible polyurethane binder containing a polyurethane resin and water is preferably used for improving dispersibility and process easiness. Water-dispersible The polyurethane binder effectively has a solid content of 10% by weight to 30% by weight, and since the thickness of the primer layer can be easily adjusted, the content range is preferable.
由於所述可水分散的聚氨基甲酸酯硬化劑與所述可水分散的聚氨基甲酸酯樹脂發生硬化，以提高交聯密度，因此添加依據本發明示例性實施例之可水分散的聚氨基甲酸酯硬化劑，使該底層塗料層提高塗覆薄膜的強度，以提供提高的黏著性與抗濕性。 Since the water-dispersible polyurethane hardener is hardened with the water-dispersible polyurethane resin to increase the crosslinking density, the water-dispersible according to an exemplary embodiment of the present invention is added. A polyurethane hardener enhances the strength of the coated film to provide improved adhesion and moisture resistance.
本發明的可水分散的聚氨基甲酸酯硬化劑較佳具有固體成分、有機溶劑以及50wt%至75wt%，更佳地60wt%至75wt%的水，該固體成分含有聚異氰酸酯。 The water-dispersible polyurethane hardener of the present invention preferably has a solid component, an organic solvent, and 50% by weight to 75% by weight, more preferably 60% by weight to 75% by weight of water, and the solid component contains a polyisocyanate.
在依據本發明示例性實施例之可水分散的聚氨基甲酸酯硬化劑中含有的聚異氰酸酯較佳為脂肪族聚異氰酸酯。 The polyisocyanate contained in the water-dispersible polyurethane hardener according to an exemplary embodiment of the present invention is preferably an aliphatic polyisocyanate.
本發明的脂肪族異氰酸酯可包括在主鏈中具有3至20個碳原子的脂肪族或脂環族異氰酸酯。例如，可使用環己烷二異氰酸酯、二環己基甲烷二異氰酸酯、異佛爾酮二異氰酸酯及其混合物。 The aliphatic isocyanate of the present invention may include an aliphatic or alicyclic isocyanate having 3 to 20 carbon atoms in the main chain. For example, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and mixtures thereof can be used.
尤其是，環己烷二異氰酸酯可提高水分散性，並且可讓該聚氨基甲酸酯樹脂均勻地交聯，使該底層塗料層可具有美觀的外觀。除此之外，可以領會的是，可防止因熱及水分而在黏著層之間產生黏著現象(黏連)，並且可提高表面交聯程度，以提供與外塗覆層的極佳的UV易黏著性。 In particular, cyclohexane diisocyanate improves water dispersibility and allows the polyurethane resin to be uniformly crosslinked, so that the primer layer can have an aesthetic appearance. In addition, it can be understood that adhesion (adhesion) between the adhesive layers due to heat and moisture can be prevented, and the degree of surface crosslinking can be improved to provide excellent UV with the outer coating layer. Easy to stick.
所述可水分散的聚氨基甲酸酯硬化劑的該異氰酸酯基的含量較佳為4.owt%至6.0wt%，更佳為4.5wt%至5.5wt%。 The content of the isocyanate group of the water-dispersible polyurethane hardener is preferably from 4. tw% to 6.0% by weight, more preferably from 4.5% by weight to 5.5% by weight.
當所述可水分散的聚氨基甲酸酯硬化劑的該異氰酸酯基的含量小於4.0wt%時，交聯密度的增加不足，以致該底層塗料層不具有該塗覆薄膜充分增加的強度，藉此不能預期到所期望的抗濕性與黏著力的改善，而當所述可水分散的聚氨基甲酸酯硬化劑的該異氰酸酯基的含量大於5.5wt%時，交聯密度過度增加，使該聚氨基甲酸酯塗料組合物中黏度迅速增加，以致與所述可水分散的聚氨基甲酸酯黏合劑的親和性會降低，並且在該塗料組合物中會產生團聚，然後，在拉伸該光學膜時，該光學膜會因斷裂或破裂而具有不佳的外觀。 When the content of the isocyanate group of the water-dispersible polyurethane hardener is less than 4.0% by weight, the increase in crosslinking density is insufficient, so that the primer layer does not have a sufficiently increased strength of the coating film, This does not anticipate the desired improvement in moisture resistance and adhesion, and when the content of the isocyanate group of the water-dispersible polyurethane hardener is more than 5.5 wt%, the crosslinking density excessively increases, The viscosity in the polyurethane coating composition is rapidly increased, so that the affinity with the water-dispersible polyurethane binder is lowered, and agglomeration occurs in the coating composition, and then, pulling When the optical film is stretched, the optical film may have a poor appearance due to breakage or cracking.
所述可水分散的聚氨基甲酸酯硬化劑的黏度較佳為2500cps以下，該黏度係在25℃(室溫)下以布氏黏度計(MODEL DV-II VISCOMETER, spindle No.#5)測得。更佳地，當本發明的聚氨基甲酸酯塗料組合物藉由包含2000cps以下的所述可水分散的聚氨基甲酸酯硬化劑而製備時，不會產生團聚。 The water-dispersible polyurethane hardener preferably has a viscosity of 2500 cps or less, and the viscosity is at 25 ° C (room temperature) by a Brookfield viscometer (MODEL DV-II VISCOMETER, Spindle No. #5) measured. More preferably, when the polyurethane coating composition of the present invention is prepared by containing the water-dispersible polyurethane hardener of 2000 cps or less, no agglomeration occurs.
為了提高依據本發明示例性實施例之可水分散的聚氨基甲酸酯硬化劑的水分散性，以及在塗料組合物中提高親和性，較佳含有有機溶劑。該有機溶劑不受限制，只要其為中極兩性的、可與水相容的有機溶劑即可，但是舉例來說，為選自由二乙二醇單甲醚、二乙二醇二甲醚、二丙二醇單甲醚、二丙二醇二甲醚、二丁二醇單甲醚以及二丁二醇二甲醚所組成的群組中的一種或兩種以上。 In order to enhance the water dispersibility of the water-dispersible polyurethane hardener according to an exemplary embodiment of the present invention, and to improve the affinity in the coating composition, it is preferred to contain an organic solvent. The organic solvent is not limited as long as it is a neutral-polar, water-compatible organic solvent, but is, for example, selected from the group consisting of diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, One or more of the group consisting of dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dibutylene glycol monomethyl ether, and dibutylene glycol dimethyl ether.
在依據本發明示例性實施例之可水分散的聚氨基甲酸酯硬化劑中，當該有機溶劑的含量連同水的剩餘含量為20wt%至40wt%時，該聚氨基甲酸酯硬化劑的水分散性會進一步提高，並且可均勻地形成交聯結構，以提高該塗覆薄膜的強度以及表面性質。 In the water-dispersible polyurethane hardener according to an exemplary embodiment of the present invention, when the content of the organic solvent together with the remaining content of water is 20% by weight to 40% by weight, the polyurethane hardener The water dispersibility is further improved, and the crosslinked structure can be uniformly formed to improve the strength and surface properties of the coated film.
依據本發明示例性實施例的聚氨基甲酸酯塗料組合物含有5wt%至10wt%之所述可水分散的聚氨基甲酸酯黏合劑、0.1wt%至1.5wt%之所述可水分散的聚氨基甲酸酯硬化劑、0.1wt%至0.5wt%的矽樹脂基潤濕劑、0.1wt%至0.5wt%的膠體二氧化矽顆粒、以及剩餘含量的水。 The polyurethane coating composition according to an exemplary embodiment of the present invention contains 5 wt% to 10 wt% of the water-dispersible polyurethane binder, 0.1 wt% to 1.5 wt% of the water-dispersible dispersion Polyurethane hardener, 0.1% to 0.5% by weight of a cerium-based wetting agent, 0.1% to 0.5% by weight of colloidal cerium oxide particles, and the remaining amount of water.
當所述可水分散的聚氨基甲酸酯黏合劑的含量小於5wt%時，塗覆性質會非常好，但黏著力的增加會不足，而當所述可水分散的聚氨基甲酸酯黏合劑的含量大於10wt%時，黏著力會非常好，但交聯密度會過度增加，致使該薄膜的外表很差，並且會降低光學性質，例如總透光率、霧度等，不適合作為光學膜。 When the content of the water-dispersible polyurethane binder is less than 5% by weight, the coating property is very good, but the increase in adhesion may be insufficient, and when the water-dispersible polyurethane is bonded When the content of the agent is more than 10% by weight, the adhesion is very good, but the crosslinking density is excessively increased, so that the appearance of the film is poor, and the optical properties such as total light transmittance, haze, etc. are lowered, and it is not suitable as an optical film. .
當所述可水分散的聚氨基甲酸酯硬化劑的含量小於0.1wt%時，沒有充分進行硬化處理，致使黏著性與黏連性的提高會不足，而當所述可水分散的聚氨基甲酸酯硬化劑的含量大於1.5wt%時，外觀問題會迅速增加，例如，像氣泡等缺陷會大量產生，並且由於增加的交聯密度，表面能可為30dyne/cm以下，該表面能的偏差在整個表面上會很大。因此，不會形成均勻的塗覆層，並且殘留不反應的硬化劑，致使黏著力與黏連性的提高會不足。 When the content of the water-dispersible polyurethane hardener is less than 0.1% by weight, the hardening treatment is not sufficiently performed, so that the improvement of adhesion and adhesion may be insufficient, and when the water-dispersible polyamino group is When the content of the formate hardener is more than 1.5% by weight, the appearance problem is rapidly increased, for example, defects such as bubbles are generated in a large amount, and the surface energy can be 30 dyne/cm or less due to the increased crosslinking density, the surface energy The deviation will be large on the entire surface. Therefore, a uniform coating layer is not formed, and an unreacted hardener remains, so that an increase in adhesion and adhesion is insufficient.
更有效的是，為了有助於提高該基膜上的塗覆性質以及提高該底層塗料層的耐熱性，在本發明的聚氨基甲酸酯塗料組合物中含有矽樹脂基潤濕劑、膠體二氧化矽顆粒。 More effectively, in order to help improve the coating property on the base film and improve the heat resistance of the primer layer, the urethane-based wetting agent and colloid are contained in the polyurethane coating composition of the present invention. Ceria particles.
該矽樹脂基潤濕劑的含量較佳為0.1wt%至0.5wt%，並且該膠體二氧化矽顆粒的含量較佳為0.1wt%至0.5wt%。另外，該膠體二氧化矽顆粒的平均粒子大小較佳為50nm至1000nm。 The content of the oxime-based wetting agent is preferably from 0.1% by weight to 0.5% by weight, and the content of the colloidal cerium oxide particles is preferably from 0.1% by weight to 0.5% by weight. Further, the colloidal cerium oxide particles preferably have an average particle size of 50 nm to 1000 nm.
在本發明中，該底層塗料層較佳具有50nm至100nm的乾燥塗覆厚度。塗覆方法不受限制，只要其明顯為本領域中已知的方法即可。例如，可執行在該聚酯薄膜的拉伸過程中於表面上進行塗覆的線上塗佈處理，在製得薄膜後可執行離線塗佈處理。兩種處理可同時進行。較佳地，由於在該線上塗佈處理過程中膜的形成與膜的塗覆同時進行，因此可降低製造成本，並且藉由拉伸擴大可改變該底層塗料層的厚度，使該線上塗佈處理更可取。 In the present invention, the primer layer preferably has a dry coating thickness of 50 nm to 100 nm. The coating method is not limited as long as it is apparently a method known in the art. For example, an in-line coating treatment for coating on a surface during stretching of the polyester film may be performed, and an off-line coating treatment may be performed after the film is produced. Both treatments can be performed simultaneously. Preferably, since the formation of the film during the coating process is performed simultaneously with the coating of the film, the manufacturing cost can be reduced, and the thickness of the primer layer can be changed by stretching to make the line coated. Processing is preferable.
依據本發明示例性實施例的光學膜具有膨脹比與膠體部分的差異。該差異係因反應產生氣泡所致，並且以下條件會適合於該光學膜：依據以下等式1測得的膨脹比為100%以上，依據以下等式2測得的膠體部分為50%至95%，以及玻璃轉換溫度(Tg)為40℃以上。 The optical film according to an exemplary embodiment of the present invention has a difference in expansion ratio from a colloidal portion. This difference is caused by the generation of bubbles by the reaction, and the following conditions are suitable for the optical film: the expansion ratio measured according to the following Equation 1 is 100% or more, and the colloid portion measured according to the following Equation 2 is 50% to 95%. %, and the glass transition temperature (Tg) is 40 ° C or more.
更佳地，當依據以下等式2測得的該膠體部分為80%至95%，並且該玻璃轉換溫度(Tg)為60℃至80℃時，可展現出最佳的抗濕性以及黏著性：[等式1]膨脹比(%)=(薄膜擱置後的重量-初始重量)/初始重量×100 More preferably, when the colloidal portion measured according to the following Equation 2 is 80% to 95%, and the glass transition temperature (Tg) is 60 ° C to 80 ° C, the best moisture resistance and adhesion can be exhibited. Properties: [Equation 1] Expansion ratio (%) = (weight after film retention - initial weight) / initial weight × 100
(在上述等式1中，薄膜擱置後的重量指的是將約1g乾燥的塗覆薄膜浸入50g蒸餾水中，在70℃下擱置該塗覆薄膜24小時之後測得的重量)，以及[等式2]膠體部分(%)=(塗覆薄膜乾燥後的重量-初始重量)/初始重量×100 (In the above Equation 1, the weight after the film is left is the weight measured by immersing about 1 g of the dried coated film in 50 g of distilled water, leaving the coated film at 70 ° C for 24 hours), and [etc. Formula 2] Colloidal part (%) = (weight after coating film drying - initial weight) / initial weight × 100
(在上述等式2中，塗覆薄膜乾燥後的重量指的是將約1g乾燥的塗覆薄膜浸入50g蒸餾水中，在70℃下擱置該塗覆薄膜24小時，並將擱置的該塗覆薄膜在120℃下乾燥3小時之後測得的重量)。 (In the above Equation 2, the weight after drying of the coated film means that about 1 g of the dried coated film is immersed in 50 g of distilled water, the coated film is left at 70 ° C for 24 hours, and the coating is left to stand. The weight of the film measured after drying at 120 ° C for 3 hours).
另外，由於外觀性質會非常好並且可與膠體部分及玻璃轉換溫度行為一起展現出最佳的抗濕性以及黏著性，因此依據本發明示例性實施例的表面能為30dyne/cm至60dyne/cm的光學膜是有效的。 In addition, the surface energy according to an exemplary embodiment of the present invention is 30 dyne/cm to 60 dyne/cm because the appearance properties are very good and can exhibit the best moisture resistance and adhesion together with the colloidal portion and the glass transition temperature behavior. The optical film is effective.
下文中，將參考示例以及比較例更詳細地說明本發明。 Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples.
用拭子擦拭底層塗料層的表面，該拭子上含有表面能測量液體(ACCU DYNE TEST表面張力測試液)。 The surface of the primer layer was wiped with a swab containing a surface energy measuring liquid (ACCU DYNE TEST surface tension test solution).
選擇數值低於樣本的預期dyne/cm指數的試劑，並用該試劑充分浸泡該拭子。在水溶液的狀態下確定表面張力指數，當與樣本表面平行時從左至右塗覆約10cm厚的該水溶液。 An agent having a value lower than the expected dyne/cm index of the sample is selected, and the swab is sufficiently soaked with the reagent. The surface tension index was determined in the state of an aqueous solution, and about 10 cm thick was applied from left to right when parallel to the sample surface.
當塗覆的該試劑的液體薄膜保持5秒以上而沒有出現塌陷或者收縮形狀時，標出用於測量樣本表面張力的該試劑的指數。 The index of the reagent used to measure the surface tension of the sample is indicated when the liquid film of the applied agent is held for more than 5 seconds without collapse or shrinkage.
當在塗覆該試劑後1秒鐘內該液體薄膜收縮或被破壞並且變成水滴或水珠形狀時，選擇具有低指數的該試劑，並進行測試。上述試驗進行十次以上，並計算平均值。 When the liquid film shrinks or is broken and becomes a water droplet or a water droplet shape within 1 second after the application of the reagent, the reagent having a low index is selected and tested. The above test was carried out more than ten times and the average value was calculated.
使用依據本發明的規格為寬*長=7cm*7cm的光學膜。利用HAZE METER(Nipon Denshoku製造的，NDH5000型)測量該樣本。 An optical film having a width * length = 7 cm * 7 cm according to the present invention was used. The sample was measured using HAZE METER (manufactured by Nipon Denshoku, Model NDH5000).
在0.4MPa的壓力條件以及每五步驟設定的溫度下使用Heat Gradient(TOYOSEIKI)，並且擠壓一板料1分鐘，1分鐘之後，取出被擠壓的該板料並確定黏連度。根據第1圖評估每一黏連度的差別。 Heat Gradient (TOYOSEIKI) was used under a pressure condition of 0.4 MPa and a temperature set every five steps, and a sheet was extruded for 1 minute. After 1 minute, the extruded sheet was taken out and the degree of adhesion was determined. The difference in each degree of adhesion was evaluated according to Figure 1.
-在恆定的加濕評估中：在20℃至25℃以及40RH%至50RH%的恆溫/恆濕室中進行評估。 - In a constant humidification evaluation: evaluation was carried out in a constant temperature/constant humidity chamber at 20 ° C to 25 ° C and 40 RH % to 50 RH %.
-加濕評估中：利用超聲波加濕器在100RH%條件下利用該薄膜進行評估。 - Humidification evaluation: The film was evaluated using an ultrasonic humidifier at 100 RH%.
將15g可水分散的聚氨基甲酸酯黏合劑與1.5g可水分散的聚氨基甲酸酯硬化劑相互混合，放到直徑為80mm、高度為15mm的圓形缽中， 以及在65℃下乾燥72小時並在120℃下乾燥3小時。將1g乾燥的塗覆薄膜浸入50g蒸餾水中，在70℃下擱置24小時，然後取出擱置的塗覆薄膜，測出膨脹比。將擱置的塗覆薄膜在120℃下乾燥3小時，然後記錄其重量，並測出膠體部分。 15 g of a water-dispersible polyurethane adhesive and 1.5 g of a water-dispersible polyurethane hardener were mixed with each other and placed in a circular crucible having a diameter of 80 mm and a height of 15 mm. And drying at 65 ° C for 72 hours and drying at 120 ° C for 3 hours. 1 g of the dried coated film was immersed in 50 g of distilled water, left at 70 ° C for 24 hours, and then the deposited coated film was taken out to measure the expansion ratio. The coated film that was left on was dried at 120 ° C for 3 hours, and then the weight was recorded, and the colloid portion was measured.
1)膨脹比(%)：將約1g乾燥的塗覆薄膜浸入50g蒸餾水中，在70℃下擱置24小時，然後取出擱置的塗覆薄膜，並記錄其重量。 1) Expansion ratio (%): About 1 g of the dried coated film was immersed in 50 g of distilled water, left at 70 ° C for 24 hours, and then the deposited coated film was taken out, and the weight thereof was recorded.
[等式1]膨脹比=(薄膜擱置後的重量-初始重量)/初始重量*100 [Equation 1] Expansion ratio = (weight after film leaving - initial weight) / initial weight * 100
2)膠體部分(%)：將擱置的塗覆薄膜在120℃下乾燥3小時，並記錄其重量。 2) Colloidal part (%): The coated film to be left was dried at 120 ° C for 3 hours, and its weight was recorded.
[等式2]膠體部分=(塗覆薄膜乾燥後的重量-初始重量)/初始重量*100 [Equation 2] Colloidal part = (weight after coating film drying - initial weight) / initial weight * 100
使用DSC(PerkinElmer DSC 7)系統，並在第二運行模式下進行測量。利用PerkinElmer DSC 7測量10mg至11mg乾燥的塗覆薄膜。 A DSC (PerkinElmer DSC 7) system was used and measurements were taken in the second mode of operation. 10 mg to 11 mg of the dried coated film was measured using a PerkinElmer DSC 7.
在以下條件下測量第一輪：0~200℃，200℃/分鐘，保持時間-3分鐘//200℃~-40℃，200℃/分鐘，保持時間-5分鐘。 The first round was measured under the following conditions: 0 to 200 ° C, 200 ° C / min, holding time - 3 minutes / / 200 ° C ~ -40 ° C, 200 ° C / min, holding time - 5 minutes.
在以下條件下測量第二輪：-40℃~200℃，20℃/分鐘。 The second round was measured under the following conditions: -40 ° C to 200 ° C, 20 ° C / min.
塗覆依據本發明示例以及比較例的聚氨基甲酸酯塗料組合物，以將稜鏡塗料組合物塗到光學膜的一個表面上，該光學膜上形成有底層塗料層，用Cross Hatch Cutter(YCC-230/1)將1cm×1cm的空間切成100個空間，藉由分離的膠帶(nichban No.405)在室溫下進行3次黏著力評估。在高溫與高濕度評估時，在高溫水熱處理(100℃，60分鐘)之後，藉由上述方法評估該稜鏡塗覆層與該底層塗料層之間的黏著力。 A polyurethane coating composition according to an example of the present invention and a comparative example was applied to apply an enamel coating composition to one surface of an optical film on which an undercoat layer was formed, using a Cross Hatch Cutter ( YCC-230/1) A space of 1 cm × 1 cm was cut into 100 spaces, and adhesion evaluation was performed three times at room temperature by a separate tape (nichban No. 405). In the evaluation of high temperature and high humidity, the adhesion between the ruthenium coating layer and the primer layer was evaluated by the above method after high temperature hydrothermal treatment (100 ° C, 60 minutes).
製備可水分散的聚氨基甲酸酯，該可水分散的聚氨基甲酸酯包括理論含量為25wt%的支鏈聚合物。 A water-dispersible polyurethane was prepared comprising a branched polymer having a theoretical content of 25% by weight.
將40wt%的聚己二酸二醇(polyethyleneadipate diol)、0.3wt%的三羥甲基丙烷以及56.7wt%的環己烷二異氰酸酯相互反應，以製備具有異氰酸酯官能基作為端基的預聚物，並將為該預聚物的端官能基的異氰酸酯與3wt%之作為離子基的硫酸氫鈉進行反應，從而製備具有該離子基且重均分子量為10,700g/mol的聚氨基甲酸酯。將20wt%製備的聚氨基甲酸酯分散到80wt%的水中，以製備固體成分為20wt%的可水分散的聚氨基甲酸酯黏合劑(1)。 40 wt% of polyethylene adipate diol, 0.3 wt% of trimethylolpropane, and 56.7 wt% of cyclohexane diisocyanate were reacted with each other to prepare a prepolymer having an isocyanate functional group as a terminal group. And a polyfunctional ester having the ionic group and having a weight average molecular weight of 10,700 g/mol was prepared by reacting an isocyanate of the terminal functional group of the prepolymer with 3 wt% of sodium hydrogen sulfate as an ionic group. 20% by weight of the prepared polyurethane was dispersed in 80% by weight of water to prepare a water-dispersible polyurethane adhesive (1) having a solid content of 20% by weight.
製備可水分散的聚氨基甲酸酯，該可水分散的聚氨基甲酸酯包括理論含量為50wt%的支鏈聚合物。 A water-dispersible polyurethane is prepared which comprises a branched polymer having a theoretical content of 50% by weight.
將40wt%的聚己二酸二醇、0.6wt%的三羥甲基丙烷以及55.9wt%的環己烷二異氰酸酯相互反應，以製備具有異氰酸酯官能基作為端基的預聚物，並將為該預聚物的端官能基的異氰酸酯與3.5wt%之作為離子基的硫酸氫鈉進行反應，從而製備具有該離子基且重均分子量為14,400g/mol的聚氨基甲酸酯。將20wt%製備的聚氨基甲酸酯分散到80wt%的水中，以製備固體成分為20wt%之可水分散的聚氨基甲酸酯黏合劑(2)。 40 wt% of polyadipate diol, 0.6 wt% of trimethylolpropane, and 55.9 wt% of cyclohexane diisocyanate are mutually reacted to prepare a prepolymer having an isocyanate functional group as a terminal group, and The terminal functional isocyanate of the prepolymer was reacted with 3.5% by weight of sodium hydrogen sulfate as an ionic group to prepare a polyurethane having the ionic group and having a weight average molecular weight of 14,400 g/mol. 20% by weight of the prepared polyurethane was dispersed in 80% by weight of water to prepare a water-dispersible polyurethane binder (2) having a solid content of 20% by weight.
製備可水分散的聚氨基甲酸酯，該可水分散的聚氨基甲酸酯包括理論含量為90wt%的支鏈聚合物。 A water-dispersible polyurethane is prepared which comprises a branched polymer having a theoretical content of 90% by weight.
將40wt%的聚己二酸二醇、1.2wt%的三羥甲基丙烷以及54.8wt%的環己烷二異氰酸酯相互反應，以製備具有異氰酸酯官能基作為端基的預聚物，並將為該預聚物的端官能基的異氰酸酯與4.0wt%之作為離子基的硫酸氫鈉進行反應，從而製備具有該離子基且重均分子量為19,000g/mol的聚氨基甲酸酯。將20wt%製備的聚氨基甲酸酯分散到80wt%的水中，以製備固體成分為20wt%之可水分散的聚氨基甲酸酯。 40 wt% of polyadipate diol, 1.2 wt% of trimethylolpropane, and 54.8 wt% of cyclohexane diisocyanate are mutually reacted to prepare a prepolymer having an isocyanate functional group as a terminal group, and The terminal functional isocyanate of the prepolymer was reacted with 4.0% by weight of sodium hydrogen sulfate as an ionic group to prepare a polyurethane having the ionic group and having a weight average molecular weight of 19,000 g/mol. 20% by weight of the prepared polyurethane was dispersed in 80% by weight of water to prepare a water-dispersible polyurethane having a solid content of 20% by weight.
將具有作為5個官能基類型的5.3%NCO成分的0.5wt%可水分散的聚氨基甲酸酯硬化劑(65wt%的固體成分，23wt%的二丙二醇二甲醚(dipropylene glycol dimethyl ether)，12wt%的水，黏度為2.070cps(@25℃))放到以上製備例1所製備的5wt%可水分散的聚氨基甲酸酯黏合劑中，進行攪拌。將0.3wt%的矽樹脂基潤濕劑(道康寧公司，聚酯矽氧烷共聚物)、0.3wt%平均粒子大小為140nm的膠體二氧化矽顆粒、以及剩餘含量的水添加到其中，然後攪拌2小時，以製備聚氨基甲酸酯塗料組合物。 0.5 wt% water-dispersible polyurethane hardener (65 wt% solids, 23 wt% dipropylene glycol dimethyl ether) having 5.3% NCO component as 5 functional groups, 12 wt% of water having a viscosity of 2.070 cps (@25 ° C) was placed in the 5 wt% water-dispersible polyurethane binder prepared in the above Preparation Example 1 and stirred. 0.3 wt% of a ruthenium-based wetting agent (Dow Corning, a polyester siloxane), 0.3 wt% of colloidal cerium oxide particles having an average particle size of 140 nm, and the remaining amount of water were added thereto, followed by stirring 2 hours to prepare a polyurethane coating composition.
將已去除水分的聚對苯二甲酸乙二醇酯(PET)薄片放到擠出機中，然後熔融擠出，用表面溫度為20℃的澆注鼓冷卻，並固化以製作厚度為2000μm的聚對苯二甲酸乙二醇酯(PET)薄片。將所製作的聚對苯二甲酸乙二醇酯(PET)薄片在80℃下沿著機器方向(MD)拉伸3.5倍，並冷卻到室溫，以製作聚對苯二甲酸乙二醇酯薄膜。然後，藉由塗佈塗裝方法將該聚氨基甲酸酯塗料組合物塗覆到該聚對苯二甲酸乙二醇酯薄膜的兩個表面上，以形成底層塗料層。通過在110℃直至150℃的溫度範圍每一秒鐘增加1℃時進行預熱與乾燥處理，將該薄膜橫向(TD)拉伸3.5倍。然後，被拉伸的薄膜在五步拉幅機中經過230℃熱處理，然後在200℃下沿著機器方向以及橫向釋放10%，並熱固定以製作188μm的雙軸向拉伸薄膜，該薄膜的兩個表面均被塗覆。在形成在該雙軸向拉伸薄膜兩個表面上的該底層塗料層中，第一塗層的乾燥塗覆厚度為80nm，第二塗層的乾燥塗覆厚度為80nm。測量並在下面的表2至表4中顯示所製備的光學膜的物理性質。 The moisture-removed polyethylene terephthalate (PET) flakes were placed in an extruder, then melt extruded, cooled with a casting drum having a surface temperature of 20 ° C, and solidified to produce a poly-thickness of 2000 μm. A sheet of ethylene terephthalate (PET). The produced polyethylene terephthalate (PET) sheet was stretched 3.5 times in the machine direction (MD) at 80 ° C and cooled to room temperature to prepare polyethylene terephthalate. film. Then, the polyurethane coating composition is applied onto both surfaces of the polyethylene terephthalate film by a coating coating method to form a primer layer. The film was stretched laterally (TD) by 3.5 times by preheating and drying treatment by increasing the temperature range of 110 ° C to 150 ° C by 1 ° C per second. Then, the stretched film was heat-treated at 230 ° C in a five-step tenter, then released at 10 ° C in the machine direction and in the transverse direction at 200 ° C, and thermally fixed to prepare a 188 μm biaxially stretched film. Both surfaces are coated. In the primer layer formed on both surfaces of the biaxially stretched film, the first coating had a dry coating thickness of 80 nm and the second coating had a dry coating thickness of 80 nm. The physical properties of the prepared optical film are measured and shown in Tables 2 to 4 below.
如下表1中所示，以與上述示例1相同的方法製備示例2與示例3的聚氨基甲酸酯塗料組合物，除了所述可水分散的聚氨基甲酸酯硬化劑的含量在示例2中變成1.0wt%以及在示例3中變成1.5wt%之外。 As shown in the following Table 1, the polyurethane coating compositions of Examples 2 and 3 were prepared in the same manner as in the above Example 1, except that the content of the water-dispersible polyurethane hardener was in Example 2 The ratio becomes 1.0 wt% and becomes 1.5 wt% in Example 3.
製作具有底層塗料層的光學膜，該底層塗料層係藉由將該聚氨基甲酸酯塗料組合物塗覆到以與上述示例1相同的方法製作的雙軸向拉伸 的該聚對苯二甲酸乙二醇酯薄膜的兩個表面上而形成，其中在該底層塗料層中，第一塗層的乾燥塗覆厚度為80nm，第二塗層的乾燥塗覆厚度為80nm。測量並在下面的表2至表4中顯示所製備的光學膜的物理性質。 An optical film having a primer layer which was applied by biaxial stretching in the same manner as in the above Example 1 was applied by applying the polyurethane coating composition Forming on both surfaces of the polyethylene terephthalate film, wherein in the primer layer, the first coating has a dry coating thickness of 80 nm, and the second coating has a dry coating thickness of 80nm. The physical properties of the prepared optical film are measured and shown in Tables 2 to 4 below.
將具有作為5個官能基類型的5.3%NCO成分的0.5wt%可水分散的聚氨基甲酸酯硬化劑(65wt%的固體成分，23wt%的二丙二醇二甲醚，12wt%的水，黏度為2.070cps(@25℃))放到以上製備例2所製備的5wt%可水分散的聚氨基甲酸酯黏合劑中，進行攪拌。將0.3wt%的矽樹脂基潤濕劑(道康寧公司，聚酯矽氧烷共聚物)、0.3wt%平均粒子大小為140nm的膠體二氧化矽顆粒、以及剩餘含量的水添加到其中，然後攪拌2小時，以製備聚氨基甲酸酯塗料組合物。 0.5 wt% water-dispersible polyurethane hardener (65 wt% solids, 23 wt% dipropylene glycol dimethyl ether, 12 wt% water, viscosity) having 5.3% NCO component as 5 functional groups 2.070 cps (@25 ° C) was placed in the 5 wt% water-dispersible polyurethane binder prepared in the above Preparation Example 2, and stirred. 0.3 wt% of a ruthenium-based wetting agent (Dow Corning, a polyester siloxane), 0.3 wt% of colloidal cerium oxide particles having an average particle size of 140 nm, and the remaining amount of water were added thereto, followed by stirring 2 hours to prepare a polyurethane coating composition.
製作具有底層塗料層的光學膜，該底層塗料層係藉由將該聚氨基甲酸酯塗料組合物塗覆到以與上述示例1相同的方法製作的雙軸向拉伸的該聚對苯二甲酸乙二醇酯薄膜的兩個表面上而形成，其中在該底層塗料層中，第一塗層的乾燥塗覆厚度為80nm，第二塗層的乾燥塗覆厚度為80nm。測量並在下面的表2至表4中顯示所製備的光學膜的物理性質。 An optical film having a primer layer formed by applying the polyurethane coating composition to the biaxially stretched polyparaphenylene produced in the same manner as in the above Example 1 was produced. The two surfaces of the ethylene glycolate film were formed, wherein in the primer layer, the first coating had a dry coating thickness of 80 nm and the second coating had a dry coating thickness of 80 nm. The physical properties of the prepared optical film are measured and shown in Tables 2 to 4 below.
如下表1中所示，以與上述示例4相同的方法製備示例5與示例6的聚氨基甲酸酯塗料組合物，除了所述可水分散的聚氨基甲酸酯硬化劑的含量在示例5中變成1.0wt%以及在示例6中變成1.5wt%之外。 The polyurethane coating compositions of Examples 5 and 6 were prepared in the same manner as in the above Example 4, as shown in Table 1 below, except that the content of the water-dispersible polyurethane hardener was in Example 5. The medium becomes 1.0 wt% and becomes 1.5 wt% in Example 6.
製作具有底層塗料層的光學膜，該底層塗料層係藉由將該聚氨基甲酸酯塗料組合物塗覆到以與上述示例1相同的方法製作的雙軸向拉伸的該聚對苯二甲酸乙二醇酯薄膜的兩個表面上而形成，其中在該底層塗料層中，第一塗層的乾燥塗覆厚度為80nm，第二塗層的乾燥塗覆厚度為80nm。測量並在下面的表2至表4中顯示所製備的光學膜的物理性質。 An optical film having a primer layer formed by applying the polyurethane coating composition to the biaxially stretched polyparaphenylene produced in the same manner as in the above Example 1 was produced. The two surfaces of the ethylene glycolate film were formed, wherein in the primer layer, the first coating had a dry coating thickness of 80 nm and the second coating had a dry coating thickness of 80 nm. The physical properties of the prepared optical film are measured and shown in Tables 2 to 4 below.
將具有作為5個官能基類型的5.3%NCO成分的0.5wt%可水分散的聚氨基甲酸酯硬化劑(65wt%的固體成分，23wt%的二丙二醇二甲醚，12wt%的水，黏度為2.070cps(@25℃))放到以上製備例3所製備的5wt%可水分散的聚氨基甲酸酯黏合劑中，進行攪拌。將0.3wt%的矽樹脂基潤濕劑(道康寧公司，聚酯矽氧烷共聚物)、0.3wt%平均粒子大小為140nm的膠體二氧化矽顆粒、以及剩餘含量的水添加到其中，然後攪拌2小時，以製備聚氨基甲酸酯塗料組合物。 0.5 wt% water-dispersible polyurethane hardener (65 wt% solids, 23 wt% dipropylene glycol dimethyl ether, 12 wt% water, viscosity) having 5.3% NCO component as 5 functional groups 2.070 cps (@25 ° C) was placed in the 5 wt% water-dispersible polyurethane binder prepared in the above Preparation Example 3, and stirred. 0.3 wt% of a ruthenium-based wetting agent (Dow Corning, a polyester siloxane), 0.3 wt% of colloidal cerium oxide particles having an average particle size of 140 nm, and the remaining amount of water were added thereto, followed by stirring 2 hours to prepare a polyurethane coating composition.
製作具有底層塗料層的光學膜，該底層塗料層係藉由將該聚氨基甲酸酯塗料組合物塗覆到以與上述示例1相同的方法製作的雙軸向拉伸的該聚對苯二甲酸乙二醇酯薄膜的兩個表面上而形成，其中在該底層塗料層中，第一塗層的乾燥塗覆厚度為80nm，第二塗層的乾燥塗覆厚度為80nm。測量並在下面的表2至表4中顯示所製備的光學膜的物理性質。 An optical film having a primer layer formed by applying the polyurethane coating composition to the biaxially stretched polyparaphenylene produced in the same manner as in the above Example 1 was produced. The two surfaces of the ethylene glycolate film were formed, wherein in the primer layer, the first coating had a dry coating thickness of 80 nm and the second coating had a dry coating thickness of 80 nm. The physical properties of the prepared optical film are measured and shown in Tables 2 to 4 below.
如下表1中所示，以與上述示例7相同的方法製備示例8與示例9的聚氨基甲酸酯塗料組合物，除了所述可水分散的聚氨基甲酸酯硬化劑的含量在示例8中變成1.0wt%以及在示例9中變成1.5wt%之外。 As shown in the following Table 1, the polyurethane coating compositions of Examples 8 and 9 were prepared in the same manner as in the above Example 7, except that the content of the water-dispersible polyurethane hardener was in Example 8. The medium becomes 1.0 wt% and becomes 1.5 wt% in Example 9.
製作具有底層塗料層的光學膜，該底層塗料層係藉由將該聚氨基甲酸酯塗料組合物塗覆到以與上述示例1相同的方法製作的雙軸向拉伸的該聚對苯二甲酸乙二醇酯薄膜的兩個表面上而形成，其中在該底層塗料層中，第一塗層的乾燥塗覆厚度為80nm，第二塗層的乾燥塗覆厚度為80nm。測量並在下面的表2至表4中顯示所製備的光學膜的物理性質。 An optical film having a primer layer formed by applying the polyurethane coating composition to the biaxially stretched polyparaphenylene produced in the same manner as in the above Example 1 was produced. The two surfaces of the ethylene glycolate film were formed, wherein in the primer layer, the first coating had a dry coating thickness of 80 nm and the second coating had a dry coating thickness of 80 nm. The physical properties of the prepared optical film are measured and shown in Tables 2 to 4 below.
如下表1中所示，以與示例1、4以及7相同的方法分別製備比較例1、2以及3的聚氨基甲酸酯塗料組合物，除了不使用所述可水分散的聚氨基甲酸酯硬化劑之外。 As shown in the following Table 1, the polyurethane coating compositions of Comparative Examples 1, 2 and 3 were separately prepared in the same manner as in Examples 1, 4 and 7, except that the water-dispersible polyurethane was not used. In addition to the ester hardener.
製作具有底層塗料層的光學膜，該底層塗料層係藉由將該聚氨基甲酸酯塗料組合物塗覆到以與上述示例1相同的方法製作的雙軸向拉伸的該聚對苯二甲酸乙二醇酯薄膜的兩個表面上而形成，其中在該底層塗料層中，第一塗層的乾燥塗覆厚度為80nm，第二塗層的乾燥塗覆厚度為80nm。測量並在下面的表2至表4中顯示所製備的光學膜的物理性質。 An optical film having a primer layer formed by applying the polyurethane coating composition to the biaxially stretched polyparaphenylene produced in the same manner as in the above Example 1 was produced. The two surfaces of the ethylene glycolate film were formed, wherein in the primer layer, the first coating had a dry coating thickness of 80 nm and the second coating had a dry coating thickness of 80 nm. The physical properties of the prepared optical film are measured and shown in Tables 2 to 4 below.
如下表1中所示，以與示例1、4以及7相同的方法分別製備比較例1-1、2-1以及3-1的聚氨基甲酸酯塗料組合物，除了使用2.5wt%的所述可水分散的聚氨基甲酸酯硬化劑之外。 As shown in the following Table 1, the polyurethane coating compositions of Comparative Examples 1-1, 2-1, and 3-1 were separately prepared in the same manner as in Examples 1, 4, and 7, except that 2.5 wt% of the materials were used. In addition to the water-dispersible polyurethane hardener.
製作具有底層塗料層的光學膜，該底層塗料層係藉由將該聚氨基甲酸酯塗料組合物塗覆到以與上述示例1相同的方法製作的雙軸向拉伸的該聚對苯二甲酸乙二醇酯薄膜的兩個表面上而形成，其中在該底層塗料層中，第一塗層的乾燥塗覆厚度為80nm，第二塗層的乾燥塗覆厚度為80nm。測量並在下面的表2至表4中顯示所製備的光學膜的物理性質。 An optical film having a primer layer formed by applying the polyurethane coating composition to the biaxially stretched polyparaphenylene produced in the same manner as in the above Example 1 was produced. The two surfaces of the ethylene glycolate film were formed, wherein in the primer layer, the first coating had a dry coating thickness of 80 nm and the second coating had a dry coating thickness of 80 nm. The physical properties of the prepared optical film are measured and shown in Tables 2 to 4 below.
將具有作為5個官能基類型的6.0wt%NCO成分的0.5wt%可水分散的聚氨基甲酸酯硬化劑(65wt%的固體成分，23wt%的二丙二醇二甲醚，12wt%的水，黏度為3500cps(@25℃))放到以上製備例3所製備的5wt%可水分散的聚氨基甲酸酯黏合劑中，進行攪拌。將0.3wt%的矽樹脂基潤濕劑(道康寧公司，聚酯矽氧烷共聚物)、0.3wt%平均粒子大小為140nm的膠體二氧化矽顆粒、以及剩餘含量的水添加到其中，然後攪拌2小時，以製備聚氨基甲酸酯塗料組合物；然而，形成了團聚。 0.5 wt% water-dispersible polyurethane hardener (65 wt% solids, 23 wt% dipropylene glycol dimethyl ether, 12 wt% water, having 6.0 wt% NCO component as 5 functional groups, The viscosity was 3,500 cps (@25 ° C)) and placed in the 5 wt% water-dispersible polyurethane adhesive prepared in the above Preparation Example 3, and stirred. 0.3 wt% of a ruthenium-based wetting agent (Dow Corning, a polyester siloxane), 0.3 wt% of colloidal cerium oxide particles having an average particle size of 140 nm, and the remaining amount of water were added thereto, followed by stirring 2 hours to prepare a polyurethane coating composition; however, agglomeration was formed.
製作具有底層塗料層的光學膜，該底層塗料層係藉由將該聚氨基甲酸酯塗料組合物塗覆到以與上述示例1相同的方法製作的雙軸向拉伸 的該聚對苯二甲酸乙二醇酯薄膜的兩個表面上而形成；然而，產生了例如氣泡等外觀缺陷，並且該底層塗料層不夠均勻到足以使其明顯可見。 An optical film having a primer layer which was applied by biaxial stretching in the same manner as in the above Example 1 was applied by applying the polyurethane coating composition The polyethylene terephthalate film is formed on both surfaces; however, appearance defects such as bubbles are generated, and the primer layer is not sufficiently uniform enough to make it visible.
從表2至表4可以理解的是，當比較不使用所述可水分散的聚氨基甲酸酯硬化劑的比較例1至3時，示例1至9在恆定加濕以及高溫與高濕度條件下顯著提高了抗黏連性以及黏著力。另外，可以理解的是，玻璃轉換溫度以及膠體部分增加。 As can be understood from Table 2 to Table 4, Examples 1 to 9 were in constant humidification and high temperature and high humidity conditions when Comparative Examples 1 to 3 in which the water-dispersible polyurethane hardener was used were compared. The adhesion resistance and adhesion are significantly improved. In addition, it can be understood that the glass transition temperature and the colloidal portion increase.
進一步地，如其中所述可水分散的聚氨基甲酸酯硬化劑的含量大於2.0wt%的比較例1-1、2-1以及3-1中所示，當過量使用所述可水分散的聚氨基甲酸酯硬化劑時，外觀問題迅速增加，例如，像氣泡等缺陷大量產生，並且由於增加的交聯密度，表面能為30dyne/cm以下，該表面能的偏差在整個表面上很大。因此，不會形成均勻的塗覆層，並且殘留不反應的硬化劑，致使黏著力與黏連性的提高會不足。 Further, as shown in Comparative Examples 1-1, 2-1, and 3-1 in which the content of the water-dispersible polyurethane hardener is more than 2.0% by weight, when the water-dispersible is used in excess When the polyurethane hardener is used, the appearance problem is rapidly increased, for example, defects such as bubbles are generated in a large amount, and the surface energy is 30 dyne/cm or less due to the increased crosslinking density, and the deviation of the surface energy is very large on the entire surface. Big. Therefore, a uniform coating layer is not formed, and an unreacted hardener remains, so that an increase in adhesion and adhesion is insufficient.
另外，從比較例4可以理解的是，該聚氨基甲酸酯硬化劑的NCO含量為6.0wt%，黏度為3500cps(@25℃)，該黏度迅速增加，並且在該聚氨基甲酸酯塗料組合物中產生團聚現象，例如膠體的形成等。進一步地，該聚氨基甲酸酯塗料組合物所塗覆的該光學膜的表面上還出現了氣泡等，並且形成了不均勻的底層塗料層，使得外觀性質顯著降低，並且對於每次測量而言，測出的物理性質存在很大偏差，從而難以確定黏著力以及抗黏連性的提高。 Further, it can be understood from Comparative Example 4 that the polyurethane hardener has an NCO content of 6.0% by weight, a viscosity of 3,500 cps (@25 ° C), the viscosity is rapidly increased, and in the polyurethane coating. Agglomeration occurs in the composition, such as formation of colloids and the like. Further, bubbles or the like are also present on the surface of the optical film coated with the polyurethane coating composition, and a non-uniform primer layer is formed, so that the appearance properties are remarkably lowered, and for each measurement In other words, there is a large deviation in the measured physical properties, making it difficult to determine the adhesion and the improvement in blocking resistance.
當匯總上述所有結果時，可以理解的是，藉由調整該底層塗料層中所使用的所述可水分散的聚氨基甲酸酯黏合劑與該硬化劑之間的比例，並包含最佳含量的所述可水分散的聚氨基甲酸酯硬化劑，可製作在高溫與高濕度條件下具有優異物理性質以適合於稜鏡片等的該光學膜。 When summarizing all of the above results, it is understood that by adjusting the ratio between the water-dispersible polyurethane binder used in the primer layer and the hardener, and including the optimum content The water-dispersible polyurethane hardener can be formed into an optical film having excellent physical properties under high temperature and high humidity conditions to be suitable for a sheet or the like.
如上所述，儘管對本發明的較佳實施例進行了說明，但本發明應被解釋為包含所有改變、修飾以及等效方案。顯然地，通過適當修改上述示例性實施例可等效地利用本發明。因此，上述說明並非意圖限制本發明的範圍，本發明的範圍由以下申請專利範圍的限定所界定。 As described above, the preferred embodiments of the invention have been described, but the invention is intended to cover all modifications, modifications and equivalents. Obviously, the present invention can be utilized equivalently by appropriately modifying the above-described exemplary embodiments. Therefore, the above description is not intended to limit the scope of the invention, which is defined by the scope of the following claims.
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| JP5446077B2 (en) * | 2007-08-17 | 2014-03-19 | 日本ポリウレタン工業株式会社 | Aqueous resin composition comprising a blocked isocyanate-containing aqueous emulsion composition as a curing agent, and an aqueous baking type paint or adhesive composition using the same |
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