TWI733862B - Polarizing film and method for producing same - Google Patents
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Abstract
本發明提供一種偏光薄膜,其係包含聚乙烯醇(A)與含硼化合物(B)之偏光薄膜,其中該含硼化合物(B)具有選自包含硼酸基(boronate group)及在水的存在下可轉化成硼酸基(boronate group)的含硼基之群組中之至少1種官能基,其特徵為偏光薄膜中之源自含硼化合物(B)的硼元素含量相對於100質量份的聚乙烯醇(A)為0.1~3質量份。以進一步含有硼酸(boric acid)且偏光薄膜中的所有硼元素含量為0.2~5質量%為佳。藉此,能夠提供一種耐濕熱性能優異的偏光薄膜。 The present invention provides a polarizing film, which is a polarizing film comprising polyvinyl alcohol (A) and a boron-containing compound (B), wherein the boron-containing compound (B) is selected from the group consisting of a boronate group and the presence in water At least one functional group in the boron-containing group that can be converted into a boronate group is characterized by the content of boron element derived from the boron-containing compound (B) in the polarizing film relative to 100 parts by mass The polyvinyl alcohol (A) is 0.1 to 3 parts by mass. Preferably, it further contains boric acid and the content of all boron elements in the polarizing film is 0.2-5 mass%. Thereby, it is possible to provide a polarizing film with excellent moisture and heat resistance.
Description
本發明係關於耐濕熱性優異的偏光薄膜及其製造方法。 The present invention relates to a polarizing film excellent in moisture and heat resistance and a method of manufacturing the same.
具有光的穿透及遮蔽功能的偏光板與使光的偏光狀態變化的液晶皆為液晶顯示器(LCD)的基本構成要素,許多偏光板為了防止偏光薄膜的褪色或是防止偏光薄膜的收縮,而具有在偏光薄膜的表面貼合有三乙酸纖維素(TAC)薄膜等保護膜的結構,作為構成偏光板的偏光薄膜,單軸拉伸聚乙烯醇薄膜(以下有時將「聚乙烯醇」稱為「PVA」)而成的基體吸附碘系色素(I3 -或I5 -等)者為主流。 The polarizing plate with the function of light penetration and shielding and the liquid crystal that changes the polarization state of light are the basic components of liquid crystal displays (LCD). It has a structure in which a protective film such as cellulose triacetate (TAC) film is attached to the surface of the polarizing film. As the polarizing film constituting the polarizing plate, a uniaxially stretched polyvinyl alcohol film (hereinafter sometimes referred to as "polyvinyl alcohol") The matrix made of "PVA") adsorbs iodine-based pigments (I 3 - or I 5 -, etc.) as the mainstream.
LCD係用於計算機及手錶等小型設備、行動電話、筆記型電腦、液晶顯示器、液晶彩色投影機、液晶電視、汽車導航系統、室內外所使用的測量儀器等廣泛的範圍中,近年來,這些設備要求薄型/輕量化。因此,LCD的各構件亦要求薄型化,但若將作為LCD構件之一的偏光板的保護膜薄型化,則擔憂防止碘系偏光薄膜的褪色的功能會下降。於是,尋求一種在高溫且高濕度下的褪色少、也就是所謂的耐濕熱性優異的碘系偏光薄膜。 LCD series are used in a wide range of small devices such as computers and watches, mobile phones, notebook computers, liquid crystal displays, liquid crystal color projectors, liquid crystal televisions, car navigation systems, indoor and outdoor measuring instruments, etc. In recent years, these The equipment is required to be thin/lightweight. Therefore, each member of the LCD is also required to be thinner, but if the protective film of the polarizing plate, which is one of the LCD members, is thinned, there is a concern that the function of preventing the discoloration of the iodine-based polarizing film may be reduced. Therefore, there is a demand for an iodine-based polarizing film that has little fading under high temperature and high humidity, that is, so-called excellent heat and humidity resistance.
此外,就改良碘系偏光薄膜的耐濕熱性之手法而言,已知有以多元醛對偏光薄膜進行交聯處理之手法(專利文獻1)或是以多元羧酸化合物對偏光薄膜進行交聯處理之方法(專利文獻2)。 In addition, as for the method of improving the heat and humidity resistance of the iodine-based polarizing film, a method of cross-linking the polarizing film with a polyhydric aldehyde (Patent Document 1) or a method of cross-linking the polarizing film with a polycarboxylic acid compound is known. Treatment method (Patent Document 2).
專利文獻1 日本特開平6-235815號公報
專利文獻2 日本特開2011-257756號公報
然而,在使用多元醛的情況下,醛容易揮發且難以管理濃度,因此在工業上實施相當困難。又,多元羧酸化合物的反應性低,需要使用酸觸媒或是在高溫下處理等,因此會有偏光薄膜著色這樣的問題。 However, in the case of using polyhydric aldehydes, the aldehydes are easily volatilized and it is difficult to manage the concentration, so it is quite difficult to implement industrially. In addition, the polycarboxylic acid compound has low reactivity and requires the use of an acid catalyst or treatment at high temperature. Therefore, there is a problem of coloring of the polarizing film.
於是,本發明的目的在於提供一種不使用酸觸媒、不需要高溫下的處理且能夠在工業上輕易地製造之耐濕熱性能優異的偏光薄膜。 Therefore, the object of the present invention is to provide a polarizing film that does not use an acid catalyst, does not require high-temperature processing, and can be easily manufactured industrially with excellent moisture and heat resistance.
本發明人等為達成上述目的而專心致力於研究,結果發現,根據包含聚乙烯醇與特定的含硼有機化合物的偏光薄膜,能夠解決上述課題,因而完成本發明。 The inventors of the present invention devoted themselves to research in order to achieve the above-mentioned object. As a result, they found that the above-mentioned problem can be solved by a polarizing film containing polyvinyl alcohol and a specific boron-containing organic compound, thus completing the present invention.
上述課題係藉由提供一種偏光薄膜來解決,該偏光薄膜係包含聚乙烯醇(A)與含硼化合物(B)之偏光薄膜,其中該含硼化合物(B)具有選自包含硼酸基(boronate group)及在水 的存在下可轉化成硼酸基(boronate group)的含硼基之群組中之至少1種官能基,其特徵為偏光薄膜中之源自含硼化合物(B)的硼元素含量相對於100質量份的聚乙烯醇(A)為0.1~3質量份。 The above problem is solved by providing a polarizing film, the polarizing film is a polarizing film comprising polyvinyl alcohol (A) and a boron-containing compound (B), wherein the boron-containing compound (B) is selected from the group consisting of boronate group) and in the water At least one functional group in the boron-containing group that can be converted into a boronate group in the presence of the polarizing film is characterized by the content of boron element derived from the boron-containing compound (B) in the polarizing film relative to 100 mass Parts of polyvinyl alcohol (A) are 0.1 to 3 parts by mass.
此時,該偏光薄膜係以進一步含有硼酸(boric acid)且偏光薄膜中的所有硼元素含量為0.2~5質量%為佳。又,亦以含硼化合物(B)具有複數個前述官能基為佳。 At this time, the polarizing film preferably further contains boric acid and the content of all boron elements in the polarizing film is 0.2-5 mass %. In addition, it is also preferable that the boron-containing compound (B) has a plurality of the aforementioned functional groups.
又,上述課題亦藉由提供前述偏光薄膜之製造方法來解決,該偏光薄膜之製造方法之特徵為在包含以二色性色素將聚乙烯醇薄膜染色之染色處理以及將該薄膜單軸拉伸之拉伸處理之偏光薄膜之製造方法中,具有將該薄膜浸漬於含硼化合物(B)的水溶液之處理。 In addition, the above-mentioned problems are also solved by providing a method for manufacturing the aforementioned polarizing film. The method for manufacturing the polarizing film is characterized by including a dyeing process of dyeing a polyvinyl alcohol film with a dichroic dye and uniaxial stretching of the film. In the method of manufacturing a polarizing film of the stretching treatment, the film is immersed in an aqueous solution of the boron-containing compound (B).
根據本發明,能夠提供耐濕熱性優異的偏光薄膜。又,根據本發明之製造方法,能夠在工業上輕易地製造此種偏光薄膜。 According to the present invention, it is possible to provide a polarizing film having excellent moisture and heat resistance. Moreover, according to the manufacturing method of the present invention, such a polarizing film can be easily manufactured industrially.
1‧‧‧源自為測定溶媒之重水之氫峰 1‧‧‧The hydrogen peak derived from heavy water used as a solvent for determination
2‧‧‧源自PVA的次甲基之氫峰 2‧‧‧The hydrogen peak of methine derived from PVA
3‧‧‧源自PVA的亞甲基之氫峰 3‧‧‧Methylene hydrogen peak derived from PVA
4‧‧‧與源自PVA的氫峰重疊之源自含硼化合物(B)所含的烴基的氫峰 4‧‧‧The hydrogen peak derived from the hydrocarbon group contained in the boron-containing compound (B) overlapping with the hydrogen peak derived from PVA
5‧‧‧未與源自PVA的氫峰重疊之源自含硼化合物(B)所含的烴基的氫峰 5‧‧‧The hydrogen peak derived from the hydrocarbon group contained in the boron-containing compound (B) that does not overlap with the hydrogen peak derived from PVA
圖1係實施例1所得到的偏光薄膜的1H-NMR圖。 FIG. 1 is a 1 H-NMR chart of the polarizing film obtained in Example 1. FIG.
本發明之偏光薄膜為一種偏光薄膜,其係包含聚乙烯醇(A)與含硼化合物(B)之偏光薄膜,其中該含硼化合物(B)具有選自包含硼酸基(boronate group)及在水的存在下可轉化成硼酸基(boronate group)的含硼基之群組中之至少1種官能基。藉由以含硼化合物(B)將聚乙烯醇交聯,偏光薄膜的耐濕熱性會提升。 The polarizing film of the present invention is a polarizing film, which is a polarizing film containing polyvinyl alcohol (A) and a boron-containing compound (B), wherein the boron-containing compound (B) is selected from the group consisting of boronate group and At least one functional group in the boron-containing group that can be converted into a boronate group in the presence of water. By cross-linking polyvinyl alcohol with the boron-containing compound (B), the moisture and heat resistance of the polarizing film is improved.
本發明中使用的含硼化合物(B)為具有選自包含硼酸基(boronate group)及在水的存在下可轉化成硼酸基(boronate group)的含硼基之群組中之至少1種官能基之有機化合物。硼酸基(boronate group)為以下述結構式(1)表示之1價取代基,具有硼原子與2個羥基及碳原子(未圖示)鍵結的結構。相對於硼酸[B(OH)3]係硼原子與3個羥基鍵結,兩者是在硼酸(boronic acid)具有硼-碳鍵結上具有差異。而且,硼酸基(boronate group)具有的硼-碳鍵結不會水解,因此在水存在的環境下也相當安定。就在水的存在下可轉化成硼酸基(boronate group)的含硼基而言,可列舉以下說明的硼酸酯基(boronic ester group)作為代表,但不限於此。 The boron-containing compound (B) used in the present invention has at least one function selected from the group consisting of a boronate group and a boron-containing group that can be converted into a boronate group in the presence of water Based organic compounds. The boronate group is a monovalent substituent represented by the following structural formula (1), and has a structure in which a boron atom is bonded to two hydroxyl groups and a carbon atom (not shown). Compared with the boron atom of boric acid [B(OH) 3 ] which is bonded with three hydroxyl groups, the two are different in that boronic acid has a boron-carbon bond. In addition, the boron-carbon bond of the boronate group does not hydrolyze, so it is quite stable in the presence of water. As for the boron-containing group that can be converted into a boronate group in the presence of water, the boronic ester group described below can be cited as a representative, but it is not limited thereto.
硼酸基(boronate group)的羥基能夠與硼酸的羥基同樣地形成醇及酯。下述結構式(2)為1分子的醇(R-OH)對硼酸基(boronate group)進行反應而得之硼酸單酯基(boronic monoester group)。此處,在硼酸基(boronate group)與PVA的羥基鍵結的情況下,結構式(2)中的R為PVA鏈,含碳基會透過硼原子鍵結至PVA鏈,偏光薄膜的耐濕熱性會提升。 The hydroxyl group of the boronate group can form an alcohol and an ester like the hydroxyl group of a boric acid. The following structural formula (2) is a boronic monoester group obtained by reacting one molecule of alcohol (R-OH) with a boronate group. Here, when the boronate group is bonded to the hydroxyl group of the PVA, R in the structural formula (2) is the PVA chain, and the carbon-containing group is bonded to the PVA chain through the boron atom. The polarizing film is resistant to humidity and heat Sex will improve.
下述結構式(3)為2分子的醇(R-OH)對硼酸基(boronate group)進行反應而得之硼酸二酯基(boronic diester group)。此處,在硼酸基(boronate group)與PVA的羥基鍵結的情況下,結構式(3)中的2個R皆為PVA 鏈,多條PVA鏈會相互交聯,所得到的偏光薄膜的耐濕熱性會有效地提升。 The following structural formula (3) is a boronic diester group obtained by reacting two molecules of alcohol (R-OH) with a boronate group. Here, when the boronate group is bonded to the hydroxyl group of the PVA, the two Rs in the structural formula (3) are both PVA Chains, multiple PVA chains will cross-link each other, and the resulting polarizing film will effectively improve the humidity and heat resistance.
就本發明所使用的含硼化合物(B)而言,可例示:甲基硼酸(methyl boronate)、乙基硼酸(ethyl boronate)、丙基硼酸(propyl boronate)、丁基硼酸(butyl boronate)、戊基硼酸(pentyl boronate)、己基硼酸(hexyl boronate)、及該等的異構物、以及苯基硼酸(phenyl boronate)等。此等在分子中具有1個選自包含硼酸基(boronate group)及在水的存在下可轉化成硼酸基(boronate group)的含硼基之群組中之至少1種官能基。 The boron-containing compound (B) used in the present invention can be exemplified by methyl boronate, ethyl boronate, propyl boronate, butyl boronate, Pentyl boronate, hexyl boronate, and their isomers, phenyl boronate, etc. These have at least one functional group in the molecule selected from the group consisting of a boronate group and a boron-containing group that can be converted into a boronate group in the presence of water.
含硼化合物(B)藉由為芳香族化合物,會有偏光薄膜的耐濕熱性提升的情況。其原因並不清楚,但推測藉由芳香環的π-π堆積作用,水分難以滲透,偏光薄膜的耐濕熱性提升效果會變高。就這種的含硼化合物(B)而言,可列舉:苯基硼酸(phenyl boronate)、1,4-苯二硼酸(1,4-benzene diboronic acid)、1,3-苯二硼酸(1,3-benzene diboronic acid)、1,3,5-苯三硼酸(1,3,5-benzene triboronic acid)等。 Since the boron-containing compound (B) is an aromatic compound, the humidity and heat resistance of the polarizing film may be improved. The reason for this is not clear, but it is speculated that the π-π accumulation effect of the aromatic ring makes it difficult for moisture to penetrate, and the effect of improving the moisture and heat resistance of the polarizing film becomes higher. Such boron-containing compounds (B) include: phenyl boronate, 1,4-benzene diboronic acid, 1,3-benzene diboronic acid (1 ,3-benzene diboronic acid), 1,3,5-benzene triboronic acid (1,3,5-benzene triboronic acid), etc.
又,含硼化合物(B)藉由在分子中具有多個選自包含硼酸基(boronate group)及在水的存在下可轉化成硼酸基(boronate group)的含硼基之群組中之至少1種官能基,偏光薄膜的耐濕熱性會有效地提升。下述結構式(4)中顯示在分子中具有2個硼酸基(boronate group)時的含硼化合物(B)。此處,X為2價的有機基,其為伸烷基或伸芳基等。在此情況下,與PVA的羥基反應形成酯的點有4個,PVA鏈會更有效地交聯。 In addition, the boron-containing compound (B) has a plurality of at least selected from the group consisting of a boronic acid group (boronate group) and a boron-containing group that can be converted into a boronic acid group (boronate group) in the molecule. One kind of functional group, the humidity and heat resistance of the polarizing film will be effectively improved. The following structural formula (4) shows a boron-containing compound (B) when it has two boronate groups in the molecule. Here, X is a divalent organic group, and it is an alkylene group, an arylene group, or the like. In this case, there are 4 points that react with the hydroxyl groups of the PVA to form esters, and the PVA chains will be more effectively cross-linked.
就具有多個前述官能基的含硼化合物(B)而言,可列舉:甲烷二硼酸(methane diboronic acid)、乙烷二硼酸(ethane diboronic acid)、丙烷二硼酸(propane diboronic acid)、丁烷二硼酸(butane diboronic acid)、戊烷二硼酸(pentane diboronic acid)、己烷二硼酸(hexane diboronic acid)、及該等的異構物、以及1,4-苯二硼酸(1,4-benzene diboronic acid)、1,3-苯二硼酸(1,3-benzene diboronic acid)、1,3,5-苯三硼酸(1,3,5-benzene triboronic acid)等。 The boron-containing compound (B) having a plurality of the aforementioned functional groups includes: methane diboronic acid, ethane diboronic acid, propane diboronic acid, butane Butane diboronic acid, pentane diboronic acid, hexane diboronic acid, and their isomers, and 1,4-benzene diboronic acid (1,4-benzene diboronic acid) diboronic acid), 1,3-benzene diboronic acid (1,3-benzene diboronic acid), 1,3,5-benzene triboronic acid (1,3,5-benzene triboronic acid), etc.
本發明之偏光薄膜中之源自含硼化合物(B)的硼元素含量相對於聚乙烯醇(A)100質量份必須為0.1~3質量份。在源自含硼化合物(B)的硼元素含量少於0.1質量份的情況下,聚乙烯醇(A)的交聯量少,提升耐濕熱性的效果不夠充分。源自含硼化合物(B)的硼元素含量較佳為0.2質量份以上,更佳為0.3質量份以上。另一方面,若使源自含硼化合物(B)的硼元素含量多於3質量份,則薄膜會變得太硬而使操作性下降,而且還有需要長處理時間等生產性下降的可能。源自含硼化合物(B)的硼元素含量較佳為2質量份以下,特佳為1質量份以下。源自含硼化合物(B)的硼元素含量係能夠藉由1H-NMR測定而得到。 The content of the boron element derived from the boron-containing compound (B) in the polarizing film of the present invention must be 0.1 to 3 parts by mass relative to 100 parts by mass of the polyvinyl alcohol (A). When the content of the boron element derived from the boron-containing compound (B) is less than 0.1 parts by mass, the amount of crosslinking of the polyvinyl alcohol (A) is small, and the effect of improving the moisture and heat resistance is insufficient. The content of the boron element derived from the boron-containing compound (B) is preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more. On the other hand, if the content of the boron element derived from the boron-containing compound (B) is more than 3 parts by mass, the film becomes too hard and the workability is lowered, and there is a possibility that the productivity may be lowered, such as requiring a long processing time. . The content of the boron element derived from the boron-containing compound (B) is preferably 2 parts by mass or less, particularly preferably 1 part by mass or less. The boron element content derived from the boron-containing compound (B) can be obtained by 1 H-NMR measurement.
本發明之偏光薄膜係以進一步含有硼酸為佳,藉此能夠在高溫下進行溼式拉伸時更有效地防止PVA溶出到水中。此時,偏光薄膜中的所有硼元素含量較佳為0.2~5質量%。此處,所有硼元素含量是指將包括源自含硼化合物(B)的硼元素含量與源自硼酸的硼元素含量的所有硼元素的含量總計的量。在偏光薄膜中的所有硼元素含量少於0.2質量%的情況下,提升耐濕熱性的效果會下降。偏光薄膜中的所有硼元素含量更佳為1質量%以上。另一方面,在偏光薄膜中的所有硼元素含量多於5質量%的情況下,會有高溫時的偏光薄膜的尺寸變化變大的情況。偏光薄膜中的所有硼元素含量更佳為4.5質量%以下。偏光薄膜中的所有硼元素含量係藉由ICP發射光譜等而求得。 The polarizing film of the present invention preferably further contains boric acid, so that it can more effectively prevent PVA from eluting into water during wet stretching at high temperature. At this time, the content of all boron elements in the polarizing film is preferably 0.2 to 5% by mass. Here, the content of all boron elements means the sum of the content of all boron elements including the content of boron elements derived from the boron-containing compound (B) and the content of boron elements derived from boric acid. In the case where the content of all boron elements in the polarizing film is less than 0.2% by mass, the effect of improving the humidity and heat resistance may decrease. The content of all boron elements in the polarizing film is more preferably 1% by mass or more. On the other hand, when the content of all boron elements in the polarizing film is more than 5% by mass, the dimensional change of the polarizing film at high temperatures may increase. The content of all boron elements in the polarizing film is more preferably 4.5% by mass or less. The content of all boron elements in the polarizing film is obtained by ICP emission spectroscopy.
本發明之偏光薄膜所含有的PVA的聚合度較佳為1,500~6,000的範圍內,更佳為1,800~5,000的範圍內,再更佳為2,000~4,000的範圍內。藉由該聚合度在1,500以上,能夠提升單軸拉伸薄膜所得到的偏光薄膜的耐久性。另一方面,藉由該聚合度在6,000以下,能夠抑制製造成本的上升或製膜時的製程進行性差的情況等。還有,本說明書中的PVA的聚合度是指根據JIS K6726-1994的記載測定的平均聚合度。 The degree of polymerization of the PVA contained in the polarizing film of the present invention is preferably in the range of 1,500 to 6,000, more preferably in the range of 1,800 to 5,000, and still more preferably in the range of 2,000 to 4,000. When the degree of polymerization is 1,500 or more, the durability of the polarizing film obtained by the uniaxially stretched film can be improved. On the other hand, when the degree of polymerization is 6,000 or less, it is possible to suppress an increase in manufacturing costs, poor process progress during film formation, and the like. In addition, the degree of polymerization of PVA in this specification means the average degree of polymerization measured in accordance with the description of JIS K6726-1994.
從單軸拉伸薄膜所得到的偏光薄膜的耐水性的點來看,本發明之偏光薄膜所含有的PVA的皂化度較佳為95莫耳%以上,更佳為96莫耳%以上,再更佳為98莫耳%以上。還有,本說明書中的PVA的皂化度是指相對於PVA所具有之藉由皂化而能夠被轉換成乙烯醇單元(-CH2-CH(OH)-)之結構單元(通常為乙烯酯單元)與乙烯醇單元的合計莫耳數而言,該乙烯醇單元的莫耳數所佔的比例(莫耳%)。該皂化度係能夠根據JIS K6726-1994的記載進行測定。 From the viewpoint of the water resistance of the polarizing film obtained by uniaxially stretching the film, the degree of saponification of PVA contained in the polarizing film of the present invention is preferably 95 mol% or more, more preferably 96 mol% or more, and More preferably, it is 98 mol% or more. In addition, the degree of saponification of PVA in this specification refers to a structural unit (usually a vinyl ester unit) that can be converted into a vinyl alcohol unit (-CH 2 -CH(OH)-) by saponification. ) And the total number of moles of vinyl alcohol units, the ratio (mole%) of the number of moles of the vinyl alcohol unit. The degree of saponification can be measured in accordance with the description of JIS K6726-1994.
本發明所使用的PVA之製造方法並沒有特殊的限定,例如可列舉:將乙烯酯單體聚合所得到之將聚乙烯酯的乙烯酯單元轉換成乙烯醇單元的方法。PVA的製造所使用的乙烯酯單體並沒有特殊限定,但例如可列舉:甲酸乙烯酯、乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、異丁酸乙烯酯、三甲基乙酸乙烯酯(vinyl pivalate)、維沙狄克酸乙烯酯(vinyl versatate)、己酸乙烯酯、辛酸乙烯酯、癸酸乙烯酯、月桂酸乙烯酯、棕櫚酸乙烯酯、硬脂酸乙烯酯、油酸乙烯酯、安息香酸乙烯酯等。從經濟性的觀點來看,較佳為乙酸乙烯酯。 The manufacturing method of the PVA used in the present invention is not particularly limited. For example, a method of converting a vinyl ester unit of a polyvinyl ester into a vinyl alcohol unit obtained by polymerizing a vinyl ester monomer can be mentioned. The vinyl ester monomer used in the manufacture of PVA is not particularly limited, but examples include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, and trimethyl vinyl acetate. (vinyl pivalate), vinyl versatate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate Esters, vinyl benzoate, etc. From the viewpoint of economic efficiency, vinyl acetate is preferred.
又,本發明所使用的PVA可為將共聚合乙烯酯單體與可與乙烯酯單體共聚合的其他單體所得到的聚乙烯酯共聚物的乙烯酯單元轉換成乙烯醇單元者。就可與乙烯酯單體共聚合的其他單體而言,例如可列舉:乙烯、丙烯、1-丁烯、異丁烯等碳數2~30的α-烯烴;(甲基)丙烯酸或其鹽;(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸十二烷酯、(甲基)丙烯酸十八烷酯等(甲基)丙烯酸酯;(甲基)丙烯醯胺;N-甲基(甲基)丙烯醯胺、N-乙基(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、二丙酮(甲基)丙烯醯胺、(甲基)丙烯醯胺丙烷磺酸或其鹽、(甲基)丙烯醯胺丙基二甲基胺或其鹽、N-羥甲基(甲基)丙烯醯胺或其衍生物等(甲基)丙烯醯胺衍生物;N-乙烯基甲醯胺、N-乙烯 基乙醯胺、N-乙烯基吡咯啶酮等N-乙烯基醯胺;甲基乙烯基醚、乙基乙烯基醚、正丙基乙烯基醚、異丙基乙烯基醚、正丁基乙烯基醚、異丁基乙烯基醚、三級丁基乙烯基醚、十二烷基乙烯基醚、硬脂基乙烯基醚等乙烯基醚;(甲基)丙烯腈等乙烯基氰(vinyl cyanide);氯乙烯、偏二氯乙烯、氟乙烯、偏二氟乙烯等鹵化乙烯;乙酸烯丙酯、氯丙烯等烯丙基化合物;順丁烯二酸或其鹽、酯或是酸酐;伊康酸或其鹽、酯或是酸酐;乙烯基三甲氧基矽烷等乙烯基矽烷基化合物;不飽和磺酸等。上述的乙烯酯共聚物可具有源自前述的其他單體的1種或2種以上之結構單元。該其他單體係在供給乙烯酯單體至聚合反應時使其預先存在於反應容器內、或是在聚合反應的進行中將其添加至反應容器內等來使用。從偏光性能的觀點來看,源自其他單體的單元的含量較佳為10莫耳%以下,更佳為5莫耳%以下,再更佳為2莫耳%以下。 In addition, the PVA used in the present invention may be obtained by converting the vinyl ester unit of the polyvinyl ester copolymer obtained by copolymerizing a vinyl ester monomer and another monomer copolymerizable with the vinyl ester monomer into a vinyl alcohol unit. As for other monomers that can be copolymerized with vinyl ester monomers, for example, ethylene, propylene, 1-butene, isobutylene, and other α-olefins with 2 to 30 carbon atoms; (meth)acrylic acid or its salts; Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate Ester, tertiary butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, etc. (meth)acrylic acid Ester; (meth)acrylamide; N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, two Acetone (meth)acrylamide, (meth)acrylamide propane sulfonic acid or its salt, (meth)acrylamide propyldimethylamine or its salt, N-methylol (meth)propylene (Meth)acrylamide derivatives such as amide or its derivatives; N-vinylamide such as N-vinylformamide, N-vinylacetamide, and N-vinylpyrrolidone; methyl Vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tertiary butyl vinyl ether, dodecyl Vinyl ethers such as vinyl ether and stearyl vinyl ether; vinyl cyanides such as (meth)acrylonitrile; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride, and vinylidene fluoride; acetic acid Allyl compounds such as allyl ester and chloropropylene; maleic acid or its salt, ester or anhydride; itaconic acid or its salt, ester or anhydride; vinyl trimethoxysilane and other vinyl silyl compounds ; Unsaturated sulfonic acid and so on. The above-mentioned vinyl ester copolymer may have one type or two or more types of structural units derived from the aforementioned other monomers. This other single system is used when supplying the vinyl ester monomer to the polymerization reaction, pre-existing in the reaction vessel, or adding it to the reaction vessel during the progress of the polymerization reaction. From the viewpoint of polarization performance, the content of the units derived from other monomers is preferably 10 mol% or less, more preferably 5 mol% or less, and still more preferably 2 mol% or less.
在上述可與乙烯酯單體共聚合的單體之中,從能夠在提高拉伸性的同時以更高的溫度進行拉伸,並且在製造光學薄膜時減少拉伸斷裂等不良的產生而更加提升光學薄膜的生產性來看,較佳為乙烯。在PVA包含乙烯單元的情況下,從如上述之拉伸性或可拉伸的溫度等的觀點來看,乙烯單元的含有率相對於構成PVA的所有結構單元的莫耳數而言,較佳為1~4莫耳%,更佳為2~3莫耳%。 Among the above-mentioned monomers that can be copolymerized with vinyl ester monomers, they can be stretched at a higher temperature while improving the stretchability, and reduce the occurrence of defects such as tensile breakage during the manufacture of optical films. From the viewpoint of improving the productivity of the optical film, ethylene is preferred. In the case where PVA contains ethylene units, from the viewpoints of stretchability or stretchable temperature as described above, the content of ethylene units relative to the number of moles of all the structural units constituting the PVA is preferably It is 1~4 mole%, more preferably 2~3 mole%.
聚合乙烯酯單體時的聚合方式可為分批聚合、半分批聚合、連續聚合、半連續聚合等任一種方式, 就聚合方法而言,可適用塊狀聚合法、溶液聚合法、懸浮聚合法、乳化聚合法等周知方法,通常會採用無溶媒或醇等溶媒中進行聚合的塊狀聚合法或溶液聚合法。在獲得高聚合度的聚乙烯酯的情況下,乳化聚合法亦為佳。溶液聚合法的溶媒並沒有特殊限定,例如為醇。溶液聚合法的溶媒所使用的醇例如為甲醇、乙醇、丙醇等低級醇。聚合液中的溶媒的使用量只要因應目標的PVA的聚合度考慮溶媒的鏈轉移來選擇即可,例如溶媒為甲醇時,較佳為從0.01~10的範圍內選擇溶媒與所有單體的質量比(溶媒/所有單體),更佳為從0.05~3的範圍內選擇溶媒與所有單體的質量比(溶媒/所有單體)。 The polymerization method when polymerizing vinyl ester monomers can be batch polymerization, semi-batch polymerization, continuous polymerization, semi-continuous polymerization, etc. As for the polymerization method, block polymerization method, solution polymerization method, and suspension polymerization method are applicable. Well-known methods such as emulsification polymerization method, generally use the block polymerization method or the solution polymerization method in which polymerization is carried out without a solvent or in a solvent such as alcohol. In the case of obtaining a polyvinyl ester with a high degree of polymerization, the emulsion polymerization method is also preferred. The solvent of the solution polymerization method is not particularly limited, and is, for example, alcohol. The alcohol used in the solvent of the solution polymerization method is, for example, a lower alcohol such as methanol, ethanol, and propanol. The amount of solvent used in the polymerization solution can be selected in accordance with the degree of polymerization of the target PVA in consideration of the chain transfer of the solvent. For example, when the solvent is methanol, it is preferable to select the quality of the solvent and all monomers from the range of 0.01 to 10 The ratio (solvent/all monomers) is more preferably to select the mass ratio of the solvent to all monomers (solvent/all monomers) from the range of 0.05 to 3.
乙烯酯單體聚合所使用的聚合起始劑只要根據聚合方法從周知的聚合起始劑、例如偶氮系起始劑、過氧化物系起始劑、氧化還原系起始劑選擇即可。偶氮系起始劑例如為2,2’-偶氮雙異丁腈、2,2’-偶氮雙(2,4-二甲基戊腈)、2,2’-偶氮雙(4-甲氧基-2,4-二甲基戊腈)。過氧化物系起始劑例如為過氧二碳酸二異丙酯、過氧二碳酸二-2-乙基己酯、過氧二碳酸二乙氧基乙酯等過氧碳酸酯系化合物;過氧新癸酸三級丁酯、過氧新癸酸-α-異丙苯酯等過氧酯(perester)系化合物;乙醯環己過磺酸(acetyl cyclohexyl sulfonyl peroxide);2-過氧苯氧基乙酸-2,4,4-三甲基戊酯;過氧化乙醯。亦可將過硫酸鉀、過硫酸銨、過氧化氫等與上述起始劑組合製成聚合起始劑。氧化還原系起始劑為例如組合上述過氧化物系起始劑與亞硫酸氫鈉、碳酸氫鈉、酒石酸、L-抗壞血酸、保 險粉(rongalite)等還原劑之聚合起始劑。聚合起始劑的使用量會隨著聚合起始劑的種類而不同,因此不能一概而定,但只要根據聚合速度進行選擇即可。例如在將2,2’-偶氮雙異丁腈或是過氧化乙醯用於聚合起始劑的情況下,相對於乙烯酯單體而言,較佳為0.01~0.2莫耳%,更佳為0.02~0.15莫耳%。聚合溫度並沒有特殊限定,但室溫~150℃左右為適當,較佳為40℃以上且為使用的溶媒的沸點以下。 The polymerization initiator used for the polymerization of vinyl ester monomers may be selected from well-known polymerization initiators, for example, azo-based initiators, peroxide-based initiators, and redox-based initiators according to the polymerization method. The azo-based initiator is, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4 -Methoxy-2,4-dimethylvaleronitrile). The peroxide-based initiator is, for example, peroxycarbonate-based compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate; Perester compounds such as tertiary butyl oxyneodecanoate and peroxyneodecanoic acid-α-cumyl; acetyl cyclohexyl sulfonyl peroxide; 2-
乙烯酯單體的聚合可在鏈轉移劑的存在下進行。鏈轉移劑為例如乙醛、丙醛等醛類;丙酮、甲基乙基酮等酮類;2-羥基乙烷硫醇等硫醇類;次膦酸鈉一水合物等次膦酸鹽類等,其中較佳使用醛類及酮類。鏈轉移劑的使用量係能夠根據使用的鏈轉移劑的鏈轉移係數及目標的PVA的聚合度來決定,但一般是以相對於乙烯酯單體100質量份為0.1~10質量份為佳。 The polymerization of vinyl ester monomers can be carried out in the presence of a chain transfer agent. Chain transfer agents are, for example, aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methyl ethyl ketone; mercaptans such as 2-hydroxyethane mercaptan; phosphinates such as sodium phosphinate monohydrate Among them, aldehydes and ketones are preferably used. The amount of the chain transfer agent used can be determined according to the chain transfer coefficient of the chain transfer agent used and the degree of polymerization of the target PVA, but it is generally preferably 0.1-10 parts by mass relative to 100 parts by mass of the vinyl ester monomer.
聚乙烯酯的皂化係能夠在例如醇或含水醇中於該聚乙烯酯溶解的狀態下進行。用於皂化的醇係可列舉例如甲醇、乙醇等低級醇,較佳為甲醇。用於皂化的醇亦可例如以其質量的40質量%以下的比例包含丙酮、乙酸甲酯、乙酸乙酯、苯等其他溶媒。用於皂化的觸媒為例如氫氧化鉀、氫氧化鈉等鹼金屬的氫氧化物、甲氧鈉等鹼觸媒、礦酸等酸觸媒。進行皂化的溫度並沒有限定,但較佳為20~60℃的範圍內。在依據皂化的進行而有凝膠狀的生成物析出的情況下,能夠粉碎生成物後進行洗淨、乾燥而得到PVA。皂化方法不限於前述的方法,能夠使用周知的方法。 The saponification system of the polyvinyl ester can be performed in a state where the polyvinyl ester is dissolved in, for example, alcohol or hydrous alcohol. Examples of alcohols used for saponification include lower alcohols such as methanol and ethanol, and methanol is preferred. The alcohol used for saponification may also contain other solvents such as acetone, methyl acetate, ethyl acetate, benzene, etc., in a proportion of 40% by mass or less of its mass. The catalyst used for saponification is, for example, hydroxides of alkali metals such as potassium hydroxide and sodium hydroxide, alkali catalysts such as sodium methoxide, and acid catalysts such as mineral acid. The temperature for performing saponification is not limited, but it is preferably in the range of 20 to 60°C. When a gel-like product precipitates due to the progress of the saponification, the product can be crushed, washed and dried to obtain PVA. The saponification method is not limited to the aforementioned method, and a well-known method can be used.
用於製造本發明之偏光薄膜之PVA薄膜除了上述PVA外,還能夠包含塑化劑。就較佳的塑化劑而言,可列舉多元醇,就具體例而言,可列舉:乙二醇、甘油、丙二醇、二乙二醇、二甘油、三乙二醇、四乙二醇、三羥甲基丙烷等,進一步能夠包含此等塑化劑的1種或2種以上。在此等之中,從提升拉伸性的效果的點來看,較佳為甘油。 In addition to the above-mentioned PVA, the PVA film used to manufacture the polarizing film of the present invention can also contain a plasticizer. As far as preferable plasticizers are concerned, polyhydric alcohols can be cited, and specific examples include: ethylene glycol, glycerin, propylene glycol, diethylene glycol, diglycerol, triethylene glycol, tetraethylene glycol, Trimethylolpropane and the like can further include one or two or more of these plasticizers. Among these, from the viewpoint of the effect of improving stretchability, glycerin is preferred.
用於製造本發明之偏光薄膜之PVA薄膜中之塑化劑的含量相對於100質量份的PVA而言,較佳為1~20質量份的範圍內,更佳為3~17質量份的範圍內,再更佳為5~15質量份的範圍內。藉由該含量在1質量份以上,薄膜的拉伸性會進一步提升。另一方面,藉由該含量在20質量份以下,而能夠抑制薄膜變得過於柔軟所導致的操作性下降。 The content of the plasticizer in the PVA film used to manufacture the polarizing film of the present invention is preferably in the range of 1-20 parts by mass, more preferably in the range of 3-17 parts by mass relative to 100 parts by mass of PVA Within, more preferably within the range of 5 to 15 parts by mass. With the content of 1 part by mass or more, the stretchability of the film will be further improved. On the other hand, when the content is 20 parts by mass or less, it is possible to suppress the decrease in workability caused by the film becoming too soft.
用於製造本發明之偏光薄膜之PVA薄膜中係能夠視情況而進一步適當地摻合填充劑、銅化合物等加工安定劑、耐候性安定劑、著色劑、紫外線吸收劑、光穩定劑、抗氧化劑、抗靜電劑、阻燃劑、其他的熱塑性樹脂、潤滑劑、香料、消泡劑、除臭劑、增量劑、剝離劑、脫模劑、補強劑、交聯劑、防黴劑、防腐劑、結晶化速度延遲劑等添加劑。 The PVA film used to manufacture the polarizing film of the present invention can be further appropriately blended with processing stabilizers such as fillers and copper compounds, weather resistance stabilizers, colorants, ultraviolet absorbers, light stabilizers, and antioxidants as appropriate. , Antistatic agents, flame retardants, other thermoplastic resins, lubricants, fragrances, defoamers, deodorants, extenders, stripping agents, mold release agents, reinforcing agents, crosslinking agents, antifungal agents, antiseptics Additives such as agents, crystallization rate retarders, etc.
用於製造本發明之偏光薄膜之PVA薄膜中之PVA及塑化劑總計所佔的比例基於PVA薄膜的質量,較佳為80質量%以上,更佳為90質量%以上,再更佳為95質量%以上。 The total proportion of PVA and plasticizer in the PVA film used to manufacture the polarizing film of the present invention is based on the quality of the PVA film, and is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95 Above mass%.
用於製造本發明之偏光薄膜之PVA薄膜的膨潤度較佳為160~240%的範圍內,更佳為170~230%的範圍內,特佳為180~220%的範圍內。藉由膨潤度在160%以上,能夠抑制結晶的極度發展,而能夠穩定地拉伸至高倍率。另一方面,藉由膨潤度在240%以下,可抑制拉伸時的溶解,即便在更高溫的條件下,也能夠進行拉伸。 The degree of swelling of the PVA film used to manufacture the polarizing film of the present invention is preferably in the range of 160-240%, more preferably in the range of 170-230%, particularly preferably in the range of 180-220%. With a swelling degree of 160% or more, the extreme development of crystals can be suppressed, and it can be stretched to a high magnification stably. On the other hand, when the degree of swelling is 240% or less, dissolution during stretching can be suppressed, and stretching can be performed even under higher temperature conditions.
用於製造本發明之偏光薄膜之PVA薄膜的厚度並沒有特殊的限制,但一般來說較佳為1~100μm,更佳為5~60μm,特佳為10~45μm左右。若該厚度太薄,在用於製造偏光薄膜的單軸拉伸處理時,會有容易產生拉伸斷裂的傾向。又,若該厚度太厚,在用於製造偏光薄膜的單軸拉伸處理時,容易產生拉伸不均。 The thickness of the PVA film used in the production of the polarizing film of the present invention is not particularly limited, but generally it is preferably 1-100 μm, more preferably 5-60 μm, and particularly preferably 10 to 45 μm. If the thickness is too thin, it tends to be easily broken during the uniaxial stretching process for producing a polarizing film. In addition, if the thickness is too thick, uneven stretching is likely to occur during the uniaxial stretching process used to manufacture the polarizing film.
用於製造本發明之偏光薄膜之PVA薄膜的寬度並沒有特殊的限制,能夠根據所製造的偏光薄膜的用途等來決定。近年來,從液晶電視或液晶顯示器正朝向大畫面發展的點來看,若使用於製造偏光薄膜之PVA薄膜的寬度在3m以上,則適用於這些用途。另一方面,若用於製造偏光薄膜之PVA薄膜的寬度太過寬,則在經實用化的裝置中製造偏光薄膜時,均一進行單軸拉伸容易變得困難,因此用於製造偏光薄膜之PVA薄膜的寬度較佳為7m以下。 The width of the PVA film used in the production of the polarizing film of the present invention is not particularly limited, and can be determined according to the use of the produced polarizing film and the like. In recent years, from the point of view that liquid crystal televisions or liquid crystal displays are moving towards large screens, if the width of the PVA film used to make the polarizing film is 3m or more, it is suitable for these applications. On the other hand, if the width of the PVA film used to manufacture the polarizing film is too wide, it is easy to be difficult to uniformly uniaxially stretch the polarizing film in a practical device. The width of the PVA film is preferably 7 m or less.
用於製造本發明之偏光薄膜之PVA薄膜之製造方法並沒有特殊的限定,可較佳地採用使製膜後的薄膜的厚度及寬度更均一的製造方法,舉例來說,能夠使用構成用於製造偏光薄膜之PVA薄膜的上述PVA、及 視需要而進一步添加的上述塑化劑、添加劑及後述的界面活性劑等之中的1種或2種以上溶解於液體介質中而成的製膜原液來製造,或是使用包含PVA、及視需要而進一步包含塑化劑、添加劑、界面活性劑、及液體介質等之中的1種或2種以上且熔融PVA的製膜原液來製造。在該製膜原液含有塑化劑、添加劑、及界面活性劑的至少1種的情況下,係以均一地混合該等成分為佳。 The manufacturing method of the PVA film used to manufacture the polarizing film of the present invention is not particularly limited. A manufacturing method that makes the thickness and width of the film more uniform can be preferably used. For example, the structure can be used A film-forming stock solution prepared by dissolving one or more of the above-mentioned PVA of the above-mentioned PVA film, and the above-mentioned plasticizer, additives, and the following surfactant, etc., which are added as necessary, in the PVA film of the polarizing film in a liquid medium It can be produced, or it can be produced using a film-forming stock solution containing PVA and, if necessary, further containing one or two or more of plasticizers, additives, surfactants, and liquid media, and molten PVA. When the film-forming stock solution contains at least one of a plasticizer, an additive, and a surfactant, it is preferable to uniformly mix these components.
就用於調製製膜原液的上述液體介質而言,可列舉例如:水、二甲基亞碸、二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯啶酮、乙二醇、甘油、丙二醇、二乙二醇、三乙二醇、四乙二醇、三羥甲基丙烷、乙二胺、二乙三胺等,能夠使用此等之中的1種或2種以上。其中,從對環境的負荷或回收性的點來看,較佳為水。 Regarding the above-mentioned liquid medium used to prepare the film-forming stock solution, for example, water, dimethyl sulfide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and ethylene two Alcohol, glycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, ethylenediamine, diethylenetriamine, etc., one or more of these can be used . Among them, from the viewpoint of load on the environment and recyclability, water is preferred.
製膜原液的揮發分率(製膜時因揮發或蒸發所去除的液體介質等揮發性成分在製膜原液中的含有比例)會隨著製膜方法、製膜條件等而變得不同,但一般來說,較佳為50~95質量%的範圍內,更佳為55~90質量%的範圍內。藉由製膜原液的揮發分率在50質量%以上,製膜原液的黏度不會變得太高,調製製膜原液時的過濾或消泡能順利地進行,而易於製造異物或缺陷少的薄膜。另一方面,藉由製膜原液的揮發分率在95質量%以下,製膜原液的濃度不會變得太低,而易於在工業上製造薄膜。 The volatile fraction of the film-forming stock solution (the content ratio of the volatile components such as the liquid medium removed by volatilization or evaporation during film-forming in the film-forming stock solution) varies depending on the film forming method, film forming conditions, etc., but Generally, it is preferably in the range of 50 to 95% by mass, and more preferably in the range of 55 to 90% by mass. With the volatile content of the film-forming stock solution being 50% by mass or more, the viscosity of the film-forming stock solution will not become too high, the filtration or defoaming when preparing the film-forming stock solution can be smoothly performed, and it is easy to produce foreign objects or defects. film. On the other hand, when the volatile fraction of the film-forming stock solution is 95% by mass or less, the concentration of the film-forming stock solution does not become too low, and it is easy to manufacture a thin film industrially.
製膜原液係以包含界面活性劑為佳,藉由包含界面活性劑,在製膜性提升而抑制薄膜的厚度不均的 產生的同時,使從用於製膜的金屬輥或帶剝離薄膜變得容易。在從包含界面活性劑的製膜原液製造PVA薄膜的情況下,該薄膜中可含有界面活性劑。上述界面活性劑的種類並沒有特殊限定,但由從金屬輥或帶的剝離性之觀點等來看,較佳為陰離子性界面活性劑或非離子性界面活性劑。 The film-forming stock solution preferably contains a surfactant. By containing the surfactant, the film-forming properties are improved and the unevenness of the film thickness is suppressed, and the film can be peeled from the metal roll or tape used for film-forming. Easy. When a PVA film is produced from a film-forming stock solution containing a surfactant, the film may contain a surfactant. The type of the surfactant is not particularly limited, but from the viewpoint of the peelability of a metal roll or belt, etc., an anionic surfactant or a nonionic surfactant is preferred.
就陰離子性界面活性劑而言,適合為例如月桂酸鉀等羧酸型;聚氧乙烯月桂基醚硫酸鹽、硫酸辛酯等硫酸酯型;十二烷基苯磺酸鹽等磺酸型等。 As for anionic surfactants, suitable are, for example, carboxylic acid types such as potassium laurate; sulfate ester types such as polyoxyethylene lauryl ether sulfate and octyl sulfate; sulfonic acid types such as dodecylbenzene sulfonate, etc. .
就非離子性界面活性劑而言,適合為例如聚氧乙烯油基醚等烷基醚型;聚氧乙烯辛基苯基醚等烷基苯基醚型;聚氧乙烯月桂酸酯等烷基酯型;聚氧乙烯月桂基胺基醚等烷基胺型;聚氧乙烯月桂酸醯胺等烷基醯胺型;聚氧乙烯聚氧丙烯醚等聚丙二醇醚型;月桂酸二乙醇醯胺、油酸二乙醇醯胺等烷醇醯胺型;聚氧化烯烯丙基苯基醚等烯丙基苯基醚型等。 As for the nonionic surfactant, suitable are, for example, alkyl ether type such as polyoxyethylene oleyl ether; alkyl phenyl ether type such as polyoxyethylene octyl phenyl ether; and alkyl group such as polyoxyethylene laurate. Ester type; Alkylamine type such as polyoxyethylene lauryl amino ether; Alkyl amine type such as polyoxyethylene lauric acid amide; Polypropylene glycol ether type such as polyoxyethylene polyoxypropylene ether; Diethanolamide laurate , Alkanol amide type such as diethanolamide oleic acid; Allyl phenyl ether type such as polyoxy allyl phenyl ether etc.
此等的界面活性劑係能夠單獨使用1種,或是組合2種以上來使用。 These surfactant systems can be used individually by 1 type or in combination of 2 or more types.
在製膜原液包含界面活性劑的情況下,其含量相對於100質量份的製膜原液所含的PVA而言,較佳為0.01~0.5質量份的範圍內,更佳為0.02~0.3質量份的範圍內,特佳為0.05~0.2質量份的範圍內。藉由該含量在0.01質量份以上,製膜性及剝離性會進一步提升。另一方面,藉由該含量在0.5質量份以下,能夠抑制界面活性劑滲出至PVA薄膜的表面而產生黏結、操作性下降。 When the film-forming stock solution contains a surfactant, its content is preferably in the range of 0.01 to 0.5 parts by mass, and more preferably 0.02 to 0.3 parts by mass relative to the PVA contained in 100 parts by mass of the film-forming stock solution It is particularly preferably in the range of 0.05 to 0.2 parts by mass. When the content is 0.01 parts by mass or more, film-forming properties and releasability are further improved. On the other hand, when the content is 0.5 parts by mass or less, it is possible to prevent the surfactant from oozing out to the surface of the PVA film to cause adhesion and decrease in workability.
就製造使用上述製膜原液製造偏光薄膜所使用的PVA薄膜時的製膜方法而言,可列舉例如:澆鑄製膜法、擠出製膜法、濕式製膜法、凝膠製膜法等。此等的製膜方法可以僅採用1種,亦可採用2種以上的組合。在這些製膜方法之中,澆鑄製膜法、擠出製膜法由於可獲得用於製造厚度及寬度均一且物性良好的偏光薄膜之PVA薄膜而較佳。製膜得到的PVA薄膜能夠視需要地進行乾燥或熱處理。 The film forming method when manufacturing the PVA film used to manufacture the polarizing film using the above-mentioned film forming stock solution includes, for example, a cast film method, an extrusion film method, a wet film method, a gel film method, etc. . Only one type of these film forming methods may be used, or a combination of two or more types may be used. Among these film forming methods, the cast film forming method and the extrusion film forming method are preferable because they can obtain a PVA film for producing a polarizing film with uniform thickness and width and good physical properties. The PVA film obtained by film formation can be dried or heat-treated as necessary.
就用於製造本發明之偏光薄膜之PVA薄膜的具體製造方法的例子而言,例如在工業上能夠較佳採用下述方法:使用T型狹縫式模、料斗板(hopper plate)、I字模、唇式塗布模(lip coater die)等,將上述的製膜原液均勻地吐出或流延在位於最上游側的旋轉之經加熱的第1輥(或帶)的周圍面上,使揮發性成分從吐出或流延於該第1輥(或帶)的周圍面上的膜的其中一面上蒸發並乾燥,接著在配置於其下游側的1個或多個旋轉之經加熱的輥的周圍面上進一步乾燥、或是使其通過熱風乾燥裝置之中來進一步乾燥後,藉由捲取裝置進行捲取。利用經加熱的輥進行的乾燥或利用熱風乾燥裝置進行的乾燥係可適當地組合來實施。 As for the specific manufacturing method of the PVA film used to manufacture the polarizing film of the present invention, for example, the following methods can be preferably adopted in industry: using a T-shaped slit mold, a hopper plate, and an I-shaped mold , Lip coater die, etc., uniformly spit out or cast the above-mentioned film-forming stock solution on the surrounding surface of the heated first roller (or belt) that is located on the most upstream side to make it volatile The components evaporate and dry from one side of the film discharged or cast on the peripheral surface of the first roll (or belt), and then around one or more rotating heated rolls arranged on the downstream side After the surface is further dried or passed through a hot-air drying device for further drying, it is wound by a winding device. Drying by a heated roll or a drying system by a hot-air drying device can be suitably combined and implemented.
製造本發明之偏光薄膜時的方法並沒有特殊的限制。適合的製造方法為在包含以二色性色素將聚乙烯醇薄膜染色之染色處理以及將該薄膜單軸拉伸之拉伸處理之偏光薄膜之製造方法中,具有將該薄膜浸漬於含硼化合物(B)的水溶液之處理之偏光薄膜之製造方法。對 於用於製造本發明之偏光薄膜之PVA薄膜,可列舉:施加染色處理、單軸拉伸處理、及視需要而進一步施加膨潤處理、硼酸交聯處理、固定處理、洗淨處理、乾燥處理、熱處理等之方法。在此情況下,膨潤處理、染色處理、硼酸交聯處理、單軸拉伸處理、固定處理等各處理的順序並沒有特殊的限制,亦能夠同時進行1個或2個以上的處理。又,亦能夠進行1個或2個以上的各處理2次以上。 The method for manufacturing the polarizing film of the present invention is not particularly limited. A suitable manufacturing method is a method of manufacturing a polarizing film including a dyeing process of dyeing a polyvinyl alcohol film with a dichroic dye and a stretching process of uniaxially stretching the film, including immersing the film in a boron-containing compound (B) A manufacturing method of polarizing film processed by aqueous solution. For the PVA film used to manufacture the polarizing film of the present invention, it can be enumerated: applying dyeing treatment, uniaxial stretching treatment, and further applying swelling treatment, boric acid crosslinking treatment, fixing treatment, washing treatment, drying treatment, Methods such as heat treatment. In this case, the order of each treatment such as swelling treatment, dyeing treatment, boric acid cross-linking treatment, uniaxial stretching treatment, and fixing treatment is not particularly limited, and one or two or more treatments can be carried out at the same time. In addition, it is also possible to perform one or two or more treatments twice or more.
膨潤處理係能夠藉由將PVA薄膜浸漬於水中來進行。就浸漬於水中時的水的溫度而言,較佳為20~40℃的範圍內,更佳為22~38℃的範圍內,再更佳為25~35℃的範圍內。又,就浸漬於水中的時間而言,例如較佳為0.1~5分鐘的範圍內,更佳為0.2~3分鐘的範圍內。還有,浸漬於水中時的水並不限於純水,可以為各種成分溶解而成的水溶液,或亦可為水與水性介質的混合物。 The swelling treatment can be performed by immersing the PVA film in water. The temperature of the water when immersed in water is preferably in the range of 20 to 40°C, more preferably in the range of 22 to 38°C, and still more preferably in the range of 25 to 35°C. In addition, the time for immersion in water is, for example, preferably in the range of 0.1 to 5 minutes, and more preferably in the range of 0.2 to 3 minutes. In addition, the water when immersed in water is not limited to pure water, and may be an aqueous solution in which various components are dissolved, or may be a mixture of water and an aqueous medium.
染色處理係能夠藉由使二色性色素與PVA薄膜接觸而進行。就二色性色素而言,通常使用碘系色素。就染色處理的時期而言,可為單軸拉伸處理前、單軸拉伸處理時、單軸拉伸處理後的任一個階段。染色處理通常會藉由將PVA薄膜浸漬於作為染色浴的含碘-碘化鉀的溶液(尤其是水溶液)中來進行。染色浴中的碘的濃度較佳為0.01~0.5質量%的範圍內,碘化鉀的濃度較佳為0.01~10質量%的範圍內。又,染色浴的溫度較佳為20~50℃,特佳為25~40℃。適合的染色時間為0.2分鐘至5分鐘。 The dyeing process can be performed by bringing the dichroic dye into contact with the PVA film. For dichroic dyes, iodine-based dyes are usually used. The timing of the dyeing treatment may be any stage before the uniaxial stretching treatment, during the uniaxial stretching treatment, and after the uniaxial stretching treatment. The dyeing treatment is usually performed by immersing the PVA film in a solution (especially an aqueous solution) containing iodine-potassium iodide as a dyeing bath. The concentration of iodine in the dye bath is preferably in the range of 0.01 to 0.5% by mass, and the concentration of potassium iodide is preferably in the range of 0.01 to 10% by mass. In addition, the temperature of the dyeing bath is preferably 20 to 50°C, particularly preferably 25 to 40°C. The suitable dyeing time is 0.2 minutes to 5 minutes.
藉由對PVA薄膜施加硼酸交聯處理,能夠在高溫下進行濕式拉伸時更有效地防止PVA溶出至水中。由此觀點來看,硼酸交聯處理係以在單軸拉伸處理之前進行為佳。硼酸交聯處理係能夠藉由在含硼酸交聯劑的水溶液中浸漬PVA薄膜來進行。就該硼酸交聯劑而言,能夠使用硼酸、硼砂等硼酸鹽等之含硼的無機化合物的1種或2種以上。含硼酸交聯劑的水溶液中之硼酸交聯劑的濃度較佳為1~15質量%的範圍內,更佳為2~7質量%的範圍內。藉由硼酸交聯劑的濃度在1~15質量%的範圍內,能夠維持充分的拉伸性。含硼酸交聯劑的水溶液亦可含有碘化鉀等助劑。含硼酸交聯劑的水溶液的溫度較佳為20~50℃的範圍內,特佳為25~40℃的範圍內。藉由使該溫度在20~50℃的範圍內,能夠有效地進行硼酸交聯。 By applying the boric acid crosslinking treatment to the PVA film, it is possible to more effectively prevent the PVA from dissolving into water during wet stretching at high temperatures. From this point of view, the boric acid crosslinking treatment is preferably performed before the uniaxial stretching treatment. The boric acid crosslinking treatment can be performed by immersing the PVA film in an aqueous solution containing a boric acid crosslinking agent. As the boric acid crosslinking agent, one or two or more types of boron-containing inorganic compounds such as boric acid and borax salts can be used. The concentration of the boric acid crosslinking agent in the aqueous solution containing the boric acid crosslinking agent is preferably in the range of 1-15% by mass, more preferably in the range of 2-7% by mass. When the concentration of the boric acid crosslinking agent is in the range of 1 to 15% by mass, sufficient stretchability can be maintained. The aqueous solution containing the boric acid crosslinking agent may also contain auxiliary agents such as potassium iodide. The temperature of the aqueous solution containing the boric acid crosslinking agent is preferably in the range of 20 to 50°C, particularly preferably in the range of 25 to 40°C. By setting the temperature in the range of 20 to 50°C, boric acid crosslinking can be effectively performed.
單軸拉伸處理係可以濕式拉伸法或乾式拉伸法中任一種來進行。在濕式拉伸法的情況下,能夠在含硼酸的水溶液中進行,或是亦能夠在上述的染色浴中或後述的固定處理浴中進行。又,在乾式拉伸法的情況下,可直接在室溫下進行單軸拉伸處理,或是亦可一面加熱一面進行單軸拉伸處理,亦或是能夠使用吸水後的PVA薄膜而在空氣中進行單軸拉伸處理。在此等之中,以濕式拉伸法為佳,而以在含硼酸的水溶液中進行單軸拉伸處理為更佳。硼酸水溶液中之硼酸的濃度較佳為0.5~6質量%的範圍內,更佳為1~5質量%的範圍內。又,硼酸水溶液亦可含有碘化鉀,其濃度係以在0.01~10質量% 的範圍內為佳。單軸拉伸處理的拉伸溫度較佳為30~90℃的範圍內,更佳為40~80℃的範圍內,特佳為50~70℃的範圍內。又,從所得到的偏光薄膜的偏光性能的點來看,單軸拉伸處理的拉伸倍率(從原料的PVA薄膜開始的總拉伸倍率)較佳為5倍以上,更佳為5.5倍以上。拉伸倍率的上限並沒有特殊的限制,但拉伸倍率較佳為8倍以下。 The uniaxial stretching treatment system can be performed by either a wet stretching method or a dry stretching method. In the case of the wet stretching method, it can be carried out in a boric acid-containing aqueous solution, or can also be carried out in the above-mentioned dyeing bath or the fixed treatment bath described later. Moreover, in the case of the dry stretching method, the uniaxial stretching process can be performed directly at room temperature, or the uniaxial stretching process can also be performed while heating, or the PVA film can be used after water absorption. Perform uniaxial stretching in air. Among these, the wet stretching method is preferred, and the uniaxial stretching treatment in an aqueous solution containing boric acid is more preferred. The concentration of boric acid in the boric acid aqueous solution is preferably in the range of 0.5 to 6% by mass, more preferably in the range of 1 to 5% by mass. In addition, the boric acid aqueous solution may contain potassium iodide, and its concentration is preferably in the range of 0.01 to 10% by mass. The stretching temperature of the uniaxial stretching treatment is preferably in the range of 30 to 90°C, more preferably in the range of 40 to 80°C, and particularly preferably in the range of 50 to 70°C. In addition, from the viewpoint of the polarization performance of the obtained polarizing film, the stretching ratio of the uniaxial stretching treatment (total stretching ratio from the raw material PVA film) is preferably 5 times or more, more preferably 5.5 times above. The upper limit of the stretching ratio is not particularly limited, but the stretching ratio is preferably 8 times or less.
在對長形的PVA薄膜進行單軸拉伸處理時的單軸拉伸處理的方向並沒有特殊的限制,能夠採用往長度方向的單軸拉伸處理或橫向單軸拉伸處理、或是所謂的斜向拉伸處理,但從得到偏光性能優異的偏光薄膜來看,較佳為往長度方向的單軸拉伸處理。往長度方向的單軸拉伸處理係能夠藉由使用具備相互平行的多個輥的拉伸裝置並改變各輥間的周速來進行。另一方面,橫向單軸拉伸處理係能夠使用拉幅型拉伸機來進行。 There are no special restrictions on the direction of the uniaxial stretching treatment when the long PVA film is uniaxially stretched. The uniaxial stretching treatment in the longitudinal direction or the transverse uniaxial stretching treatment, or the so-called However, from the viewpoint of obtaining a polarizing film with excellent polarizing properties, uniaxial stretching in the longitudinal direction is preferred. The uniaxial stretching process in the longitudinal direction can be performed by using a stretching device provided with a plurality of rolls parallel to each other and changing the peripheral speed between the rolls. On the other hand, the transverse uniaxial stretching treatment system can be performed using a tenter type stretching machine.
當製造偏光薄膜時,為了加強二色性色素(碘系色素等)對PVA薄膜的吸附,以在單軸拉伸處理後進行固定處理為佳。就用於固定處理的固定處理浴而言,能夠較佳地使用含有含硼化合物(B)的水溶液。又,亦可視需要地在固定處理浴中添加硼酸、碘化合物、金屬化合物等。固定處理浴的溫度較佳為15~60℃,特佳為25~40℃。 When manufacturing a polarizing film, in order to strengthen the adsorption of the dichroic dye (iodine-based dye, etc.) to the PVA film, it is better to perform a fixing treatment after the uniaxial stretching treatment. As for the fixing treatment bath used for the fixing treatment, an aqueous solution containing the boron-containing compound (B) can be preferably used. In addition, boric acid, iodine compounds, metal compounds, etc. may be added to the fixed treatment bath as needed. The temperature of the fixed treatment bath is preferably 15-60°C, particularly preferably 25-40°C.
含硼化合物(B)可在染色處理、硼酸交聯處理、單軸拉伸處理、固定處理中的任一步驟中吸附於偏光薄膜上,但從不對單軸拉伸處理時的斷裂造成影響, 特佳為在固定處理時進行吸附。又,含硼化合物(B)可不僅使用一種,亦可混合兩種以上來使用。含硼化合物(B)的水溶液濃度較佳為0.05~15質量%,特佳為0.1質量%~10質量%。含硼化合物(B)的水溶液濃度若低於0.05質量%時,有時吸附變慢,水溶液濃度若高於15質量%時,偏光薄膜表面有時會有含硼化合物(B)的析出物產生。又,從提升偏光性能的點來看,含有含硼化合物(B)的水溶液係以含有碘化鉀等助劑為佳。又,處理浴的溫度較佳為10~70℃,更佳為設為20~60℃,特佳為設為20℃~50℃。溫度若過低,則在處理浴中有時會有含硼化合物(B)析出。又,溫度若過高,則難以在較溫和的條件下輕易地在工業上製造。 The boron-containing compound (B) can be adsorbed on the polarizing film in any step of dyeing treatment, boric acid cross-linking treatment, uniaxial stretching treatment, and fixing treatment, but it never affects the breakage during uniaxial stretching treatment. It is particularly preferred to perform adsorption during the fixation process. In addition, not only one type of boron-containing compound (B) may be used, but two or more types may be mixed and used. The concentration of the aqueous solution of the boron-containing compound (B) is preferably 0.05 to 15% by mass, particularly preferably 0.1% to 10% by mass. When the concentration of the boron-containing compound (B) in the aqueous solution is less than 0.05% by mass, the adsorption sometimes becomes slow, and when the concentration of the aqueous solution is higher than 15% by mass, the boron-containing compound (B) may precipitate on the surface of the polarizing film. . In addition, from the viewpoint of improving the polarization performance, the aqueous solution containing the boron-containing compound (B) preferably contains an auxiliary agent such as potassium iodide. In addition, the temperature of the treatment bath is preferably 10 to 70°C, more preferably 20 to 60°C, and particularly preferably 20 to 50°C. If the temperature is too low, the boron-containing compound (B) may precipitate in the treatment bath. In addition, if the temperature is too high, it will be difficult to manufacture easily industrially under relatively mild conditions.
在固定處理時使含硼化合物(B)吸附於偏光薄膜的情況下之合適的製造方法係依序施以膨潤處理、硼酸交聯處理、單軸拉伸處理、固定處理,之後亦可進一步視需要地依序施以選自洗淨處理、乾燥處理及熱處理中之1個以上的處理。 A suitable manufacturing method in the case where the boron-containing compound (B) is adsorbed on the polarizing film during the fixing treatment is to sequentially apply the swelling treatment, the boric acid cross-linking treatment, the uniaxial stretching treatment, and the fixing treatment. If necessary, one or more treatments selected from washing treatment, drying treatment, and heat treatment are sequentially applied.
洗淨處理通常是將薄膜浸漬於水、蒸餾水、純水等中來進行。此時,從提升偏光性能的點來看,用於洗淨處理的水溶液係以將碘化鉀等碘化物作為助劑而含有為佳,該碘化物的濃度較佳為設為0.5~10質量%。又,洗淨處理中的水溶液的溫度通常為5~50℃,較佳為10~45℃,更佳為15~40℃。就經濟性的觀點來看,水溶液的溫度越低越不好,水溶液的溫度若太高,則有時偏光性能會降低。 The washing treatment is usually performed by immersing the film in water, distilled water, pure water, or the like. At this time, from the viewpoint of improving the polarization performance, the aqueous solution used for the cleaning treatment preferably contains an iodide such as potassium iodide as an auxiliary agent, and the concentration of the iodide is preferably 0.5 to 10% by mass. In addition, the temperature of the aqueous solution in the washing treatment is usually 5 to 50°C, preferably 10 to 45°C, and more preferably 15 to 40°C. From an economic point of view, the lower the temperature of the aqueous solution, the worse, and if the temperature of the aqueous solution is too high, the polarization performance may decrease.
乾燥處理的條件並沒有特殊的限制,但以在30~150℃的範圍內的溫度下進行乾燥為佳,特佳為在50~130℃的範圍內的溫度下進行乾燥。藉由在30~150℃的範圍內的溫度下進行乾燥,容易獲得尺寸穩定性優異的偏光薄膜。 The conditions of the drying treatment are not particularly limited, but the drying is preferably performed at a temperature in the range of 30 to 150°C, and particularly preferably the drying is performed at a temperature in the range of 50 to 130°C. By drying at a temperature in the range of 30 to 150°C, it is easy to obtain a polarizing film with excellent dimensional stability.
藉由在乾燥處理後進行熱處理,能夠得到尺寸穩定性更優異的偏光薄膜。此處,熱處理是指將水分含量為5%以下的乾燥處理後的偏光薄膜進一步加熱而使偏光薄膜的尺寸穩定性提升之處理。熱處理的條件並沒有特殊的限制,但較佳為在60℃~150℃的範圍內進行熱處理,特佳為在70℃~150℃的範圍內進行熱處理。若在比60℃還低的溫度下進行熱處理,則因熱處理造成的尺寸穩定化效果會不夠充分;若在比150℃還高的溫度下進行熱處理,則有時偏光薄膜會激烈產生紅變。 By performing the heat treatment after the drying treatment, a polarizing film with more excellent dimensional stability can be obtained. Here, the heat treatment refers to a process of further heating the dried polarizing film with a moisture content of 5% or less to improve the dimensional stability of the polarizing film. The conditions of the heat treatment are not particularly limited, but the heat treatment is preferably performed in the range of 60°C to 150°C, and particularly preferably the heat treatment is performed in the range of 70°C to 150°C. If the heat treatment is performed at a temperature lower than 60°C, the dimensional stabilization effect caused by the heat treatment will not be sufficient; if the heat treatment is performed at a temperature higher than 150°C, the polarizing film may be intensely reddened.
如上述方式進行所得到的偏光薄膜的耐濕熱性能係能夠以在高溫且高濕度下之源自PVA-碘錯合物的顏色的褪色作為指標來進行評價。具體來說,能夠以使2片偏光薄膜疊合成正交偏光(crossed nicol)時之褪色後的吸光度D(610nm)相對於褪色前的吸光度C(610nm)的百分率(吸光度殘存率)進行評價。在60℃/90%RH下褪色8小時後的吸光度殘存率較佳為22%以上,更佳為25%以上。 The humidity and heat resistance of the polarizing film obtained as described above can be evaluated using the color fading derived from the PVA-iodine complex under high temperature and high humidity as an index. Specifically, it can be evaluated as the percentage (absorbance residual ratio) of the absorbance D (610 nm) after fading to the absorbance C (610 nm) before fading when the two polarizing films are laminated into crossed nicol. The residual rate of absorbance after fading for 8 hours at 60°C/90%RH is preferably 22% or more, more preferably 25% or more.
偏光薄膜通常在其兩面或單面上貼合光學性透明且具有機械強度的保護膜而作成偏光板來使用。就保護膜而言,可使用三乙酸纖維素(TAC)薄膜、乙酸-丁 酸纖維素(CAB)薄膜、丙烯酸系薄膜、聚酯系薄膜等。又,就貼合用的接著劑而言,可列舉PVA系接著劑或胺基甲酸酯系接著劑等,但其中較佳為PVA系接著劑。 The polarizing film is usually used as a polarizing plate by bonding an optically transparent and mechanically strong protective film on both sides or one side. As the protective film, cellulose triacetate (TAC) film, cellulose acetate-butyrate (CAB) film, acrylic film, polyester film, etc. can be used. In addition, the adhesive for bonding includes a PVA-based adhesive, a urethane-based adhesive, and the like, but among them, a PVA-based adhesive is preferred.
如上述方式進行所得到的偏光板係能夠在塗布丙烯酸系等黏著劑後,貼合於玻璃基板而作為LCD的構件來使用。亦可同時與相位差薄膜或視角提升薄膜、亮度提升薄膜等進行貼合。 The polarizing plate system obtained as described above can be used as a member of LCD after applying an adhesive such as acrylic, and then bonding it to a glass substrate. It can also be laminated with retardation film, viewing angle enhancement film, brightness enhancement film, etc. at the same time.
以下透過實施例更詳細地說明本發明,但本發明不因此等的實施例而受到任何限定。還有,將在以下的實施例及比較例中所採用的各測定或評價方法示於下方。 Hereinafter, the present invention will be explained in more detail through examples, but the present invention is not limited in any way by these examples. In addition, each measurement or evaluation method used in the following Examples and Comparative Examples is shown below.
[PVA薄膜的膨潤度] [Swelling degree of PVA film]
將PVA薄膜裁切成5cm×10cm,浸漬於30℃的蒸餾水1000mL中30分鐘。之後,取出PVA薄膜,用濾紙擦拭PVA薄膜表面的水分,測定浸漬後的PVA薄膜質量(質量E)。之後,將PVA薄膜置入105℃的乾燥機中乾燥16小時後,測定乾燥後的PVA薄膜質量(質量F)。將質量E與質量F的值代入下述計算式(5)中,而算出PVA薄膜的膨潤度。 The PVA film was cut into 5 cm×10 cm and immersed in 1000 mL of distilled water at 30° C. for 30 minutes. After that, the PVA film was taken out, the moisture on the surface of the PVA film was wiped with filter paper, and the quality of the PVA film after immersion (mass E) was measured. After that, the PVA film was placed in a dryer at 105° C. and dried for 16 hours, and then the quality of the dried PVA film (mass F) was measured. The values of mass E and mass F are substituted into the following calculation formula (5) to calculate the swelling degree of the PVA film.
膨潤度(%)=(質量E/質量F)×100 (5) Swelling degree (%)=(quality E/quality F)×100 (5)
[偏光薄膜的光學特性] [Optical properties of polarizing film]
(1)穿透率Ts的測定 (1) Determination of transmittance Ts
從以下的實施例或比較例中所得到的偏光薄膜的中央部,沿著偏光薄膜的拉伸方向取4cm、沿著寬度方向 取2cm的樣品2片,使用具有積分球的分光光度計(日本分光股份有限公司製「V7100」),依據JIS Z 8722(物體顏色的測定方法),進行C光源、2°視野的可見光區域的可見度校正,針對1片樣品,測定相對於長度方向傾斜+45°時的光線穿透率與傾斜-45°時的光線穿透率,求得該等的平均值Ts1(%)。針對另一片的樣品,以同樣的方式進行,測定傾斜+45°時的光線穿透率與傾斜-45°時的光線穿透率,求得該等的平均值Ts2(%)。以下述計算式(6)將Ts1與Ts2平均,作為偏光薄膜的穿透率Ts(%)。 From the central part of the polarizing film obtained in the following examples or comparative examples, two samples were taken 4 cm along the stretching direction of the polarizing film and 2 cm along the width direction, and a spectrophotometer with an integrating sphere (Japan "V7100" manufactured by Seiko Co., Ltd.), in accordance with JIS Z 8722 (Method for Measuring Object Color), the visibility of C light source and 2° field of view in the visible light region is corrected. For one sample, the measurement is inclined +45° with respect to the longitudinal direction. Obtain the average value Ts1(%) of the light transmittance at time and the light transmittance at -45°. For another piece of sample, proceed in the same way, measure the light transmittance when tilted +45° and the light transmittance when tilted -45°, and obtain the average value Ts2 (%) of these. The Ts1 and Ts2 are averaged by the following calculation formula (6), and used as the transmittance Ts (%) of the polarizing film.
Ts=(Ts1+Ts2)/2 (6) Ts=(Ts1+Ts2)/2 (6)
(2)偏光度V的測定 (2) Measurement of polarization degree V
針對在上述穿透率Ts的測定中使用的2片樣品,使用具有積分球的分光光度計(日本分光股份有限公司製「V7100」),依據JIS Z 8722(物體顏色的測定方法),進行C光源、2°視野的可見光區域的可見度校正來測定以其拉伸方向相互正交的方式進行重疊時的光線穿透率T⊥(%)與以其拉伸方向呈平行的方式進行重疊時的光線穿透率T//(%)。將測定的T//(%)與T⊥(%)代入下述計算式(7),求得偏光度V(%)。 For the two samples used in the above-mentioned measurement of transmittance Ts, use a spectrophotometer with an integrating sphere ("V7100" manufactured by JASCO Corporation), and perform C in accordance with JIS Z 8722 (Method for Measuring Object Color) Visibility correction of the visible light area of the light source and 2° field of view is used to measure the light transmittance T⊥(%) when overlapped so that the stretching directions are orthogonal to each other, and when overlapped so that the stretching directions are parallel to each other. Light transmittance T//(%). Substitute the measured T//(%) and T⊥(%) into the following calculation formula (7) to obtain the degree of polarization V(%).
V={(T//-T⊥)/(T//+T⊥)}1/2×100 (7) V={(T//-T⊥)/(T//+T⊥)} 1/2 ×100 (7)
[耐濕熱性能] [Damp and heat resistance]
將2片偏光薄膜分別固定於金屬框,疊合成正交偏光,以分光光度計測定初期(0小時)的吸光度C(610nm)。再將固定於金屬框的偏光薄膜靜置於60℃/90%RH的環境下8小時後,疊合成正交偏光,以分光光度計測定8 小時後的吸光度D(610nm)。將吸光度D/吸光度C×100的值設為殘存率(%),作為源自PVA-碘錯合物的顏色的褪色的指標。 Two polarizing films were respectively fixed to a metal frame and stacked to form a cross-polarized light, and the initial (0 hour) absorbance C (610 nm) was measured with a spectrophotometer. Then the polarized film fixed on the metal frame was placed in a 60°C/90%RH environment for 8 hours, then superimposed into a cross-polarized light, and the absorbance D (610nm) after 8 hours was measured by a spectrophotometer. The value of absorbance D/absorbance C×100 was defined as a residual rate (%) as an index of the color fading derived from the PVA-iodine complex compound.
[相對於聚乙烯醇(A)100質量份之源自含硼化合物(B)的硼元素含量的測定] [Determination of the content of boron element derived from the boron-containing compound (B) relative to 100 parts by mass of polyvinyl alcohol (A)]
將在23℃/50%RH下控制濕度16小時的偏光薄膜以重水溶解,使其成為0.005質量%,將以旋轉蒸發器濃縮成0.15質量%的溶液作為1H-NMR的測定樣品。1H-NMR(日本電子股份有限公司製JNM-AL400:400MHz)測定係在80℃下進行,使用ALICE2(日本電子股份有限公司製)並以下述方法進行解析。針對測定所得到的1H-NMR圖表,調整相位使基線趨於平緩後,將平均點設定為20並自動進行基線的校正。接著,以作為測定溶媒的重水的峰位於4.65ppm的方式將其自動設定為參考(reference)。之後,如同圖1,將含硼化合物(B)所含的烴基的氫峰積分,求得其峰面積。此時,以將未與源自PVA的氫峰重疊之含硼化合物(B)所含的烴基的氫峰面積加總的結果(面積G)作為峰面積的基準,以含硼化合物(B)的該烴基的氫數與面積G的值成為相同的方式進行設定。接著,將1.7ppm~2.4ppm的範圍的氫峰作為與源自PVA的亞甲基之氫峰及源自PVA的亞甲基之氫峰重疊之含硼化合物(B)所含的烴基的氫峰的總計,而求得峰面積(面積H)。之後,算出從面積H扣除與源自PVA的亞甲基之氫峰重疊之含硼化合物(B)的烴基的氫數而得之面積I。將以此等方法求得的值代入下述計算式(8) 中,並算出相對於聚乙烯醇(A)100質量份之源自含硼化合物(B)的硼元素含量。還有,下述計算式(8)的X、Y分別為未與PVA的峰重疊之含硼化合物(B)所含的烴基的氫數以及含硼化合物(B)每1個分子的硼數。還有,計算式(8)為使用未改質的PVA時所使用的式,在使用經改質的PVA作為原料時,必須要適當地變更計算式(8)。 The polarizing film whose humidity was controlled at 23° C./50% RH for 16 hours was dissolved in heavy water to make 0.005% by mass, and a solution concentrated to 0.15% by mass by a rotary evaporator was used as a 1 H-NMR measurement sample. The 1 H-NMR (JNM-AL400: 400MHz, manufactured by JEOL Ltd.) measurement system was performed at 80°C, and analysis was performed by the following method using ALICE2 (manufactured by JEOL Ltd.). For the 1 H-NMR chart obtained by the measurement, after adjusting the phase so that the baseline becomes flat, the average point is set to 20 and the baseline is automatically corrected. Next, it is automatically set as a reference so that the peak of heavy water as a measurement solvent is located at 4.65 ppm. Thereafter, as in FIG. 1, the hydrogen peaks of the hydrocarbon groups contained in the boron-containing compound (B) are integrated to obtain the peak area. At this time, the sum (area G) of the hydrogen peak area of the hydrocarbon group contained in the boron-containing compound (B) that does not overlap with the hydrogen peak derived from PVA is used as the peak area standard, and the boron-containing compound (B) The number of hydrogen of the hydrocarbon group and the value of the area G are set so that the value becomes the same. Next, let the hydrogen peak in the range of 1.7 ppm to 2.4 ppm be the hydrogen peak of the hydrocarbon group contained in the boron-containing compound (B) that overlaps the hydrogen peak derived from the methylene group derived from PVA and the hydrogen peak derived from the methylene group derived from PVA. The total of the peaks, and the peak area (area H) is obtained. Then, the area I obtained by subtracting the hydrogen number of the hydrocarbon group of the boron-containing compound (B) that overlaps with the hydrogen peak of the methylene group derived from PVA from the area H was calculated. The value obtained by such a method is substituted into the following calculation formula (8), and the content of the boron element derived from the boron-containing compound (B) relative to 100 parts by mass of the polyvinyl alcohol (A) is calculated. In addition, X and Y of the following calculation formula (8) are the number of hydrogen in the hydrocarbon group contained in the boron-containing compound (B) that does not overlap the peak of PVA, and the number of boron per molecule of the boron-containing compound (B) . In addition, the calculation formula (8) is used when unmodified PVA is used, and when the modified PVA is used as a raw material, the calculation formula (8) must be changed appropriately.
相對於聚乙烯醇(A)100質量份之源自含硼化合物(B)的硼元素含量(質量份)={(面積G/X)/(面積I/2)}×{(10.811×Y)/44.0526}×100 (8) The boron element content (parts by mass) derived from the boron-containing compound (B) relative to 100 parts by mass of polyvinyl alcohol (A) = {(area G/X)/(area I/2))×{(10.811×Y )/44.0526)×100 (8)
10.811為硼的原子量,44.0526為未改質的PVA的重覆單元每1莫耳的分子量。還有,圖1的1H-NMR圖表為測定實施例1的偏光薄膜的圖表,相對於聚乙烯醇(A)100質量份之源自含硼化合物(B)的硼元素含量係將小數點第2位無條件進位而成為0.5質量份。 10.811 is the atomic weight of boron, and 44.0526 is the molecular weight per 1 mol of repeated units of unmodified PVA. In addition, the 1 H-NMR chart in FIG. 1 is a chart for measuring the polarizing film of Example 1. The boron element content derived from the boron-containing compound (B) of 100 parts by mass of polyvinyl alcohol (A) is a decimal point The second place is unconditionally carried and becomes 0.5 parts by mass.
[偏光薄膜中的所有硼元素含量(質量%)的算出] [Calculation of all boron content (mass%) in polarizing film]
測定在23℃/50%RH下控制濕度16小時的偏光薄膜的質量(J(g)),將偏光薄膜溶解於20mL的蒸餾水中,使其成為0.005質量%。將溶解偏光薄膜的水溶液作為測定樣品,測定其質量(K(g))。之後,使用島津製作所製Multi-Type型ICP發射光譜分析裝置(ICP)來測定測定樣品的硼濃度(L(ppm))。之後,將於下述計算式(9)中代入該值而算出得到的值設為偏光薄膜中的所有硼元素含量(質量%)。 The mass (J(g)) of the polarizing film whose humidity was controlled at 23° C./50% RH for 16 hours was measured, and the polarizing film was dissolved in 20 mL of distilled water to make it 0.005 mass%. The aqueous solution in which the polarizing film is dissolved is used as a measurement sample, and its mass (K(g)) is measured. After that, a Multi-Type ICP emission spectrometer (ICP) manufactured by Shimadzu Corporation was used to measure the boron concentration (L (ppm)) of the measurement sample. After that, the value obtained by substituting this value into the following calculation formula (9) is used as the total boron element content (mass %) in the polarizing film.
偏光薄膜中的所有硼元素含量(質量%) =[(L×10-6×K)/J]×100 (9) The content of all boron in the polarizing film (mass%) =[(L×10 -6 ×K)/J]×100 (9)
[實施例1] [Example 1]
包含100質量份的PVA(皂化度99.9莫耳%、聚合度2400)、10質量份的甘油作為塑化劑、以及0.1質量份的聚氧乙烯月桂基醚硫酸鈉作為界面活性劑,使用PVA含有率為10質量%的水溶液作為製膜原液,在80℃的金屬輥上將其乾燥,藉由將所得到的薄膜在熱風乾燥機中以120℃的溫度熱處理10分鐘,將膨潤度調整成200%,以製造厚度為30μm的PVA薄膜。 Contains 100 parts by mass of PVA (degree of saponification: 99.9 mol%, degree of polymerization: 2400), 10 parts by mass of glycerin as a plasticizer, and 0.1 parts by mass of sodium polyoxyethylene lauryl ether sulfate as a surfactant, using PVA to contain An aqueous solution with a rate of 10% by mass was used as the film-forming stock solution, which was dried on a metal roll at 80°C, and the resulting film was heat-treated in a hot air dryer at 120°C for 10 minutes to adjust the degree of swelling to 200 % To produce a PVA film with a thickness of 30μm.
從如上述進行所得到的PVA薄膜的寬度方向中央部,以寬度5cm×長度5cm的範圍能夠進行單軸拉伸的方式,裁切出寬度5cm×長度9cm的樣品。將該樣品浸漬於30℃的純水30秒鐘,同時沿長度方向單軸拉伸1.1倍,並進行膨潤處理。接著,浸漬於含有碘0.04質量%及碘化鉀4.0質量%的水溶液(染色處理浴)(溫度30℃)60秒鐘,同時沿長度方向單軸拉伸2.2倍(於整體為2.4倍),並使其吸附碘。接著,浸漬於以硼酸為3質量%及碘化鉀為3質量%的比例含有之水溶液(硼酸交聯處理浴)(溫度30℃),同時沿長度方向單軸拉伸1.2倍(於整體為2.7倍)。再浸漬於以硼酸為4質量%及碘化鉀為6質量%的比例含有之58℃的水溶液(單軸拉伸處理浴),沿長度方向單軸拉伸至整體成為6.0倍。之後,浸漬於以1,4-丁烷二硼酸(1,4-butane diboronic acid)為0.5質量%及碘化鉀為4質量%的比例含有之水溶液(固定處理浴)(溫度30℃)100秒 鐘。最後,在60℃下乾燥4分鐘來製造偏光薄膜。將乾燥後的2片偏光薄膜分別固定於金屬框,疊合成正交偏光時的吸光度(610nm)為3.9。 From the center part in the width direction of the PVA film obtained as described above, a sample having a width of 5 cm × a length of 9 cm was cut out so as to be uniaxially stretched in a range of 5 cm in width × 5 cm in length. This sample was immersed in pure water at 30°C for 30 seconds, while being uniaxially stretched 1.1 times in the longitudinal direction, and subjected to swelling treatment. Next, immersed in an aqueous solution (dyeing bath) (temperature 30°C) containing 0.04% by mass of iodine and 4.0% by mass of potassium iodide for 60 seconds, while uniaxially stretching 2.2 times (2.4 times as a whole) in the longitudinal direction, and making It adsorbs iodine. Next, it was immersed in an aqueous solution (boric acid cross-linking treatment bath) containing 3% by mass of boric acid and 3% by mass of potassium iodide (at a temperature of 30°C), and at the same time uniaxially stretched 1.2 times in the longitudinal direction (2.7 times as a whole) ). It was immersed in a 58°C aqueous solution (uniaxial stretching treatment bath) containing 4% by mass of boric acid and 6% by mass of potassium iodide, and uniaxially stretched to 6.0 times the entire length in the longitudinal direction. Then, immerse in an aqueous solution (fixed treatment bath) (temperature 30°C) containing 0.5% by mass of 1,4-butane diboronic acid and 4% by mass of potassium iodide for 100 seconds Bell. Finally, it was dried at 60°C for 4 minutes to produce a polarizing film. The two polarized films after drying were respectively fixed to a metal frame, and the absorbance (610 nm) when the cross-polarized light was superimposed was 3.9.
測定所得到的偏光薄膜的1H-NMR並進行分析後,由於在1.0~1.3ppm出現未與源自PVA的氫峰重疊的1,4-丁烷二硼酸(1,4-butane diboronic acid)的氫峰,因此將該峰面積(面積G)設定為4,接著算出峰出現在1.7~2.4ppm的範圍的PVA的亞甲基的氫的峰面積(面積H)。由於存在與PVA的亞甲基的氫峰重疊的1,4-丁烷二硼酸(1,4-butane diboronic acid)的氫峰,因此從面積H扣除相當於與PVA的亞甲基重疊的氫峰之1,4-丁烷二硼酸(1,4-butane diboronic acid)的氫數4而算出面積I。將此等的值代入計算式(8)後,得到相對於聚乙烯醇(A)100質量份之源自含硼化合物(B)的硼含量為0.5質量份。
After measuring and analyzing the 1 H-NMR of the obtained polarizing film, 1,4-butane diboronic acid (1,4-butane diboronic acid), which did not overlap with the hydrogen peak derived from PVA, appeared at 1.0 to 1.3 ppm. Therefore, the peak area (area G) is set to 4, and then the peak area (area H) of hydrogen of the methylene group of PVA whose peak appears in the range of 1.7 to 2.4 ppm is calculated. Since the hydrogen peak of 1,4-butane diboronic acid (1,4-butane diboronic acid) overlaps with the hydrogen peak of the methylene group of PVA, the hydrogen corresponding to the methylene group of PVA is subtracted from the area H The
再者,將以同樣的方法製作的偏光薄膜0.00099g(質量J)溶解於20mL的蒸餾水,製作ICP測定用的測定樣品。測定所製作的測定用樣品的質量後,得到質量為20.03g(質量K)。之後,進行ICP測定後,得到測定樣品的硼濃度為1.24ppm(硼濃度L)。將此等的值代入計算式(9)後,得到相對於偏光薄膜之所有硼元素含量為2.5質量%。又,使用所得到的偏光薄膜,透過上述的方法評價偏光薄膜的光學特性及耐濕熱性能。將以上的結果彙整示於表1。 Furthermore, 0.00099 g (mass J) of the polarizing film produced in the same manner was dissolved in 20 mL of distilled water to produce a measurement sample for ICP measurement. After measuring the mass of the prepared sample for measurement, the mass was 20.03 g (mass K). After that, after the ICP measurement, the boron concentration of the measurement sample was 1.24 ppm (boron concentration L). After substituting these values into the calculation formula (9), it is obtained that the content of all boron elements relative to the polarizing film is 2.5% by mass. In addition, the obtained polarizing film was used to evaluate the optical properties and moisture and heat resistance of the polarizing film by the above-mentioned method. The above results are summarized in Table 1.
還有,在實施例2~4及比較例1~3中,一面浸漬於以相對於1質量份的碘為100質量份的碘化鉀的比例含有之水溶液(染色處理浴)(溫度30℃)60秒鐘,一 面沿長度方向單軸拉伸2.2倍(於整體為2.4倍)並吸附碘。此時,染色處理浴的碘或碘化鉀濃度係以將乾燥後的2片偏光薄膜分別固定於金屬框且疊合成正交偏光時的吸光度(610nm)從3.6變成4.2的方式進行調整。 In addition, in Examples 2 to 4 and Comparative Examples 1 to 3, one side was immersed in an aqueous solution containing potassium iodide in a ratio of 100 parts by mass to 1 part by mass of iodine (dyeing treatment bath) (temperature 30°C) 60 Seconds, one The surface is uniaxially stretched 2.2 times in the length direction (2.4 times as a whole) and adsorbs iodine. At this time, the concentration of iodine or potassium iodide in the dyeing bath was adjusted so that the absorbance (610 nm) of the two polarized films after drying was fixed to a metal frame and stacked to form a cross-polarized light from 3.6 to 4.2.
[實施例2] [Example 2]
除了固定處理浴使用以0.5質量%的比例含有1,3-丙烷二硼酸(1,3-propane diboronic acid)以及以3質量%的比例含有碘化鉀之水溶液(溫度30℃)以外,與實施例1同樣地製作偏光薄膜,進行各種測定或評價。將結果示於表1。 Except that the fixed treatment bath uses 0.5% by mass of 1,3-propane diboronic acid (1,3-propane diboronic acid) and 3% by mass of potassium iodide in an aqueous solution (temperature 30°C), the same as in Example 1. The polarizing film was produced in the same manner, and various measurements or evaluations were performed. The results are shown in Table 1.
[實施例3] [Example 3]
除了固定處理浴使用以1.0質量%的比例含有苯基硼酸(phenyl boronate)以及以2.0質量%的比例含有碘化鉀之水溶液(溫度30℃)以外,與實施例1同樣地製作偏光薄膜,進行各種測定或評價。將結果示於表1。實施例3為參考例。 A polarizing film was produced in the same manner as in Example 1, except that an aqueous solution (temperature 30°C) containing phenyl boronate at a ratio of 1.0% by mass and potassium iodide at a ratio of 2.0% by mass was used in the fixed treatment bath, and various measurements were performed. Or evaluation. The results are shown in Table 1. Example 3 is a reference example.
[實施例4] [Example 4]
除了固定處理浴使用以4.0質量%的比例含有正丙基硼酸(n-propyl boronate)以及以3.0質量%的比例含有碘化鉀之水溶液(溫度30℃)以外,與實施例1同樣地製作偏光薄膜,進行各種測定或評價。將結果示於表1。實施例4為參考例。 A polarizing film was produced in the same manner as in Example 1, except that an aqueous solution (temperature 30°C) containing n-propyl boronate at a ratio of 4.0% by mass and potassium iodide at a ratio of 3.0% by mass was used for the fixed treatment bath. Perform various measurements or evaluations. The results are shown in Table 1. Example 4 is a reference example.
[比較例1] [Comparative Example 1]
除了固定處理浴使用以2質量%的比例含有硼酸以及以3質量%的比例含有碘化鉀之水溶液(溫度30℃)以外,與實施例1同樣地製作偏光薄膜,進行各種測定或評價。將結果示於表1。 A polarizing film was produced in the same manner as in Example 1, except that an aqueous solution (temperature 30°C) containing boric acid at a ratio of 2% by mass and potassium iodide at a ratio of 3% by mass was used in the fixed treatment bath, and various measurements and evaluations were performed. The results are shown in Table 1.
[比較例2] [Comparative Example 2]
除了固定處理浴使用以1.0質量%的比例含有硼酸以及以3質量%的比例含有碘化鉀之水溶液(溫度30℃)以外,與實施例1同樣地製作偏光薄膜,進行各種測定或評價。將結果示於表1。 A polarizing film was produced in the same manner as in Example 1, except that an aqueous solution (temperature 30°C) containing boric acid at a ratio of 1.0% by mass and potassium iodide at a ratio of 3% by mass was used for the fixed treatment bath, and various measurements and evaluations were performed. The results are shown in Table 1.
[比較例3] [Comparative Example 3]
除了固定處理浴使用以0.5質量%的比例含有硼酸以及以3質量%的比例含有碘化鉀之水溶液(溫度30℃)以外,與實施例1同樣地製作偏光薄膜,進行各種測定或評價。將結果示於表1。 A polarizing film was produced in the same manner as in Example 1, except that an aqueous solution (temperature 30°C) containing boric acid at a ratio of 0.5% by mass and potassium iodide at a ratio of 3% by mass was used in the fixed treatment bath, and various measurements and evaluations were performed. The results are shown in Table 1.
比較實施例1及2與比較例2,可知即便偏光薄膜中的所有硼元素含量為相同或更少,實施例1及2的吸光度殘存率就是比比較例2還高。又,比較實施例3及4與比較例1,可知即便偏光薄膜中的所有硼元素含量為相同或更少,實施例3及4的吸光度殘存率就是比比較例1還高。由以上可知,符合本發明之規定的實施例1~4的偏光薄膜具有優異的耐濕熱性能。 Comparing Examples 1 and 2 with Comparative Example 2, it can be seen that even if the content of all boron elements in the polarizing film is the same or less, the residual absorbance ratio of Examples 1 and 2 is higher than that of Comparative Example 2. In addition, comparing Examples 3 and 4 with Comparative Example 1, it can be seen that even if the content of all boron elements in the polarizing film is the same or less, the residual absorbance ratios of Examples 3 and 4 are higher than those of Comparative Example 1. From the above, it can be seen that the polarizing films of Examples 1 to 4 that meet the requirements of the present invention have excellent moisture and heat resistance.
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