TWI636066B - Blank film for optical film manufacturing and manufacturing method of optical film - Google Patents
Blank film for optical film manufacturing and manufacturing method of optical film Download PDFInfo
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- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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Abstract
提供一種延伸性優異、可生產性良好地製造光學薄膜,而且可容易地製造光學特性及色相均優良的光學薄膜之光學薄膜製造用坯材薄膜、及使用其之光學薄膜之製造方法。 Provided are a raw material film for optical film manufacturing, which is capable of producing an optical film with excellent extensibility and good productivity, and an optical film having excellent optical characteristics and hue, and a method for producing an optical film using the same.
一種光學薄膜製造用坯材薄膜,其係含有包含乙烯醇單元、及下述式(1)所示之結構單元的含有羥甲基之乙烯醇系聚合物;及一種光學薄膜之製造方法,其係具有使用該光學薄膜製造用坯材薄膜來實施單軸延伸的步驟。 A raw material film for manufacturing an optical film, which is a vinyl alcohol polymer containing a methylol group containing a vinyl alcohol unit and a structural unit represented by the following formula (1); and a method for manufacturing an optical film, The method includes the step of performing uniaxial stretching using the raw material film for optical film production.
Description
本發明係有關於一種包含具有1,3-二醇結構的含有羥甲基之乙烯醇系聚合物的供製造偏光薄膜等光學薄膜的坯材薄膜、及使用其之光學薄膜之製造方法。 The present invention relates to a raw material film for producing an optical film such as a polarizing film including a methylol-containing vinyl alcohol polymer having a 1,3-diol structure, and a method for producing an optical film using the same.
具有透光及遮光機能的偏光板,與改變光之偏光狀態的液晶同為液晶顯示器(LCD)的基本構成要素。大部分的偏光板係具有在偏光薄膜的表面貼合三乙酸纖維素(TAC)薄膜等保護膜的結構,就構成偏光板的偏光薄膜而言,在對乙烯醇系聚合物薄膜(以下,有時將「乙烯醇系聚合物」稱為「PVA」)實施單軸延伸而成的基質上吸附有碘系色素(I3 -或I5 -等)或二色性有機染料等二色性色素者為其主流。 A polarizing plate having a light transmitting and light blocking function is the same as a basic constituent element of a liquid crystal display (LCD), as is a liquid crystal that changes the polarization state of light. Most polarizing plates have a structure in which a protective film such as a cellulose triacetate (TAC) film is laminated on the surface of the polarizing film. As for the polarizing film constituting the polarizing plate, the vinyl alcohol polymer film (hereinafter, there are ("Vinyl alcohol polymer" is referred to as "PVA"), and dichroic dyes such as iodine dyes (I 3 - or I 5 - etc.) or dichroic organic dyes are adsorbed on a substrate obtained by uniaxial stretching. For its mainstream.
LCD於計算機及手錶等小型機器、行動電話、筆記型電腦、液晶螢幕、液晶彩色投影機、液晶電視、車載用導航系統、屋內外所使用之測量儀器等廣範圍漸付諸使用,近年來,尤其要求顯示品質的高級化。隨之,對於偏光薄膜亦要求高性能化,具體而言,係要求偏光度或穿透度高、光學特性優良,而且色相或耐久性亦優異的偏光薄膜。 LCDs are gradually being used in a wide range of small devices such as computers and watches, mobile phones, notebook computers, LCD screens, LCD color projectors, LCD TVs, car navigation systems, and measuring instruments used indoors and outdoors. In recent years, In particular, advanced display quality is required. Accordingly, high performance is also required for polarizing films. Specifically, polarizing films are required to have high polarization or transmittance, excellent optical characteristics, and excellent hue and durability.
此外,已知有數種包含改質PVA的光學薄膜製造用坯材薄膜。舉例來說,已知包含含有0.01~1莫耳%之羧酸基或ω-羥基-α-烯烴基等親水性官能基的特定之PVA的偏光膜的坯材用聚乙烯醇薄膜,其延伸‧配向處理性及二色性物質之吸附處理性優良(參照專利文獻1等)。又,已知包含側鏈含有1,2-二醇鍵結的特定PVA的特定之光學用PVA薄膜,其光學特性及延伸性優良(參照專利文獻2)。 In addition, several kinds of raw material films for optical film production including modified PVA are known. For example, it is known that a polyvinyl alcohol film for a polarizing film of a polarizing film containing a specific PVA containing a hydrophilic functional group such as a carboxylic acid group or an ω-hydroxy-α-olefin group at 0.01 to 1 mole% is extended. ‧Excellent alignment treatment and dichroic substance adsorption treatment (refer to Patent Document 1, etc.). Further, it is known that a specific optical PVA film including a specific PVA having a 1,2-diol bond in a side chain has excellent optical characteristics and extensibility (see Patent Document 2).
[專利文獻1]日本特開平8-201626號公報 [Patent Document 1] Japanese Unexamined Patent Publication No. 8-201626
[專利文獻2]日本特開2009-24076號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2009-24076
然而,使用以往周知之包含改質PVA的光學薄膜製造用坯材薄膜時,在獲得光學特性及色相均優良的光學薄膜方面,尚有進一步改良的空間。此外,使用以往周知之包含改質PVA的光學薄膜製造用坯材薄膜時,特別是在連續製造光學薄膜的情況等,依舊容易發生延伸斷裂等問題,於光學薄膜的生產性方面亦有進一步改良的空間。 However, when using a conventionally known raw material film for optical film manufacturing including modified PVA, there is still room for further improvement in obtaining an optical film having excellent optical characteristics and hue. In addition, when using a conventionally known blank film for optical film manufacturing including modified PVA, especially in the case of continuous production of optical films, problems such as stretch fracture are still prone to occur, and the productivity of optical films has been further improved. Space.
因此,本發明係以提供一種延伸性優異、可生產性良好地製造光學薄膜,而且可容易地製造光學特性及色相均優良的光學薄膜之光學薄膜製造用坯材薄膜、及使用其之光學薄膜之製造方法為目的。 Therefore, the present invention is to provide an optical film for manufacturing an optical film, which is excellent in extensibility and good producibility, and can easily produce an optical film having excellent optical characteristics and hue, and an optical film using the same. Manufacturing method for the purpose.
本發明人等為達成上述目的而致力重複進行研究的結果發現,根據一種薄膜可解決上述課題,該薄膜含有主鏈上包含具有1,3-二醇結構之特定結構單元的含有羥甲基之PVA,並基於該見解進一步重複進行研究而完成本發明。 The present inventors have repeatedly conducted research to achieve the above-mentioned object, and found that the above-mentioned problem can be solved by a thin film containing a methylol group-containing material containing a specific structural unit having a 1,3-diol structure on the main chain. PVA, and based on this knowledge, further repeated research to complete the present invention.
即,本發明係有關於:[1]一種光學薄膜製造用坯材薄膜,其係含有包含乙烯醇單元、及下述式(1)所示之結構單元的含有羥甲基之PVA:
根據本發明,茲提供一種延伸性優異、可生產性良好地製造光學薄膜,而且可容易地製造光學特性及色相均優良的光學薄膜之光學薄膜製造用坯材薄膜、及使用其之光學薄膜之製造方法。 According to the present invention, there is provided an optical film for manufacturing an optical film which is capable of producing an optical film with excellent extensibility and good productivity, and which can easily produce an optical film having excellent optical characteristics and hue, and an optical film using the same. Production method.
本發明之光學薄膜製造用坯材薄膜係含有包含乙烯醇單元、及下述式(1)所示之結構單元的含有羥甲基之PVA。 The raw material film for producing an optical film of the present invention contains a methylol group-containing PVA containing a vinyl alcohol unit and a structural unit represented by the following formula (1).
本發明之光學薄膜製造用坯材薄膜,其所含的含有羥甲基之PVA包含上述式(1)所示之具有1,3-二醇結構的結構單元,藉此可提升延伸性。此外,根據本發明之光學薄膜製造用坯材薄膜,可容易地製造光學特性 及色相均優良的光學薄膜。就可獲得如上優點的理由而言,雖非本發明之任何限定,惟茲認為:藉由式(1)所示之結構單元會使結晶性降低;因基於1,3-二醇結構的高氫鍵鍵結力所產生的影響。 The raw material film for producing an optical film of the present invention contains a methylol-containing PVA containing a structural unit having a 1,3-diol structure represented by the above formula (1), thereby improving elongation. In addition, according to the blank film for producing an optical film of the present invention, optical characteristics can be easily produced. Optical film with excellent hue. For reasons of obtaining the advantages described above, although it is not a limitation of the present invention, it is considered that the crystallinity is lowered by the structural unit represented by the formula (1); The effect of hydrogen bonding.
含有羥甲基之PVA中的式(1)所示之結構單元的含有率不特別限定,惟設構成含有羥甲基之PVA的總結構單元的莫耳數為100莫耳%時,較佳為0.1~2莫耳%之範圍內,更佳為0.2~1.9莫耳%之範圍內,再佳為0.3~1.8莫耳%之範圍內。使該含有率為0.1莫耳%以上,藉此可進一步提升薄膜的延伸性,並可獲得色相更優良的光學薄膜。另一方面,使該含有率為2莫耳%以下,藉此可更有效防止光學薄膜製造時薄膜的溶解,並可獲得光學特性更優良的光學薄膜。此外,本說明書中,「結構單元」係指構成聚合物的重複單元。 The content rate of the structural unit represented by the formula (1) in the methylol-containing PVA is not particularly limited, but it is preferable that the molar number of the total structural unit constituting the methylol-containing PVA is 100 mole%. It is in the range of 0.1 to 2 mol%, more preferably in the range of 0.2 to 1.9 mol%, and even more preferably in the range of 0.3 to 1.8 mol%. By setting the content rate to 0.1 mol% or more, the extensibility of the film can be further improved, and an optical film having a better hue can be obtained. On the other hand, when the content is 2 mol% or less, the film can be more effectively prevented from dissolving during the production of the optical film, and an optical film having more excellent optical characteristics can be obtained. In addition, in this specification, a "structural unit" means the repeating unit which comprises a polymer.
含有羥甲基之PVA的聚合度較佳為1,500~6,000之範圍內,更佳為1,800~5,000之範圍內,再佳為2,000~4,000之範圍內。使該聚合度為1,500以上,藉此可進一步提升對薄膜實施單軸延伸所得之偏光薄膜等光學薄膜的耐久性。另一方面,使該聚合度為6,000以下,藉此可抑制製造成本的上升、製膜時的步驟通過性不良等。此外,本說明書中的含有羥甲基之PVA的聚合度係指依據JIS K6726-1994之記載所測定的平均聚合度。 The degree of polymerization of hydroxymethyl-containing PVA is preferably in the range of 1,500 to 6,000, more preferably in the range of 1,800 to 5,000, and even more preferably in the range of 2,000 to 4,000. By setting the polymerization degree to 1,500 or more, the durability of optical films such as polarizing films obtained by uniaxially stretching the films can be further improved. On the other hand, by setting the degree of polymerization to 6,000 or less, it is possible to suppress an increase in manufacturing cost, a poor processability during film formation, and the like. In addition, the polymerization degree of hydroxymethyl-containing PVA in this specification means the average polymerization degree measured based on the description of JIS K6726-1994.
基於對薄膜實施單軸延伸所得之偏光薄膜等光學薄膜的耐水性觀點,含有羥甲基之PVA的皂化度較佳為95莫耳%以上,更佳為96莫耳%以上,再佳為98莫耳 %以上。此外,本說明書中的含有羥甲基之PVA的皂化度,係指相對於含有羥甲基之PVA所具有的可藉由皂化轉換成乙烯醇單元(-CH2-CH(OH)-)的結構單元(典型上為乙烯酯單元)與乙烯醇單元的合計莫耳數而言,該乙烯醇單元之莫耳數所占的比例(莫耳%)。該皂化度可參酌所有式(1)所示之結構單元或其衍生物的量後,依據JIS K6726-1994之記載來測定。 From the viewpoint of water resistance of an optical film such as a polarizing film obtained by uniaxially stretching the film, the saponification degree of the PVA containing methylol group is preferably 95 mol% or more, more preferably 96 mol% or more, and even more preferably 98 More than%. In addition, the saponification degree of the PVA containing a methylol group in this specification refers to the content of the PVA containing a methylol group which can be converted into a vinyl alcohol unit (-CH 2 -CH (OH)-) by saponification. In terms of the total mole number of the structural unit (typically a vinyl ester unit) and the vinyl alcohol unit, the proportion (mole%) of the mole number of the vinyl alcohol unit. The degree of saponification can be measured in accordance with the description of JIS K6726-1994 after taking into account the amounts of all the structural units or derivatives thereof represented by formula (1).
含有羥甲基之PVA之製造方法不特別限定。例如,可舉出下述方法:將乙烯酯系單體、及可與其共聚合並可轉換成式(1)所示之結構單元的不飽和單體共聚合,再將所得乙烯酯系共聚物的乙烯酯單元,轉換成乙烯醇單元,而將來自可轉換成式(1)所示之結構單元的不飽和單體的結構單元,轉換成式(1)所示之結構單元。將可轉換成式(1)所示之結構單元的不飽和單體的具體實例,以下式(2)示出。 The manufacturing method of a methylol group containing PVA is not specifically limited. For example, there can be mentioned a method of copolymerizing a vinyl ester-based monomer and an unsaturated monomer which can be copolymerized therewith and can be converted into a structural unit represented by formula (1), and then the obtained vinyl ester-based copolymer is copolymerized. The vinyl ester unit is converted into a vinyl alcohol unit, and the structural unit derived from an unsaturated monomer that can be converted into a structural unit represented by formula (1) is converted into a structural unit represented by formula (1). Specific examples of the unsaturated monomer that can be converted into the structural unit represented by the formula (1) are shown in the following formula (2).
式(2)中,R表示碳數1~10之烷基。作為R之結構不特別限定,其一部分可具有分支、環狀結構。又,其一部分可經其他的官能基取代。R較佳為碳數1~5之烷基,而作為該烷基之實例,可列舉甲基、乙基、正 丙基、異丙基、正丁基、異丁基、三級丁基、戊基等直鏈或具有分支的烷基。又,作為R可具有的取代基,可列舉烷氧基、鹵素原子、氫氧基等。此外,存在複數個的R可彼此相同或相異。 In formula (2), R represents an alkyl group having 1 to 10 carbon atoms. The structure of R is not particularly limited, and a part thereof may have a branched or cyclic structure. Moreover, a part of them may be substituted with another functional group. R is preferably an alkyl group having 1 to 5 carbon atoms, and examples of the alkyl group include methyl, ethyl, and n- Linear or branched alkyl groups such as propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, and pentyl. Examples of the substituent that R may have include an alkoxy group, a halogen atom, and a hydroxyl group. In addition, a plurality of Rs may be the same or different from each other.
作為式(2)所示之不飽和單體,可列舉例如1,3-二乙醯氧-2-亞甲基丙烷、1,3-二丙醯氧-2-亞甲基丙烷、1,3-二丁醯氧-2-亞甲基丙烷等。其中,基於製造容易性觀點,較佳使用1,3-二乙醯氧-2-亞甲基丙烷。 Examples of the unsaturated monomer represented by the formula (2) include 1,3-diethylfluorenyloxy-2-methylenepropane, 1,3-dipropanyloxy-2-methylenepropane, and 1, 3-dibutoxo-2-methylenepropane and the like. Among them, from the viewpoint of ease of production, 1,3-diacetoxy-2-methylenepropane is preferably used.
式(2)所示之不飽和單體,一般而言比起PVA之改質所使用的其他烯丙基型不飽和單體(例如烯丙基環氧丙基醚等),較容易與乙烯酯系單體進行共聚合反應。從而,聚合時的改質量或聚合度的限制較少,容易獲得改質量及聚合度較高的含有羥甲基之PVA。再者,由於可減少聚合結束時所殘留之未反應的該不飽和單體的量,因此本發明之含有羥甲基之PVA在工業上製造時的環境面及成本面亦優良。 The unsaturated monomer represented by formula (2) is generally easier to interact with ethylene than other allyl unsaturated monomers (such as allyl epoxypropyl ether) used in the modification of PVA. The ester monomer is copolymerized. Therefore, there are fewer restrictions on the quality or degree of polymerization during polymerization, and it is easy to obtain a methylol-containing PVA having a high quality and degree of polymerization. Furthermore, since the amount of the unreacted unsaturated monomer remaining at the end of the polymerization can be reduced, the methylol-containing PVA of the present invention is also excellent in environmental and cost aspects when manufactured industrially.
含有羥甲基之PVA之製造所使用的乙烯酯系單體不特別限定,可列舉例如甲酸乙烯酯、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、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、苯甲酸乙烯酯等。基於經濟性觀點,較佳為乙酸乙烯酯。 The vinyl ester monomer used in the production of methylol-containing PVA is not particularly limited, and examples thereof include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, and trimethyl Vinyl acetate, vinyl versatate, vinyl hexanoate, vinyl octoate, vinyl decanoate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate , Vinyl benzoate, etc. From the viewpoint of economy, vinyl acetate is preferred.
將式(2)所示之不飽和單體與乙烯酯系單體共聚合時的聚合方式可為批次聚合、半批次聚合、連續 聚合、半連續聚合等任一種方式,作為聚合方法,可應用塊狀聚合法、溶液聚合法、懸浮聚合法、乳化聚合法等周知之方法。通常採用在無溶劑或醇類等溶劑中進行聚合的塊狀聚合法或溶液聚合法。欲獲得高聚合度之乙烯酯系共聚物時,乳化聚合法亦佳。溶液聚合法的溶劑不特別限定,係為例如醇類。溶液聚合法的溶劑所使用的醇類為例如甲醇、乙醇、丙醇等的低級醇。聚合系統中的溶劑的用量只要依據目標之含有羥甲基之PVA的聚合度,考量溶劑的連鎖轉移來選擇即可,例如溶劑為甲醇時,以溶劑與聚合系統所含之總單體的質量比{=(溶劑)/(總單體)}計,可由較佳為0.01~10之範圍內,更佳為0.05~3之範圍內選擇。 When the unsaturated monomer represented by formula (2) is copolymerized with a vinyl ester monomer, the polymerization method may be batch polymerization, semi-batch polymerization, or continuous polymerization. Either polymerization, semi-continuous polymerization, or the like. As the polymerization method, known methods such as a block polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method can be applied. Usually, a block polymerization method or a solution polymerization method in which polymerization is performed in a solvent such as a solvent or an alcohol is used. When a vinyl ester copolymer having a high degree of polymerization is desired, an emulsion polymerization method is also preferred. The solvent of the solution polymerization method is not particularly limited, and is, for example, an alcohol. The alcohol used in the solvent of the solution polymerization method is, for example, a lower alcohol such as methanol, ethanol, or propanol. The amount of solvent used in the polymerization system can be selected according to the polymerization degree of the target methyl PVA containing methyl alcohol and the chain transfer of the solvent. For example, when the solvent is methanol, the mass of the solvent and the total monomer contained in the polymerization system is used. The ratio {= (solvent) / (total monomer)} can be selected from the range of preferably 0.01 to 10, more preferably 0.05 to 3.
式(2)所示之不飽和單體與乙烯酯系單體的共聚合所使用的起始劑,只要視聚合方法而由周知之聚合起始劑,例如偶氮系起始劑、過氧化物系起始劑、氧化還原系起始劑中選出即可。偶氮系起始劑為例如2,2’-偶氮二異丁腈、2,2’-偶氮二(2,4-二甲基戊腈)、2,2’-偶氮二(4-甲氧基-2,4-二甲基戊腈)等。過氧化物系起始劑為例如二異丙基過氧化二碳酸酯、二-2-乙基己基過氧化二碳酸酯、二乙氧基乙基過氧化二碳酸酯等過氧化碳酸酯化合物;三級丁基過氧化新癸酸酯、α-異丙苯過氧化新癸酸酯等過氧化酯化合物;乙醯環己磺醯基過氧化物;2,4,4-三甲基戊基-2-過氧化苯氧乙酸酯;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而構成聚合起始劑。氧化還原系起始劑為例如將上 述過氧化物起始劑與亞硫酸氫鈉、碳酸氫鈉、酒石酸、L-抗壞血酸、雕白粉(rongalit)等還原劑組合而成的聚合起始劑。由於聚合起始劑的用量會因聚合起始劑的種類而異,故無法一概論定,但只要依據聚合速度來選擇即可。例如聚合起始劑使用2,2’-偶氮二異丁腈或者過氧化乙醯時,相對於乙烯酯系單體,較佳為0.01~0.2莫耳%,更佳為0.02~0.15莫耳%。聚合溫度不特別限定,室溫~150℃左右屬合適,較佳為40℃以上且為使用之溶劑的沸點以下。 The initiator used in the copolymerization of the unsaturated monomer represented by the formula (2) and the vinyl ester monomer may be a known polymerization initiator depending on the polymerization method, such as an azo initiator and a peroxide. What is necessary is just to select among a system initiator and a redox system initiator. The azo-based initiator is, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4 -Methoxy-2,4-dimethylvaleronitrile) and the like. Peroxide-based initiators are percarbonate compounds such as diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, diethoxyethylperoxydicarbonate; Peroxy ester compounds such as tertiary butyl peroxydecanoate, α-cumene peroxy neodecanoate; acetamidinecyclohexylsulfonyl peroxide; 2,4,4-trimethylpentyl -2-Phenoxyacetate; Acetyl peroxide. A polymerization initiator may be constituted by combining potassium persulfate, ammonium persulfate, hydrogen peroxide, and the like with the above-mentioned initiator. The redox-based initiator is, for example, The polymerization initiator is a combination of a peroxide initiator and a reducing agent such as sodium bisulfite, sodium bicarbonate, tartaric acid, L-ascorbic acid, and rongalit. Since the amount of the polymerization initiator varies depending on the type of the polymerization initiator, it cannot be generalized, but it can be selected according to the polymerization speed. For example, when 2,2'-azobisisobutyronitrile or acetamidine peroxide is used as the polymerization initiator, it is preferably 0.01 to 0.2 mol%, and more preferably 0.02 to 0.15 mol relative to vinyl ester monomers. %. The polymerization temperature is not particularly limited, and it is suitable from about room temperature to about 150 ° C, and preferably above 40 ° C and below the boiling point of the solvent used.
式(2)所示之不飽和單體與乙烯酯系單體的共聚合可於鏈轉移劑存在下進行。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-羥基乙硫醇等硫醇類;次膦酸鈉單水合物等次膦酸鹽類。其中可適當地使用醛類及酮類。鏈轉移劑的用量,可依據所使用之鏈轉移劑的鏈轉移常數以及目標之含有羥甲基之PVA的聚合度來決定,一般而言,相對於100質量份乙烯酯系單體,較佳為0.1~10質量份。 The copolymerization of the unsaturated monomer represented by the formula (2) and the vinyl ester-based monomer can be performed 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; thiols such as 2-hydroxyethyl mercaptan; and phosphinates such as sodium phosphinate monohydrate. Among them, aldehydes and ketones can be suitably used. The amount of chain transfer agent can be determined according to the chain transfer constant of the chain transfer agent used and the degree of polymerization of the target methylol group-containing PVA. Generally speaking, it is better than 100 parts by mass of vinyl ester monomers. It is 0.1 to 10 parts by mass.
透過將藉式(2)所示之不飽和單體與乙烯酯系單體的共聚合所得的乙烯酯系共聚物皂化,可得上述之含有羥甲基之PVA。透過將該乙烯酯系共聚物皂化,乙烯酯系共聚物中的乙烯酯單元即轉換成乙烯醇單元。又,來自式(2)所示之不飽和單體的結構單元的酯鍵亦經皂化而轉換成式(1)所示之具有1,3-二醇結構的結構單元。因此,在皂化後縱使未進一步進行水解等反應仍可製造該含有羥甲基之PVA。 By saponifying a vinyl ester copolymer obtained by copolymerizing an unsaturated monomer represented by formula (2) and a vinyl ester monomer, the above-mentioned PVA containing methylol can be obtained. By saponifying the vinyl ester-based copolymer, the vinyl ester unit in the vinyl ester-based copolymer is converted into a vinyl alcohol unit. In addition, the ester bond derived from the structural unit of the unsaturated monomer represented by the formula (2) is converted into a structural unit having a 1,3-diol structure represented by the formula (1) by saponification. Therefore, after saponification, the methylol-containing PVA can be produced without further performing a reaction such as hydrolysis.
乙烯酯系共聚物的皂化可在例如將該乙烯酯系共聚物溶於醇類或含水醇類的狀態下進行。皂化所使用的醇類,可列舉例如甲醇、乙醇等的低級醇,較佳為甲醇。皂化所使用的醇類,亦能以例如其質量的40質量%以下的比例含有丙酮、乙酸甲酯、乙酸乙酯、苯等其他溶劑。皂化所使用的觸媒為例如氫氧化鉀、氫氧化鈉等鹼金屬之氫氧化物、甲氧鈉等鹼觸媒、礦酸等酸觸媒。進行皂化的溫度未予限定,較合適為20~60℃之範圍內。隨著皂化進行而有凝膠狀之生成物析出時,將生成物粉碎後,加以清洗、乾燥,可得含有羥甲基之PVA。皂化方法不限於前述方法,可應用周知方法。 The saponification of the vinyl ester copolymer can be performed, for example, in a state where the vinyl ester copolymer is dissolved in an alcohol or a water-containing alcohol. Examples of the alcohol used for saponification include lower alcohols such as methanol and ethanol, and methanol is preferred. The alcohol used for saponification can also contain other solvents, such as acetone, methyl acetate, ethyl acetate, and benzene, in the ratio of 40 mass% or less of its mass, for example. Catalysts used for saponification are, 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 at which the saponification is performed is not limited, but it is more preferably within a range of 20 to 60 ° C. When a gel-like product precipitates with the progress of saponification, the product is pulverized, washed, and dried to obtain PVA containing methylol. The saponification method is not limited to the aforementioned method, and a known method can be applied.
含有羥甲基之PVA可進一步含有除了式(1)所示之結構單元、乙烯醇單元及乙烯酯單元以外的其他結構單元。作為該其他結構單元,可列舉例如:來自可與乙烯酯系單體共聚合之乙烯性不飽和單體的結構單元。又,亦可含有:來自上述可與乙烯酯系單體共聚合並可轉換成式(1)所示之結構單元的不飽和單體的結構單元(未藉由皂化轉換成式(1)所示之結構單元的結構單元)。 The methylol group-containing PVA may further contain a structural unit other than the structural unit represented by formula (1), a vinyl alcohol unit, and a vinyl ester unit. Examples of the other structural unit include a structural unit derived from an ethylenically unsaturated monomer copolymerizable with a vinyl ester-based monomer. In addition, it may contain a structural unit derived from an unsaturated monomer which can be copolymerized with the vinyl ester-based monomer and can be converted into a structural unit represented by formula (1) (which is not converted into formula (1) by saponification). The structural unit shown in the structural unit).
設構成含有羥甲基之PVA之總結構單元的莫耳數為100莫耳%時,含有羥甲基之PVA中的式(1)所示之結構單元、乙烯醇單元及乙烯酯單元的合計所占的比例較佳為80莫耳%以上,更佳為90莫耳%以上,再佳為95莫耳%以上,亦可為99莫耳%以上。 When the mole number of the total structural unit constituting the PVA containing methylol group is 100 mole%, the total of the structural unit, vinyl alcohol unit, and vinyl ester unit represented by formula (1) in the methyl alcohol-containing PVA is assumed. The proportion is preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and also 99 mol% or more.
作為上述乙烯性不飽和單體,係為例如乙烯 、丙烯、正丁烯、異丁烯、1-己烯等α-烯烴類;丙烯酸及其鹽;具丙烯酸酯基之不飽和單體;甲基丙烯酸及其鹽;具甲基丙烯酸酯基之不飽和單體;丙烯醯胺、N-甲基丙烯醯胺、N-乙基丙烯醯胺、N,N-二甲基丙烯醯胺、二丙酮丙烯醯胺、丙烯醯胺丙烷磺酸及其鹽、丙烯醯胺丙基二甲胺及其鹽(例如四級鹽)等丙烯醯胺衍生物;甲基丙烯醯胺、N-甲基甲基丙烯醯胺、N-乙基甲基丙烯醯胺、甲基丙烯醯胺丙烷磺酸及其鹽、甲基丙烯醯胺丙基二甲胺及其鹽(例如四級鹽)等甲基丙烯醯胺衍生物;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、十二基乙烯基醚、十八基乙烯基醚、2,3-二乙醯氧-1-乙烯氧基丙烷等乙烯基醚類;丙烯腈、甲基丙烯腈等氰化乙烯基類;氯乙烯、氟乙烯等鹵化乙烯類;二氯亞乙烯、二氟亞乙烯等二鹵化亞乙烯類;2,3-二乙醯氧-1-烯丙基氧基丙烷、氯化烯丙基等烯丙基化合物;順丁烯二酸、衣康酸、富馬酸等不飽和二羧酸及其鹽或其酯類;乙烯基三甲氧矽烷等乙烯基矽烷基化合物;乙酸異丙烯酯等。此等當中,由可提升延伸性並可在更高的溫度下實施延伸,且於光學薄膜製造時可減少延伸斷裂等問題的發生而進一步提升光學薄膜的生產性言之,較佳為乙烯。含有羥甲基之PVA包含乙烯單元時,基於如上述之延伸性或可延伸溫度等觀點,設構成含有羥甲基之PVA的總結構單元的莫耳數為100莫耳%時,乙烯單元的含有率較佳為1~4莫耳%,特佳為2~3莫耳%。 Examples of the ethylenically unsaturated monomer include ethylene. , Propylene, n-butene, isobutylene, 1-hexene and other α-olefins; acrylic acid and its salts; unsaturated monomers with acrylate groups; methacrylic acid and its salts; unsaturated with methacrylate groups Monomers; acrylamide, N-methacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetone acrylamide, acrylamide propanesulfonic acid and its salts, Acrylamide derivatives such as acrylamine propyldimethylamine and its salts (such as quaternary salts); methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, Methacrylamidine propanesulfonic acid and its salts, methacrylamidine propyl dimethylamine and its salts (such as quaternary salts), and other methacrylamidine derivatives; 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 ether, octadecyl vinyl ether Ethers, vinyl ethers such as 2,3-diacetoxy-1-vinyloxypropane; vinyl cyanides such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride and vinyl fluoride; Dihalogenated vinylidene such as dichloroethylene, difluoroethylene, etc .; allyl compounds such as 2,3-diethylacetoxy-1-allyloxypropane, chlorinated allyl; maleic acid , Itaconic acid, fumaric acid and other unsaturated dicarboxylic acids and their salts or their esters; vinyl silane compounds such as vinyl trimethoxysilane; isopropenyl acetate and the like. Among these, the productivity of the optical film can be further improved by improving the extensibility and carrying out the stretching at a higher temperature, and reducing the occurrence of problems such as elongation breakage during the manufacture of the optical film. In particular, ethylene is preferred. When the methylol-containing PVA contains an ethylene unit, based on the extensibility or elongation temperature as described above, when the molar number of the total structural unit constituting the methylol-containing PVA is 100 mole%, The content rate is preferably 1 to 4 mole%, and particularly preferably 2 to 3 mole%.
含有羥甲基之PVA中的式(1)所示之結構單元、乙烯醇單元及其他任意構成單元的排列次序無特別限制,可為隨機、嵌段、交替等任一種。 The arrangement order of the structural unit, the vinyl alcohol unit, and other arbitrary constituent units represented by formula (1) in the methylol-containing PVA is not particularly limited, and may be any of random, block, and alternate.
本發明之光學薄膜製造用坯材薄膜除上述含有羥甲基之PVA外亦可含有塑化劑。作為較佳之塑化劑可舉出多元醇,作為具體實例,可列舉乙二醇、丙三醇、丙二醇、二乙二醇、二丙三醇、三乙二醇、四乙二醇、三羥甲基丙烷等。本發明之光學薄膜製造用坯材薄膜可含有此等塑化劑的1種或2種以上。此等當中,基於延伸性提升效果等觀點,較佳為丙三醇。 The raw material film for producing an optical film of the present invention may contain a plasticizer in addition to the above-mentioned hydroxymethyl-containing PVA. Examples of preferred plasticizers include polyhydric alcohols. Specific examples include ethylene glycol, glycerol, propylene glycol, diethylene glycol, diglycerol, triethylene glycol, tetraethylene glycol, and trihydroxy alcohol. Methylpropane and the like. The raw material film for producing an optical film of the present invention may contain one or two or more of these plasticizers. Among these, glycerin is preferred from the viewpoints of elongation improving effect and the like.
本發明之光學薄膜製造用坯材薄膜之塑化劑的含量,相對於其所含的含有羥甲基之PVA100質量份而言,較佳為1~20質量份之範圍內,更佳為3~17質量份之範圍內,再佳為5~15質量份之範圍內。使該含量為1質量份以上,可進一步提升薄膜的延伸性。另一方面,使該含量為20質量份以下,則可抑制薄膜過於柔軟而使操作處理性下降的情況。 The content of the plasticizer of the raw material film for optical film manufacturing of the present invention is preferably within a range of 1 to 20 parts by mass, more preferably 3 to 100 parts by mass of PVA containing methylol groups. It is in a range of ~ 17 parts by mass, and even more preferably in a range of 5 to 15 parts by mass. When the content is 1 part by mass or more, the stretchability of the film can be further improved. On the other hand, when the content is 20 parts by mass or less, it is possible to prevent the film from being too soft and lowering the handling properties.
本發明之光學薄膜製造用坯材薄膜中,可進一步視需求適當摻混填充劑、銅化合物等的加工穩定劑、耐候性穩定劑、著色劑、紫外線吸收劑、光穩定劑、抗氧化劑、抗靜電劑、難燃劑、其他熱塑性樹脂、潤滑劑、香料、消泡劑、消臭劑、增量劑、剝離劑、脫模劑、補強劑、交聯劑、防黴劑、防腐劑、結晶化速度延緩劑等添加劑。 In the raw material film for optical film manufacturing of the present invention, processing stabilizers, weather stabilizers, colorants, ultraviolet absorbers, light stabilizers, antioxidants, Static agents, flame retardants, other thermoplastic resins, lubricants, fragrances, defoamers, deodorants, extenders, release agents, mold release agents, reinforcing agents, cross-linking agents, mold inhibitors, preservatives, crystals Additives such as chemical retarder.
基於光學薄膜製造用坯材薄膜的質量,本發 明之光學薄膜製造用坯材薄膜中的含有羥甲基之PVA及塑化劑的合計所占的比例較佳為80質量%以上,更佳為90質量%以上,再佳為95質量%以上。 Based on the quality of the blank film for optical film manufacturing, the present invention The total ratio of the methylol-containing PVA and the plasticizer in Mingzhi's optical film manufacturing film is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more.
本發明之光學薄膜製造用坯材薄膜的膨潤度較佳為160~240%之範圍內,更佳為170~230%之範圍內,特佳為180~220%之範圍內。使膨潤度為160%以上,藉此可極力抑制結晶化的進行,可穩定地實施延伸至高倍率。另一方面,使膨潤度為240%以下,藉此可抑制延伸時的溶解,縱使在更高溫的條件下仍可實施延伸。此外,本說明書中,光學薄膜製造用坯材薄膜的膨潤度係指將光學薄膜製造用坯材薄膜浸漬於30℃的蒸餾水中30分鐘時的質量除以浸漬後於105℃乾燥16小時後的質量所得之值的百分率,具體而言可藉由實施例中的後述方法來測定。 The swelling degree of the blank film for optical film manufacturing of the present invention is preferably in the range of 160 to 240%, more preferably in the range of 170 to 230%, and particularly preferably in the range of 180 to 220%. By making the degree of swelling to 160% or more, the progress of crystallization can be suppressed as much as possible, and the stretching can be performed stably to a high magnification. On the other hand, when the degree of swelling is 240% or less, the dissolution during stretching can be suppressed, and the stretching can be performed even at a higher temperature. In addition, in this specification, the swelling degree of a raw material film for optical film manufacturing refers to the mass when the raw material film for optical film manufacturing is immersed in distilled water at 30 ° C for 30 minutes divided by the mass after impregnation and drying at 105 ° C for 16 hours. The percentage of the value obtained by mass can be specifically measured by the method mentioned later in an Example.
本發明之光學薄膜製造用坯材薄膜的厚度不特別限制,一般較佳為1~100μm左右,再佳為5~75μm左右,特佳為10~60μm左右。該厚度如過薄,在用以製造偏光薄膜等光學薄膜的單軸延伸處理時,有容易發生延伸斷裂的傾向。又,該厚度如過厚,則在用以製造光學薄膜的單軸延伸處理時有容易發生延伸不均的傾向。 The thickness of the blank film for optical film manufacturing of the present invention is not particularly limited, but is generally preferably about 1 to 100 μm, more preferably about 5 to 75 μm, and particularly preferably about 10 to 60 μm. If the thickness is too thin, the film tends to be easily stretched during uniaxial stretching for producing an optical film such as a polarizing film. Moreover, if this thickness is too thick, there is a tendency that uneven stretching is liable to occur during uniaxial stretching processing for producing an optical film.
本發明之光學薄膜製造用坯材薄膜的寬度不特別限制,可視待製造之光學薄膜的用途等來決定。近年來,基於推進液晶電視或液晶螢幕的大畫面化而言,若將光學薄膜製造用坯材薄膜的寬度形成3m以上,則適用於此等用途。另一方面,光學薄膜製造用坯材薄膜的 寬度如過大,則在以實用化之裝置製造光學薄膜時均勻地進行單軸延伸本身易更趨困難,因此,光學薄膜製造用坯材薄膜的寬度較佳為7m以下。 The width of the raw material film for producing an optical film of the present invention is not particularly limited, and may be determined depending on the application of the optical film to be produced and the like. In recent years, in order to advance the enlargement of a liquid crystal television or a liquid crystal screen, if the width of a raw material film for optical film production is 3 m or more, it is suitable for these applications. On the other hand, the material film for optical film manufacturing If the width is too large, it is easier and more difficult to uniformly uniaxially stretch the optical film in a practical device. Therefore, the width of the blank film for optical film production is preferably 7 m or less.
本發明之光學薄膜製造用坯材薄膜之製造方法不特別限定,可較佳地採用製膜後之薄膜的厚度及寬度呈更均勻的製造方法,例如,可使用下述製膜原液來製造:使構成光學薄膜製造用坯材薄膜的上述含有羥甲基之PVA、及視需求進一步使上述之塑化劑、添加劑及後述之界面活性劑等中的1種或2種以上,溶於液體介質中而成的製膜原液;或包含含有羥甲基之PVA、及視需求進一步包含塑化劑、添加劑、界面活性劑及液體介質等中的1種或2種以上,且含有羥甲基之PVA已融解的製膜原液。該製膜原液含有塑化劑、添加劑及界面活性劑的至少1種時,係以使此等成分均勻混合為佳。 The manufacturing method of the raw material film for optical film manufacturing of the present invention is not particularly limited, and a manufacturing method in which the thickness and width of the film after film formation are more uniform can be preferably used. For example, the following film forming stock solution can be used for manufacturing: One or two or more of the above-mentioned plasticizers, additives, and surfactants described later are dissolved in the liquid medium, as required, of the methylol-containing PVA constituting the raw material film for optical film manufacturing, as required. A film-forming stock solution obtained from the above; or PVA containing methylol, and optionally one or more of plasticizers, additives, surfactants, and liquid media, etc., and containing methylol PVA melted film-forming stock solution. When the film-forming dope contains at least one of a plasticizer, an additive, and a surfactant, it is preferable to uniformly mix these components.
作為調製製膜原液所使用的上述液體介質,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、丙三醇、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,能使用此等當中的1種或2種以上。其中,就環境負擔或回收性而言較佳為水。 Examples of the liquid medium used for preparing the film-forming stock solution include water, dimethylmethylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene glycol, and propyl. Triol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, ethylenediamine, diethylenetriamine, etc., one or two or more of these can be used. Among these, water is preferable in terms of environmental burden or recyclability.
製膜原液的揮發分率(製膜時藉由揮發、蒸發所去除之液體介質等的揮發性成分於製膜原液中的含有比例)雖因製膜方法、製膜條件等而異,一般而言,較佳為50~95質量%之範圍內,更佳為55~90質量%之範圍內,再佳為60~85質量%之範圍內。使製膜原液的揮發分 率為50質量%以上,藉此製膜原液的黏度便不會過高,可順利進行製膜原液調製時的過濾或脫泡,而容易製造雜質或缺陷較少的薄膜。另一方面,使製膜原液的揮發分率為95質量%以下,藉此製膜原液的濃度不會過低,工業上薄膜的製造變得容易。 The volatile content of the film-forming raw liquid (the proportion of the volatile components in the film-forming raw liquid of the liquid medium and the like removed by evaporation and evaporation during film-forming) varies depending on the film-forming method and film-forming conditions, etc. In other words, it is preferably in the range of 50 to 95% by mass, more preferably in the range of 55 to 90% by mass, and even more preferably in the range of 60 to 85% by mass. Make the volatiles of the film-forming stock solution The ratio is 50% by mass or more, so that the viscosity of the film-forming dope will not be too high, and filtering or defoaming during the preparation of the film-forming dope can be smoothly performed, and a thin film with less impurities or defects is easily produced. On the other hand, by setting the volatile content of the film-forming dope to 95% by mass or less, the concentration of the film-forming dope is not excessively low, and industrial production of a thin film becomes easy.
製膜原液係以含有界面活性劑為佳。透過含有界面活性劑,可提升製膜性並抑制薄膜厚度不均的產生,同時亦使薄膜從製膜所使用之金屬輥或帶剝離變得容易。自含有界面活性劑的製膜原液製造光學薄膜製造用坯材薄膜時,該薄膜中可含有界面活性劑。上述之界面活性劑的種類不特別限定,基於從金屬輥或帶的剝離性觀點等,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 dope is preferably containing a surfactant. By including a surfactant, the film-forming property can be improved and the uneven thickness of the film can be suppressed. At the same time, the film can be easily peeled from the metal roller or belt used for film-making. When a raw material film for optical film manufacturing is produced from a film-forming dope containing a surfactant, the film may contain a surfactant. The type of the above-mentioned surfactant is not particularly limited, and is preferably an anionic surfactant or a nonionic surfactant from the standpoint of releasability from a metal roll or a belt.
作為陰離子性界面活性劑,合適者為例如月桂酸鉀等的羧酸型;聚氧乙烯月桂基醚硫酸鹽、硫酸辛酯等的硫酸酯型;十二烷基苯磺酸酯等的磺酸型等。 Suitable anionic surfactants are, for example, carboxylic acid types such as potassium laurate; sulfate types such as polyoxyethylene lauryl ether sulfate and octyl sulfate; and sulfonic acids such as dodecylbenzenesulfonate Type and so on.
作為非離子系界面活性劑,合適者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;聚氧伸烷基烯丙基苯基醚等烯丙基苯基醚型等。 Suitable nonionic surfactants are, for example, alkyl ether types such as polyoxyethylene oleyl ether; alkylphenyl ether types such as polyoxyethylene octylphenyl ether; alkyl esters such as polyoxyethylene laurate Type; alkylamine types such as polyoxyethylene laurylamine ether; alkylamine types such as polyoxyethylene laurate amine; polypropylene glycol ether types such as polyoxyethylene polyoxypropylene ether; diethanolamine laurate, Alkanolamines such as diethanolamine oleate and allylphenylethers such as polyoxyalkylene allylphenyl ether.
此等界面活性劑可單獨使用1種、或組合使用2種以上。 These surfactants can be used singly or in combination of two or more kinds.
當製膜原液含有界面活性劑時,相對於製膜原液所含的含有羥甲基之PVA100質量份,其含量較佳為0.01~0.5質量份之範圍內,更佳為0.02~0.3質量份之範圍內,特佳為0.05~0.1質量份之範圍內。使該含量為0.01質量份以上,可進一步提升製膜性及剝離性。另一方面,使該含量為0.5質量份以下,可抑制界面活性劑自光學薄膜製造用坯材薄膜的表面滲出而發生黏連,導致操作處理性降低的情況。 When the film-forming dope contains a surfactant, the 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 100 parts by mass of methylol-containing PVA contained in the film-forming dope. Within the range, particularly preferred is within a range of 0.05 to 0.1 parts by mass. When the content is 0.01 parts by mass or more, film-forming properties and peelability can be 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 from the surface of the base film for optical film production and causing blocking, which may reduce handling properties.
作為使用上述製膜原液來製造光學薄膜製造用坯材薄膜時的製膜方法,可列舉例如流延製膜法、擠出製膜法、濕式製膜法、膠體製膜法等。此等製膜方法可僅採用1種,亦可組合採用2種以上。此等製膜方法當中,基於可得厚度及寬度均勻且物性良好的光學薄膜製造用坯材薄膜而言,流延製膜法、擠出製膜法較佳。製成之薄膜可視需求進行乾燥或熱處理。 Examples of the film forming method in the case of using the above-mentioned film forming stock solution to produce a thin film for optical film production include a casting film forming method, an extrusion film forming method, a wet film forming method, and a colloidal film method. These film forming methods may be used alone or in combination of two or more. Among these film-forming methods, a cast film method and an extrusion film-forming method are preferred in terms of obtaining a raw material film for optical film production with uniform thickness and width and good physical properties. The produced film can be dried or heat-treated as required.
作為本發明之光學薄膜製造用坯材薄膜的具體製造方法之例,於工業上可較佳採用例如此方法:使用T字縫模、斗板(hopper plate)、I字模、唇塗布模具(lip coater die)等,將上述製膜原液均勻地排出或流延至位於最上游側之旋轉並經加熱的第1輥(或者帶)的周面上,使揮發性成分從被排出或流延至該第1輥(或者帶)的周面上的膜的一面蒸發而乾燥,接著在配置於其下游側之1根或多根旋轉並經加熱的輥的周面上進一步進行乾燥,或使其通過熱風乾燥裝置內而進一步進行乾燥後以捲繞裝置予以捲繞。亦可適當組合經由加熱輥所進行之乾燥 與經由熱風乾燥裝置所進行之乾燥來實施。 As an example of a specific manufacturing method of the blank film for manufacturing an optical film of the present invention, for example, this method can be preferably used industrially: using a T-shaped slit die, a hopper plate, an I-shaped die, and a lip coating die coater die), etc., to uniformly discharge or cast the above-mentioned film-forming dope to the peripheral surface of the first rotating (heated) roll (or belt) located on the most upstream side, so that volatile components are discharged or cast to the first One side of the film on the peripheral surface of one roll (or belt) evaporates to dry, and is further dried on the peripheral surface of one or more rotating and heated rolls arranged on the downstream side, or passed through hot air After being further dried in the drying device, it is wound by a winding device. Can also be appropriately combined with drying by heating roller And drying by a hot air drying device.
本發明之光學薄膜製造用坯材薄膜係作為供製造光學薄膜的坯材薄膜使用。作為此類光學薄膜,可列舉例如偏光薄膜或相位差薄膜等。此種光學薄膜可藉由例如使用本發明之光學薄膜製造用坯材薄膜實施單軸延伸等處理的方法來製造。 The raw material film for manufacturing an optical film of the present invention is used as a raw material film for manufacturing an optical film. Examples of such an optical film include a polarizing film and a retardation film. Such an optical film can be manufactured by the method of performing processing, such as uniaxial stretching, using the blank film for optical film manufacturing of this invention.
使用本發明之光學薄膜製造用坯材薄膜製造偏光薄膜時的方法不特別限制,可採用向來所採用的任何方法。作為此類方法,可列舉例如對本發明之光學薄膜製造用坯材薄膜實施染色及單軸延伸、或對含有染料的本發明之光學薄膜製造用坯材薄膜實施單軸延伸的方法。作為供製造偏光薄膜的更具體方法,可舉出對本發明之光學薄膜製造用坯材薄膜,實施膨潤、染色、單軸延伸、及視需求進一步實施交聯處理、固定處理、乾燥、熱處理等的方法。此時,膨潤、染色、交聯處理、單軸延伸、固定處理等的各處理的順序不特別限制,也可同時進行1種或2種以上之處理。又,亦能以2次或其以上進行各處理的1種或2種以上。 The method for manufacturing a polarizing film using the blank film for optical film manufacturing of the present invention is not particularly limited, and any method conventionally used can be adopted. Examples of such a method include a method of dyeing and uniaxially stretching the raw material film for optical film manufacturing of the present invention, or uniaxially stretching the raw material film for optical film manufacturing of the present invention containing a dye. As a more specific method for manufacturing a polarizing film, the raw material film for optical film manufacturing of the present invention may be swelled, dyed, uniaxially stretched, and further subjected to cross-linking treatment, fixing treatment, drying, heat treatment, etc. as required. method. At this time, the order of each treatment such as swelling, dyeing, crosslinking treatment, uniaxial stretching, and fixing treatment is not particularly limited, and one or two or more treatments may be performed simultaneously. In addition, one or two or more kinds of each treatment can be performed twice or more.
膨潤可藉由將光學薄膜製造用坯材薄膜浸漬於水中來進行。就浸漬於水中時之水的溫度而言,較佳為20~40℃之範圍內,更佳為22~38℃之範圍內,再佳為25~35℃之範圍內。又,就浸漬於水中的時間而言,例如較佳為0.1~5分鐘之範圍內,更佳為0.5~3分鐘之範圍內。再者,浸漬於水中時的水不限於純水,可為溶有各種成分的水溶液,亦可為水與水性介質的混合物。 Swelling can be performed by immersing a raw material film for optical film production in water. The temperature of 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 even more preferably in the range of 25 to 35 ° C. The time for immersion in water is, for example, preferably within a range of 0.1 to 5 minutes, and more preferably within a range of 0.5 to 3 minutes. 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 a mixture of water and an aqueous medium.
染色可藉由使光學薄膜製造用坯材薄膜接觸二色性色素來進行。作為二色性色素,一般係使用碘系色素。就染色的時間點而言,可為單軸延伸前、單軸延伸時、單軸延伸後任一階段。染色一般係藉由將光學薄膜製造用坯材薄膜浸漬於作為染色浴之含有碘-碘化鉀的溶液(特別是水溶液)中來進行,在本發明中亦適合採用此種染色方法。染色浴中的碘的濃度較佳為0.01~0.5質量%之範圍內,碘化鉀的濃度較佳為0.01~10質量%之範圍內。又,染色浴的溫度係以設為20~50℃,特別是25~40℃為佳。 Dyeing can be performed by contacting a raw material film for optical film manufacturing with a dichroic dye. As a dichroic pigment, an iodine-based pigment is generally used. The time point of dyeing can be any stage before uniaxial extension, during uniaxial extension, or after uniaxial extension. Dyeing is generally performed by immersing a raw material film for optical film manufacturing in a solution (particularly, an aqueous solution) containing iodine-potassium iodide as a dyeing bath, and this dyeing method is also suitably used in the present invention. The concentration of iodine in the dyeing bath is preferably within a range of 0.01 to 0.5% by mass, and the concentration of potassium iodide is preferably within a range of 0.01 to 10% by mass. The temperature of the dyeing bath is preferably 20 to 50 ° C, and particularly preferably 25 to 40 ° C.
透過對光學薄膜製造用坯材薄膜實施交聯處理,在高溫下實施濕式延伸時能更有效防止含有羥甲基之PVA在水中溶出。基於此觀點,交聯處理較佳在使其接觸二色性色素的處理後,即在單軸延伸前進行。交聯處理可藉由將光學薄膜製造用坯材薄膜浸漬於含有交聯劑的水溶液來進行。作為該交聯劑,可使用硼酸、硼砂等的硼酸鹽等硼化合物的1種或2種以上。含有交聯劑的水溶液中之交聯劑的濃度較佳為1~15質量%之範圍內,更佳為2~7質量%之範圍內,再佳為3~6質量%之範圍內。使交聯劑的濃度處於1~15質量%之範圍內,可維持充分的延伸性。含有交聯劑的水溶液亦可含有碘化鉀等助劑。含有交聯劑的水溶液的溫度係以設為20~50℃之範圍內,特別是25~40℃之範圍內為佳。使該溫度處於20~50℃之範圍內,則可效率良好地進行交聯。 By performing a cross-linking treatment on the raw material film for optical film manufacturing, it is possible to more effectively prevent PVA containing methylol from dissolving in water when wet stretching is performed at a high temperature. From this viewpoint, the cross-linking treatment is preferably performed after the treatment for contacting the dichroic pigment, that is, before the uniaxial stretching. The crosslinking treatment can be performed by immersing a raw material film for optical film production in an aqueous solution containing a crosslinking agent. As this crosslinking agent, one or two or more kinds of boron compounds such as borate such as boric acid and borax can be used. The concentration of the crosslinking agent in the aqueous solution containing the crosslinking agent is preferably in the range of 1 to 15% by mass, more preferably in the range of 2 to 7% by mass, and even more preferably in the range of 3 to 6% by mass. When the concentration of the crosslinking agent is in the range of 1 to 15% by mass, sufficient extensibility can be maintained. The aqueous solution containing a crosslinking agent may contain adjuvants, such as potassium iodide. The temperature of the aqueous solution containing a crosslinking agent is preferably within a range of 20 to 50 ° C, and particularly preferably within a range of 25 to 40 ° C. When the temperature is in the range of 20 to 50 ° C, crosslinking can be performed efficiently.
單軸延伸可採濕式延伸法或乾式延伸法任一 種來進行。如採濕式延伸法時,可在含有硼酸的水溶液中進行,亦可在上述之染色浴中或後述之固定處理浴中進行。又,如採乾式延伸法時,可直接在室溫進行延伸,亦可一面加熱一面進行延伸,亦可使用吸水後的光學薄膜製造用坯材薄膜在空氣中進行。此等當中,較佳為濕式延伸法,更佳為在含有硼酸的水溶液中實施單軸延伸。硼酸水溶液中之硼酸的濃度較佳為0.5~6.0質量%之範圍內,更佳為1.0~5.0質量%之範圍內,特佳為1.5~4.0質量%之範圍內。又,硼酸水溶液亦可含有碘化鉀,其濃度係以設於0.01~10質量%之範圍內為佳。 Uniaxial extension can use either wet or dry extension method To carry out. For example, in the wet-drawing method, it can be performed in an aqueous solution containing boric acid, or it can be performed in the dyeing bath described above or in a fixed treatment bath described later. In the case of the dry stretching method, stretching may be performed at room temperature directly, or heating may be performed while stretching, or a raw material film for optical film manufacturing after water absorption may be used in the air. Among these, a wet stretching method is preferred, and uniaxial stretching is more preferably performed in an aqueous solution containing boric acid. The concentration of boric acid in the boric acid aqueous solution is preferably within a range of 0.5 to 6.0% by mass, more preferably within a range of 1.0 to 5.0% by mass, and particularly preferably within a range of 1.5 to 4.0% by mass. The boric acid aqueous solution may contain potassium iodide, and its concentration is preferably set in a range of 0.01 to 10% by mass.
單軸延伸的延伸溫度較佳為30~90℃之範圍內,更佳為40~80℃之範圍內,特佳為50~70℃之範圍內。 The uniaxial stretching temperature 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.
又,基於所得偏光薄膜的偏光性能觀點,單軸延伸的延伸倍率較佳為6.8倍以上,更佳為6.9倍以上,特佳為7.0倍以上。延伸倍率的上限不特別限制,延伸倍率較佳為8倍以下。 Moreover, from the viewpoint of the polarization performance of the obtained polarizing film, the stretching magnification of uniaxial stretching is preferably 6.8 times or more, more preferably 6.9 times or more, and particularly preferably 7.0 times or more. The upper limit of the stretching magnification is not particularly limited, and the stretching magnification is preferably 8 times or less.
對長尺寸光學薄膜製造用坯材薄膜實施單軸延伸時之單軸延伸的方向無特別限制,可採用朝長度方向的單軸延伸或橫向單軸延伸,惟由可得偏光性能優良的偏光薄膜而言,較佳為朝長度方向的單軸延伸。朝長度方向的單軸延伸可使用具備相互平行的複數個輥的延伸裝置,改變各輥間的周速來進行。另一方面,橫向單軸延伸可使用拉幅型延伸機來進行。 There is no particular limitation on the direction of uniaxial extension when uniaxial stretching is performed on a long-length optical film manufacturing blank film. A uniaxial extension in the longitudinal direction or a uniaxial extension in the lateral direction can be used, but a polarizing film with excellent polarization performance can be obtained It is preferable to extend uniaxially in the longitudinal direction. The uniaxial extension in the longitudinal direction can be performed by changing the peripheral speed between the rollers using an extension device having a plurality of rollers parallel to each other. On the other hand, transverse uniaxial stretching can be performed using a tenter type stretching machine.
在偏光薄膜製造之際,為使二色性色素(碘系色素等)對薄膜的吸附更強固,係以進行固定處理為佳。 作為固定處理所使用的固定處理浴,可使用含有硼酸、硼砂等硼化合物的1種或2種以上的水溶液。又,亦可視需求在固定處理浴中添加碘化合物或金屬化合物。固定處理浴中之硼化合物的濃度係以一般為2~15質量%,特別是3~10質量%左右為佳。藉著使該濃度處於2~15質量%之範圍內,可使二色性色素的吸附更加強固。固定處理浴的溫度係以15~60℃,特別是25~40℃為佳。 In the case of manufacturing a polarizing film, it is preferable to perform a fixing treatment in order to make the film more strongly adsorbed by a dichroic dye (such as an iodine dye). As the fixed treatment bath used for the fixed treatment, an aqueous solution containing one or two or more boron compounds such as boric acid and borax can be used. In addition, an iodine compound or a metal compound may be added to the fixed processing bath as required. The concentration of the boron compound in the fixed treatment bath is generally 2 to 15% by mass, and particularly preferably about 3 to 10% by mass. When the concentration is in the range of 2 to 15% by mass, the adsorption of the dichroic pigment can be further strengthened. The temperature of the fixed treatment bath is preferably 15 to 60 ° C, especially 25 to 40 ° C.
乾燥之條件不特別限制,惟較佳在30~150℃之範圍內,特別是50~130℃之範圍內的溫度下進行乾燥。藉著在30~150℃之範圍內的溫度進行乾燥,可使易獲得尺寸穩定性優良的偏光薄膜。 The drying conditions are not particularly limited, but drying is preferably performed at a temperature in a range of 30 to 150 ° C, particularly in a range of 50 to 130 ° C. By drying at a temperature in the range of 30 to 150 ° C, a polarizing film having excellent dimensional stability can be easily obtained.
如上所得之偏光薄膜,通常係在其兩面或單面貼合光學上呈透明且具有機械強度之保護膜,作成偏光板而使用。作為保護膜,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,作為用於貼合之接著劑,可列舉PVA系接著劑、胺基甲酸酯系接著劑等,其中較合適為PVA系接著劑。 The polarizing film obtained as described above is usually a protective film that is optically transparent and mechanically bonded on both sides or one side of the film, and is used as a polarizing plate. As the protective film, cellulose triacetate (TAC) film, acetic acid can be used. Cellulose butyrate (CAB) film, acrylic film, polyester film, etc. Examples of the adhesive used for bonding include PVA-based adhesives, urethane-based adhesives, and the like. Among them, PVA-based adhesives are more suitable.
如上所得之偏光板,可在塗覆丙烯酸系等的黏著劑之後貼合於玻璃基板,作成LCD的零件而使用。同時,亦可與相位差薄膜、視角提升薄膜、亮度提升薄膜等貼合。 The polarizing plate obtained as described above can be used as an LCD part after being adhered to a glass substrate after being coated with an acrylic-based adhesive. At the same time, it can also be laminated with retardation film, viewing angle enhancement film, and brightness enhancement film.
以下,根據實施例對本發明更詳細地加以說明,惟本發明不受此等實施例任何限定。此外,以下示 出以下實施例及比較例中所採用的各測定或評定方法。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by these examples. In addition, the following Each measurement or evaluation method used in the following examples and comparative examples is given.
PVA的一次結構Primary structure of PVA
以下實施例及比較例所使用的PVA(實施例中的含有羥甲基之PVA或比較例中的各種改質PVA)的一次結構係利用270MHz 1H-NMR進行分析。1H-NMR測定時的溶劑係使用氘化DMSO。 The primary structure of the PVA used in the following examples and comparative examples (PVA containing methylol in the examples or various modified PVA in the comparative examples) was analyzed by 270 MHz 1 H-NMR. The solvent used in the 1 H-NMR measurement was deuterated DMSO.
光學薄膜製造用坯材薄膜的膨潤度Swelling degree of the base film for optical film manufacturing
將以下實施例或比較例所得的光學薄膜製造用坯材薄膜切成1.5g,予以浸漬於30℃的蒸餾水中30分鐘。浸漬30分鐘後取出該薄膜,以濾紙吸取表面的水,求得質量「N」。接著將該薄膜以105℃之乾燥機乾燥16小時後,求得質量「M」。由所得的質量「N」及「M」,依下述式(3)算出光學薄膜製造用坯材薄膜的膨潤度。 The raw material film for optical film production obtained in the following examples or comparative examples was cut into 1.5 g, and immersed in distilled water at 30 ° C. for 30 minutes. After being immersed for 30 minutes, the film was taken out, and the surface water was absorbed by a filter paper to obtain a mass "N". Then, the film was dried in a dryer at 105 ° C. for 16 hours, and the mass “M” was obtained. From the obtained masses "N" and "M", the degree of swelling of the raw material film for optical film manufacturing was calculated according to the following formula (3).
膨潤度(%)=100×N/M (3) Swelling (%) = 100 × N / M (3)
光學薄膜製造用坯材薄膜的延伸性Extensibility of blank film for optical film manufacturing
自以下實施例或比較例所得的光學薄膜製造用坯材薄膜的寬度方向中央部,切出寬5cm×長8cm之樣品以使寬5cm×長5cm之範圍可實施單軸延伸。將該樣品浸漬於30℃之純水之同時朝長度方向實施單軸延伸達1.5倍。接著,予以浸漬於以0.03質量%及3.0質量%之比例含有碘及碘化鉀的水溶液(染色浴)(溫度30℃)60秒同時朝長度方向實施單軸延伸達1.6倍(全體而言為2.4倍)而使碘吸附。其次,予以浸漬於以3質量%及3質量%之比例含有硼酸及碘化鉀的水溶液(交聯浴)(溫度30℃),同時朝長度方向實施單軸延伸達1.1倍(全體而言為2.6倍)。進而,予以浸 漬於以4質量%及6質量%之比例含有硼酸及碘化鉀的水溶液(延伸浴),同時朝長度方向實施單軸延伸至斷裂為止,以相對於延伸前之光學薄膜製造用坯材薄膜的長度而言斷裂時的長度的倍率作為極限延伸倍率。惟,就延伸浴的溫度而言,係自適當的溫度起按每1℃變更而測定限界延伸倍率,並選擇使限界延伸倍率變為最高的溫度。 From the central portion in the width direction of the blank film for manufacturing an optical film obtained in the following examples or comparative examples, a sample having a width of 5 cm × a length of 8 cm was cut so that a range of 5 cm × 5 cm in length could be uniaxially stretched. This sample was immersed in pure water at 30 ° C while being uniaxially extended up to 1.5 times in the longitudinal direction. Next, it was immersed in an aqueous solution (dyeing bath) (temperature: 30 ° C.) containing iodine and potassium iodide in a ratio of 0.03% by mass and 3.0% by mass for 60 seconds while performing uniaxial extension in the longitudinal direction by 1.6 times (2.4 times for the whole). ) To adsorb iodine. Next, it was immersed in an aqueous solution (crosslinking bath) containing boric acid and potassium iodide (temperature: 30 ° C.) at a ratio of 3% by mass and 3% by mass, and uniaxially extended 1.1 times in the longitudinal direction (2.6 times as a whole). ). Further, dipping It is stained with an aqueous solution (extension bath) containing boric acid and potassium iodide at a ratio of 4% by mass and 6% by mass, and uniaxially extended in the longitudinal direction until it breaks, so as to be equal to the length of the blank film for optical film manufacturing before stretching The ratio of the length at the time of breaking is regarded as the limit extension ratio. However, as for the temperature of the extension bath, the limit extension magnification is measured every 1 ° C change from an appropriate temperature, and the temperature at which the limit extension magnification is maximized is selected.
偏光薄膜的光學特性(二色性比)Optical properties of polarizing film (dichroic ratio)
(1)穿透率Ts的測定 (1) Measurement of transmittance Ts
自以下實施例或比較例所得的偏光薄膜的中央部,沿偏光薄膜的長度方向採取2片2cm之樣品,利用附積分球之分光光度計(日本分光股份有限公司製「V7100」),基於JIS Z 8722(物體色之測定方法),進行C光源、2°視野之可見光區域的可見度(visibility)校正,針對一片樣品,測定與長度方向傾斜+45°時的光穿透率與傾斜-45°時的光穿透率,求出彼等之平均值Ts1(%)。針對另一片樣品亦同樣地測定傾斜+45°時的光穿透率與傾斜-45°時的光穿透率,求出彼等之平均值Ts2(%)。依下述式(4)將Ts1與Ts2加以平均,以其為偏光薄膜的穿透率Ts(%)。 From the central portion of the polarizing film obtained in the following examples or comparative examples, two 2 cm samples were taken along the length of the polarizing film, and a spectrophotometer with an integrating sphere ("V7100" manufactured by JASCO Corporation) was used based on JIS. Z 8722 (Measurement method of object color). Correct the visibility of the visible light region of C light source and 2 ° visual field. For a piece of sample, measure the light transmittance and tilt -45 ° when tilted by + 45 ° from the longitudinal direction. The light transmittance at this time was calculated as their average Ts1 (%). The light transmittance at a tilt of + 45 ° and the light transmittance at a tilt of -45 ° were similarly measured for another sample, and their average Ts2 (%) was obtained. Ts1 and Ts2 are averaged according to the following formula (4), and this is taken as the transmittance Ts (%) of the polarizing film.
Ts=(Ts1+Ts2)/2 (4) Ts = (Ts1 + Ts2) / 2 (4)
(2)偏光度V的測定 (2) Measurement of polarization degree V
以與上述「(1)穿透率Ts的測定」之情形同樣的方式,測定將上述穿透率Ts的測定中所採取的2片樣品以使其長度方向呈平行的方式重疊時的光穿透率T//(%)、以使 長度方向呈正交的方式重疊時的光穿透率T⊥(%),依下述式(5)求出偏光度V(%)。 In the same manner as in the case of "(1) Measurement of the transmittance Ts" described above, the light transmission when the two samples taken in the measurement of the transmittance Ts are overlapped so that their longitudinal directions are parallel is measured. Transmittance T // (%), so that The light transmittance T⊥ (%) when the longitudinal directions are overlapped so as to be orthogonal, and the degree of polarization V (%) is obtained by the following formula (5).
V={(T//-T⊥)/(T//+T⊥)}1/2×100 (5) V = ((T //-T⊥) / (T // + T⊥)) 1/2 × 100 (5)
(3)穿透率44%時之二色性比的算出 (3) Calculation of dichroism ratio at 44% transmittance
在以下各實施例及比較例中,將染色浴中之碘的濃度及碘化鉀的濃度各在0.02~0.04質量%及2.0~4.0質量%之各範圍內改變4次(惟,設碘的濃度:碘化鉀的濃度=1:100)而進行同樣的操作,製成二色性色素的吸附量與各實施例或比較例所製造之偏光薄膜相異的4片偏光薄膜。對此4片偏光薄膜各者,以上述方法求出穿透率Ts(%)及偏光度V(%),並按各實施例及比較例,以穿透率Ts(%)為橫軸、偏光度V(%)為縱軸,將亦包含根據由各實施例或比較例所得之偏光薄膜的穿透率Ts(%)及偏光度V(%)的1點的合計5點繪製成圖形而求取近似曲線,並由該近似曲線,求出穿透率Ts(%)為44%時的偏光度V44(%)。 In each of the following examples and comparative examples, the concentration of iodine and the concentration of potassium iodide in the dyeing bath were changed 4 times in each of the ranges of 0.02 to 0.04% by mass and 2.0 to 4.0% by mass (but, the iodine concentration was set: The concentration of potassium iodide = 1: 100), and the same operation was performed to produce four polarizing films having different adsorption amounts of the dichroic pigments from the polarizing films produced in the respective examples or comparative examples. For each of the four polarizing films, the transmittance Ts (%) and the polarization degree V (%) were obtained by the above method, and according to the examples and comparative examples, the transmittance Ts (%) was taken as the horizontal axis, The degree of polarization V (%) is the vertical axis, and a total of 5 points including 1 point of the transmittance Ts (%) and the degree of polarization V (%) of the polarizing film obtained from each example or comparative example are also plotted. An approximate curve is obtained, and from this approximate curve, the polarization degree V 44 (%) when the transmittance Ts (%) is 44% is obtained.
由所得偏光度V44(%),依下述式(6)求出穿透率44%時的二色性比,以其為偏光性能的指標。 From the obtained polarization degree V 44 (%), a dichroism ratio at a transmittance of 44% was obtained according to the following formula (6), and this was used as an index of polarization performance.
穿透率44%時的二色性比=log(44/100-44/100×V44/100)/log(44/100+44/100×V44/100) (6) Transmittance of 44% when the dichroic ratio = log (44 / 100-44 / 100 × V 44/100) / log (44/100 + 44/100 × V 44/100) (6)
偏光薄膜的色相(平行b值)Hue (parallel b-value) of polarizing film
在上述之「偏光薄膜的光學特性(二色性比)」中,在求取二色性色素的吸附量相異的4片偏光薄膜的偏光度V時,係於穿透率T//(%)及穿透率T⊥(%)測定時測定Lab,以穿透率T//(%)之測定時的b值為平行b值、以穿透 率T⊥(%)之測定時的b值為正交b值。按各實施例及比較例,以平行b值為橫軸、正交b值為縱軸,將亦包含根據由各實施例或比較例所得之偏光薄膜的平行b值及正交b值的1點的合計5點繪製成圖形而求取近似曲線,並由該近似曲線,求出正交b值為-4時的平行b值。此外,平行b值愈接近0則偏光薄膜的色相愈良好。 In the above-mentioned "optical characteristics of polarizing film (dichroic ratio)", when determining the polarization degree V of four polarizing films having different adsorption amounts of dichroic pigments, it is based on the transmittance T // ( %) And transmittance T⊥ (%) are measured during the measurement of Lab, and the b value during the measurement of the transmittance T // (%) is parallel to the b value. The b value at the time of measuring the ratio T⊥ (%) is an orthogonal b value. According to each embodiment and comparative example, the parallel b value is the horizontal axis and the orthogonal b value is the vertical axis. The parallel b value and the orthogonal b value of the polarizing film obtained from the respective embodiments or comparative examples are also included. A total of 5 points were drawn into a graph to obtain an approximate curve. From the approximate curve, a parallel b-value when the orthogonal b-value was -4 was obtained. In addition, the closer the parallel b value is to 0, the better the hue of the polarizing film.
[實施例1] [Example 1]
(1)將包含:作為改質PVA之100質量份藉由將乙酸乙烯酯與1,3-二乙醯氧-2-亞甲基丙烷的共聚物皂化所得的表1所示之含有羥甲基之PVA、作為塑化劑之10質量份的丙三醇、及作為界面活性劑之0.1質量份的聚氧乙烯月桂基醚硫酸鈉,且改質PVA的含有率為10質量%的水溶液,作為製膜原液使用,透過將其在80℃之金屬輥上乾燥,並對所得薄膜在熱風乾燥機中以既定溫度實施熱處理1分鐘而將膨潤度調整為200%,製成厚度為30μm的光學薄膜製造用坯材薄膜。 (1) 100 parts by mass of modified PVA is contained in the methylol-containing group shown in Table 1 obtained by saponifying a copolymer of vinyl acetate and 1,3-diacetoxy-2-methylenepropane Based PVA, 10 parts by mass of glycerin as a plasticizer, and 0.1 parts by mass of polyoxyethylene lauryl ether sodium sulfate as a surfactant, and a modified PVA containing 10% by mass of an aqueous solution, Used as a film-forming stock solution, by drying it on a metal roll at 80 ° C., and subjecting the obtained film to heat treatment in a hot-air dryer at a predetermined temperature for 1 minute to adjust the swelling degree to 200% to produce an optical thickness of 30 μm The raw material film for film production.
使用所得光學薄膜製造用坯材薄膜,依上述方法評定延伸性。將結果示於表1。 Using the obtained raw material film for optical film manufacture, the extensibility was evaluated by the method described above. The results are shown in Table 1.
(2)自上述(1)所得的光學薄膜製造用坯材薄膜的寬度方向中央部,切出寬5cm×長8cm之樣品以使寬5cm×長5cm之範圍可實施單軸延伸的方式。將該樣品浸漬於30℃之純水之同時朝長度方向實施單軸延伸達1.5倍。接著,予以浸漬於以0.03質量%及3.0質量%之比例含有碘及碘化鉀的水溶液(染色浴)(溫度30℃)60秒同時朝長度方向實施單軸延伸達1.6倍(全體而言為2.4倍)而使 碘吸附。其次,予以浸漬於以3質量%及3質量%之比例含有硼酸及碘化鉀的水溶液(交聯浴)(溫度30℃),同時朝長度方向實施單軸延伸達1.1倍(全體而言為2.6倍)。進而,予以浸漬於以4質量%及6質量%之比例含有硼酸及碘化鉀的水溶液(延伸浴)(上述「光學薄膜製造用坯材薄膜的延伸性」中所求得之使極限延伸倍率變為最高的溫度),同時朝長度方向實施單軸延伸至比極限延伸倍率低0.2倍的倍率。其後,予以浸漬於以3質量%之比例含有碘化鉀的水溶液(清洗浴)(溫度30℃)5秒,最終於60℃乾燥4分鐘而製成偏光薄膜。 (2) From the central portion in the width direction of the blank film for optical film manufacturing obtained in the above (1), a sample having a width of 5 cm × a length of 8 cm was cut so that a range of 5 cm × 5 cm in length could be uniaxially stretched. This sample was immersed in pure water at 30 ° C while being uniaxially extended up to 1.5 times in the longitudinal direction. Next, it was immersed in an aqueous solution (dyeing bath) (temperature: 30 ° C.) containing iodine and potassium iodide in a ratio of 0.03% by mass and 3.0% by mass for 60 seconds while performing uniaxial extension in the longitudinal direction by 1.6 times (2.4 times for the whole). ) And Iodine adsorption. Next, it was immersed in an aqueous solution (crosslinking bath) containing boric acid and potassium iodide (temperature: 30 ° C.) at a ratio of 3% by mass and 3% by mass, and uniaxially extended 1.1 times in the longitudinal direction (2.6 times as a whole). ). Furthermore, it was immersed in an aqueous solution (extension bath) containing boric acid and potassium iodide in the proportions of 4% by mass and 6% by mass (the extensibility of the raw material film for optical film production described above) so that the ultimate elongation ratio becomes (The highest temperature), and uniaxial stretching is performed in the length direction to a magnification that is 0.2 times lower than the limit stretching magnification. Thereafter, it was immersed in an aqueous solution (washing bath) (temperature: 30 ° C.) containing potassium iodide in a proportion of 3% by mass for 5 seconds, and finally dried at 60 ° C. for 4 minutes to prepare a polarizing film.
使用所得偏光薄膜,依上述方法評定偏光薄膜的光學特性(二色性比)及色相(平行b值)。將結果示於表1。 Using the obtained polarizing film, the optical characteristics (dichroic ratio) and hue (parallel b value) of the polarizing film were evaluated according to the methods described above. The results are shown in Table 1.
[比較例1~3] [Comparative Examples 1 to 3]
除了於實施例1中分別使用:替代改質PVA之將乙酸乙烯酯之均聚物皂化所得的表1所示之未改質PVA(比較例1);作為改質PVA之藉由將乙酸乙烯酯與3,4-二乙醯氧-1-丁烯的共聚物皂化所得的表1所示之改質PVA(比較例2);或作為改質PVA之藉由將乙酸乙烯酯與衣康酸的共聚物皂化所得的表1所示之改質PVA(比較例3)以外,係以與實施例1同樣的方式製造光學薄膜製造用坯材薄膜及偏光薄膜,並進行各測定或評定。將結果示於表1。 Except that they were used separately in Example 1: unmodified PVA shown in Table 1 (Comparative Example 1) obtained by saponifying a vinyl acetate homopolymer instead of modified PVA; as modified PVA, vinyl acetate was used. The modified PVA shown in Table 1 (Comparative Example 2) obtained by saponifying a copolymer of an ester and 3,4-diacetamido-1-butene; or, as a modified PVA, vinyl acetate and Itacone Except for the modified PVA (Comparative Example 3) shown in Table 1 obtained by saponification of an acid copolymer, a base film and a polarizing film for optical film production were produced in the same manner as in Example 1, and each measurement or evaluation was performed. The results are shown in Table 1.
[實施例2~4] [Examples 2 to 4]
除了於實施例1中分別使用:作為改質PVA之藉由將乙酸乙烯酯與1,3-二乙醯氧-2-亞甲基丙烷的共聚物皂化所得的表1所示之含有羥甲基之PVA(實施例2及3);或作 為改質PVA之藉由將乙酸乙烯酯、1,3-二乙醯氧-2-亞甲基丙烷與乙烯的三元共聚物皂化所得的表1所示之含有羥甲基之PVA(實施例4)以外,係以與實施例1同樣的方式製造光學薄膜製造用坯材薄膜及偏光薄膜,並進行各測定或評定。將結果示於表1。 Except that they were used separately in Example 1: As a modified PVA, the methylol-containing compounds shown in Table 1 were obtained by saponifying a copolymer of vinyl acetate and 1,3-diacetoxy-2-methylenepropane. Based PVA (Examples 2 and 3); or In order to modify PVA, a methylol-containing PVA shown in Table 1 obtained by saponifying a terpolymer of vinyl acetate, 1,3-diethylacetoxy-2-methylenepropane and ethylene (implementation) Except for Example 4), a blank film and a polarizing film for optical film production were produced in the same manner as in Example 1, and each measurement or evaluation was performed. The results are shown in Table 1.
由以上結果可明確得知,滿足本發明之規定的實施例1~4之光學薄膜製造用坯材薄膜其延伸性優良,可生產性良好地製造光學薄膜。又,由於延伸性高,可擴大所得光學薄膜的面積,亦可獲得更多量的光學薄膜。又,除上述以外,已知根據滿足本發明之規定的實施例1~4之光學薄膜製造用坯材薄膜,可容易地製造光學特性及色相均優良的光學薄膜。再者,在使用進一步包含乙烯單元的含有羥甲基之PVA的實施例4中,已知可進一步提升延伸性,同時亦可提高可延伸溫度,能夠生產性更良好地製造光學薄膜。 From the above results, it is clear that the raw material films for optical film manufacturing of Examples 1 to 4 satisfying the requirements of the present invention are excellent in extensibility and can be manufactured with good productivity. Moreover, since the stretchability is high, the area of the obtained optical film can be enlarged, and a larger amount of optical film can be obtained. Furthermore, in addition to the above, it is known that according to the raw material films for optical film production of Examples 1 to 4 that satisfy the requirements of the present invention, it is easy to produce optical films having excellent optical characteristics and hue. Furthermore, in Example 4 using a methylol group-containing PVA further containing an ethylene unit, it is known that the extensibility can be further improved, and at the same time, the extensibility temperature can be increased, and an optical film can be produced with better productivity.
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