TW201930525A - Curable composition, optical laminate and image display device - Google Patents
Curable composition, optical laminate and image display device Download PDFInfo
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Abstract
Description
本發明係有關於硬化性組成物。又，本發明係有關於包含由該硬化性組成物的硬化物所構成的硬化物層之光學積層體、及包含該光學積層體之畫像顯示裝置。 The present invention relates to a curable composition. Moreover, the present invention relates to an optical layered body including a cured layer composed of a cured product of the curable composition, and an image display device including the optical layered body.
近年來，畫像顯示裝置係在以智慧型手機和平板電腦型終端設備作為代表之移動式機器用途和以汽車導航系統作為代表之車輛用機器用途發展。在此種用途，因為相較於先前的室內用TV用途，可能暴露在嚴酷的環境，所以提升裝置的耐久性係成為課題。 In recent years, the image display device has been developed for use in mobile-type machines represented by smart phones and tablet-type terminal devices, and in vehicle applications represented by car navigation systems. In such a use, since it is likely to be exposed to a severe environment as compared with the conventional indoor TV use, the durability of the lifting device is a problem.
構成液晶顯示裝置等之光學構件例如光學積層體亦同樣地被要求耐久性。亦即，被組裝於液晶顯示裝置等之光學構件，係有被放置在高溫或高溫高濕環境下、或被放置在重複高溫及低溫的環境下之情形，光學構件係被要求即便在該等環境下光學特性亦不劣化。 An optical member constituting a liquid crystal display device or the like, for example, an optical layered body is similarly required to have durability. In other words, the optical member to be incorporated in a liquid crystal display device or the like is placed in an environment of high temperature, high temperature, high humidity, or placed in an environment of repeated high temperature and low temperature, and optical members are required to be even in such an environment. The optical properties are not deteriorated in the environment.
作為光學積層體可舉出包含由硬化性組成物的硬化物所構成的硬化物層之光學積層體。此種光學積層體的一個例子為偏光板。例如日本特開2009-008860號公 報(專利文獻1)，係揭示一種將透明保護膜隔著硬化物層(接著劑層)層積在偏光片上而成之偏光板。 An optical layered body including a cured layer composed of a cured product of a curable composition is exemplified as the optical layered body. An example of such an optical laminate is a polarizing plate. For example, Japanese Laid-Open Patent Publication No. 2009-008860 (Patent Document 1) discloses a polarizing plate in which a transparent protective film is laminated on a polarizer via a cured layer (adhesive layer).
[專利文獻1] 日本特開2009-008860號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-008860
本發明之目的係提供一種即便在如上述的嚴酷環境下亦顯示良好的耐熱耐久性(耐熱性)之硬化性組成物。 An object of the present invention is to provide a curable composition which exhibits excellent heat resistance durability (heat resistance) even in the above-described severe environment.
本發明之另一目的係提供一種包含由硬化性組成物的硬化物所構成的硬化物層且耐熱性良好之光學積層體、及包含該光學積層體之畫像顯示裝置。 Another object of the present invention is to provide an optical layered body comprising a cured layer composed of a cured product of a curable composition and having excellent heat resistance, and an image display device including the optical layered body.
本發明係提供一種以下顯示之硬化性組成物、光學積層體、畫像顯示裝置、及偏光板用接著劑組成物。 The present invention provides a curable composition, an optical layered body, an image display device, and an adhesive composition for a polarizing plate which are shown below.
[1]一種硬化性組成物，係含有：含唑啉基的聚合物(A)、鋅化合物(B)、以及選自由具有羧基的化合物(C)及化合物(C)的酸酐所組成群組之至少1種。 [1] A curable composition comprising: The oxazoline group polymer (A), the zinc compound (B), and at least one selected from the group consisting of the compound (C) having a carboxyl group and the acid anhydride of the compound (C).
[2]如[1]所述之硬化性組成物，更含有：促進含唑啉基的聚合物(A)的唑啉基與具有羧基的化合物(C)的羧基反應之化合物(D)。 [2] The curable composition according to [1], further comprising: a promoting inclusion Oxazolinyl polymer (A) Compound (D) wherein an oxazoline group reacts with a carboxyl group of a compound (C) having a carboxyl group.
[3]一種光學積層體，係包含光學膜、及由[1]或[2]所述之硬化性組成物的硬化物所構成之第1硬化物層。 [3] An optical layered body comprising an optical film and a first cured layer composed of a cured product of the curable composition according to [1] or [2].
[4]如[3]所述之光學積層體，係依序包含前述光學膜、前述第1硬化物層、及第1熱塑性樹脂膜。 [4] The optical layered product according to [3], wherein the optical film, the first cured layer, and the first thermoplastic resin film are sequentially included.
[5]如[4]所述之光學積層體，係依序包含第2熱塑性樹脂膜、第2硬化物層、前述光學膜、前述第1硬化物層、及前述第1熱塑性樹脂膜。 [5] The optical layered product according to [4], wherein the second thermoplastic resin film, the second cured layer, the optical film, the first cured layer, and the first thermoplastic resin film are sequentially included.
[6]如[3]至[5]項中任一項所述之光學積層體，其中前述光學膜為偏光片。 [6] The optical layered body according to any one of [3] to [5] wherein the optical film is a polarizer.
[7]一種畫像顯示裝置，係包含[3]至[6]項中任一項所述之光學積層體、及畫像顯示元件。 [7] An image display device comprising the optical layered body according to any one of [3] to [6], and an image display element.
[8]一種偏光板用接著劑組成物，係含有含唑啉基的聚合物(A)、及鋅化合物(B)。 [8] An adhesive composition for a polarizing plate, which contains An oxazoline group polymer (A) and a zinc compound (B).
本發明能夠提供一種即便在如上述嚴荷的環 境下亦顯示良好的耐熱性之硬化性組成物。 The present invention can provide a curable composition which exhibits excellent heat resistance even in an environment as described above.
能夠提供一種包含由硬化性組成物的硬化物所構成的硬化物層且耐熱性良好之光學積層體、及包含該光學積層體之畫像顯示裝置。 An optical layered body comprising a cured layer composed of a cured product of a curable composition and having good heat resistance, and an image display device including the optical layered body can be provided.
10‧‧‧第1熱塑性樹脂膜 10‧‧‧1st thermoplastic resin film
15‧‧‧第1硬化物層 15‧‧‧1st hardened layer
20‧‧‧第2熱塑性樹脂膜 20‧‧‧2nd thermoplastic resin film
25‧‧‧第2硬化物層 25‧‧‧2nd hardened layer
30‧‧‧光學膜 30‧‧‧Optical film
40‧‧‧黏著劑層 40‧‧‧Adhesive layer
第1圖係顯示本發明之光學積層體的一個例子之概略剖面圖。 Fig. 1 is a schematic cross-sectional view showing an example of an optical layered body of the present invention.
第2圖係顯示本發明之光學積層體的層結構的另一個例子之概略剖面圖。 Fig. 2 is a schematic cross-sectional view showing another example of the layer structure of the optical layered body of the present invention.
第3圖係顯示本發明之光學積層體的層結構的另一個例子之概略剖面圖。 Fig. 3 is a schematic cross-sectional view showing another example of the layer structure of the optical layered body of the present invention.
第4圖係顯示本發明之光學積層體的層結構的另一個例子之概略剖面圖。 Fig. 4 is a schematic cross-sectional view showing another example of the layer structure of the optical layered body of the present invention.
第5圖係顯示本發明之光學積層體的層結構的另一個例子之概略剖面圖。 Fig. 5 is a schematic cross-sectional view showing another example of the layer structure of the optical layered body of the present invention.
第6圖係顯示本發明之光學積層體的層結構的另一個例子之概略剖面圖。 Fig. 6 is a schematic cross-sectional view showing another example of the layer structure of the optical layered body of the present invention.
<硬化性組成物> <Sclerosing composition>
本發明之硬化性組成物係含有含唑啉基的聚合物(A)、及鋅化合物(B)。 The curable composition of the present invention contains An oxazoline group polymer (A) and a zinc compound (B).
以下，將本發明之硬化性組成物亦稱為「硬化性組成物(S)」。將由硬化性組成物(S)的硬化物所構成之硬化物層亦稱為「第1硬化物層」。 Hereinafter, the curable composition of the present invention is also referred to as "curable composition (S)". The cured layer composed of the cured product of the curable composition (S) is also referred to as a "first cured layer".
含唑啉基的聚合物(A)係在分子內具有唑啉基之聚合物，以在側鏈具有唑啉基之聚合物為佳。 Contain The oxazoline group polymer (A) has a molecule An oxazoline-based polymer having a side chain The oxazoline group polymer is preferred.
含唑啉基的聚合物(A)的骨架結構係沒有特別限制，例如能夠包含選自(甲基)丙烯酸骨架、苯乙烯骨架、烯烴骨架、酯骨架、碳酸酯骨架等之1種以上的骨架。 Contain The skeletal structure of the oxazoline group-containing polymer (A) is not particularly limited, and for example, one or more kinds of skeletons selected from the group consisting of a (meth)acrylic acid skeleton, a styrene skeleton, an olefin skeleton, an ester skeleton, and a carbonate skeleton can be contained.
在本說明書，所謂「(甲基)丙烯酸」係表示選自由丙烯酸及甲基丙烯酸所組成群組之至少1種。針對「(甲基)丙烯醯基」及「(甲基)丙烯酸酯」等的記載亦同理。 In the present specification, the term "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The same applies to the descriptions of "(meth)acrylonitrile" and "(meth)acrylate".
含唑啉基的聚合物(A)係可在上述骨架結構的側鏈具有唑啉基。 Contain The oxazoline group polymer (A) may have a side chain of the above skeleton structure Oxazolinyl.
含唑啉基的聚合物(A)亦可含有在側鏈具有唑啉基的結構單元(源自含唑啉基的單體之結構單元)、及不具有唑啉基的結構單元。 Contain The oxazoline group polymer (A) may also have a side chain Structural unit of oxazoline group The structural unit of the oxazoline group monomer), and does not have A structural unit of an oxazoline group.
含唑啉基的聚合物(A)的較佳一個例子為含唑啉基的(甲基)丙烯酸系聚合物，該含唑啉基的(甲基)丙烯酸系聚合物係含有由(甲基)丙烯酸骨架所構成的骨架結構作為結構單元的主成分之共聚合成分，且在側鏈導入有具有唑啉基的結構單元(源自含唑啉基的單體之結構單元)。 Contain A preferred example of the oxazoline group polymer (A) is Oxazolyl (meth)acrylic polymer, which contains The (meth)acrylic polymer of the oxazoline group contains a skeleton structure composed of a (meth)acrylic acid skeleton as a main component of a structural unit, and has a side chain introduced therein. Structural unit of oxazoline group a structural unit of an oxazoline group monomer).
作為含唑啉基的聚合物(A)，係除了由含唑啉基的單體共聚合而成者以外，亦可為藉由將聚合物的側鏈官能基改性而使其含有唑啉基而成者。 As containing Oxazolyl-based polymer (A) In addition to the copolymerization of the oxazoline group monomer, it may be modified by modifying the side chain functional group of the polymer. An oxazoline group.
作為唑啉基例如可舉出2-唑啉基、3-唑啉基、4-唑啉基等。唑啉基係較佳為2-唑啉基等。 As The oxazoline group can be exemplified by 2 Oxazolinyl, 3- Oxazolinyl, 4- Oxazolinyl and the like. The oxazoline group is preferably 2- Oxazolinyl and the like.
作為上述含唑啉基的單體可舉出2-異丙烯基-2-唑啉、乙烯基-2-唑啉等。 As the above 2-isopropenyl-2- exemplified as the oxazoline group monomer Oxazoline, vinyl-2- Oxazoline and the like.
含唑啉基的聚合物(A)之重量平均分子量係以5000以上為佳，較佳為10000以上。從提高光學積層體的耐熱性、在光學積層體中光學膜與第1硬化物層之間的密著性、第1硬化物層與第1熱塑性樹脂膜之間的密著性的觀點而言，重量平均分子量為上述範圍是有利。 Contain The weight average molecular weight of the oxazoline group polymer (A) is preferably 5,000 or more, preferably 10,000 or more. From the viewpoint of improving the heat resistance of the optical laminate, the adhesion between the optical film and the first cured layer in the optical laminate, and the adhesion between the first cured layer and the first thermoplastic resin film. It is advantageous that the weight average molecular weight is in the above range.
含唑啉基的聚合物(A)的重量平均分子量通常為1000000以下。 Contain The weight average molecular weight of the oxazoline group polymer (A) is usually 1,000,000 or less.
含唑啉基的聚合物(A)的重量平均分子量係能夠以使用凝膠滲透層析法(GPC)而得到的標準聚苯乙烯換算值之方式測定。 Contain The weight average molecular weight of the oxazoline group polymer (A) can be measured as a standard polystyrene equivalent value obtained by gel permeation chromatography (GPC).
含唑啉基的聚合物(A)之唑啉基量(含唑啉基的聚合物(A)之每1g固形物的唑啉基的莫耳數)係較佳為0.4mmol/g．solid以上。唑啉基量小於上述範圍時，對光學積層體的耐熱性為不利。從該觀點而言、含唑啉基的聚合物之唑啉基量係較佳為3mmol/g．solid以上，更佳為5mmol/g．solid以上且9mmol/g．solid以下。 Contain Oxazolinyl polymer (A) Azoline group amount (including 1 g of solids of the oxazoline-based polymer (A) The molar number of the oxazoline group is preferably 0.4 mmol/g. Solid above. When the amount of the oxazoline group is less than the above range, the heat resistance of the optical layered product is disadvantageous. From this point of view, including Oxazolyl-based polymer The amount of oxazoline groups is preferably 3 mmol/g. More than solid, more preferably 5mmol / g. Above solid and 9mmol/g. Solid below.
唑啉基量的上限係沒有特別限制，通常為 50mmol/g．solid以下。 The upper limit of the amount of the oxazoline group is not particularly limited and is usually 50 mmol/g. Solid below.
含唑啉基的聚合物(A)係以水系亦即水溶性聚合物、或水分散性的聚合物為佳。從第1硬化物層的光學特性之觀點而言，含唑啉基的聚合物(A)係較佳為水溶性聚合物。 Contain The oxazoline group-containing polymer (A) is preferably a water-based polymer, or a water-dispersible polymer. From the viewpoint of the optical properties of the first cured layer, The oxazoline group polymer (A) is preferably a water-soluble polymer.
作為含唑啉基的聚合物(A)，亦可使用市售品。具體而言，可舉出：日本觸媒股份有限公司製EPOCROSS WS-300、EPOCROSS WS-500、EPOCROSS WS-700(均為商品名)等含唑啉基的丙烯酸聚合物；日本觸媒股份有限公司製EPOCROSS K-1000 Series、EPOCROSS K-2000 Series、EPOCROSS RPS Series(均為商品名)等含唑啉基的丙烯酸/苯乙烯聚合物。 As containing As the oxazoline group polymer (A), a commercially available product can also be used. Specific examples include EPOCROSS WS-300, EPOCROSS WS-500, and EPOCROSS WS-700 (all trade names) manufactured by Nippon Shokubai Co., Ltd. An oxazoline-based acrylic polymer; EPOCROSS K-1000 Series, EPOCROSS K-2000 Series, and EPOCROSS RPS Series (all trade names) manufactured by Nippon Shokubai Co., Ltd. An oxazoline based acrylic/styrene polymer.
含唑啉基的聚合物(A)係能夠併用2種以上而使用。 Contain The oxazoline group polymer (A) can be used in combination of two or more kinds.
從光學積層體的耐熱性和光學特性、在光學積層體中光學膜與第1硬化物層之間的密著性、第1硬化物層與第1熱塑性樹脂膜之間的密著性、以及第1硬化物層的耐水性之觀點而言，含唑啉基的聚合物(A)係以EPOCROSS WS-300、EPOCROSS WS-500、EPOCROSS WS-700等含唑啉基的丙烯酸聚合物為佳。 The heat resistance and optical properties of the optical laminate, the adhesion between the optical film and the first cured layer in the optical laminate, the adhesion between the first cured layer and the first thermoplastic resin film, and From the viewpoint of water resistance of the first cured layer, The oxazoline group polymer (A) is contained in EPOCROSS WS-300, EPOCROSS WS-500, EPOCROSS WS-700, etc. An oxazoline-based acrylic polymer is preferred.
將硬化性組成物(S)的固形物濃度設為100質量%時，含唑啉基的聚合物(A)之含量係以5質量%以上且95質量%以下為佳，較佳為10質量%以上且90質量%以下，更佳為20質量%以上且85質量%以下。使含唑啉 基的聚合物(A)之含量成為上述範圍內，從提升光學積層體的耐熱性、在光學積層體中光學膜與第1硬化物層之間的密著性、第1硬化物層與第1熱塑性樹脂膜之間的密著性之觀點而言是較佳。 When the solid content concentration of the curable composition (S) is 100% by mass, The content of the oxazoline group-containing polymer (A) is preferably 5% by mass or more and 95% by mass or less, preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 85% by mass or less. . Make The content of the oxazoline group-containing polymer (A) is within the above range, and the heat resistance of the optical laminate, the adhesion between the optical film and the first cured layer in the optical laminate, and the first cured layer are improved. It is preferable from the viewpoint of the adhesion between the first thermoplastic resin film.
所謂固形物濃度係指在硬化性組成物(S)所含有的溶劑以外的成分之合計濃度。 The solid content concentration refers to the total concentration of components other than the solvent contained in the curable composition (S).
鋅化合物(B)係含有鋅元素之化合物。硬化性組成物(S)可含有1種鋅化合物(B)，亦可含有2種以上的鋅化合物(B)。 The zinc compound (B) is a compound containing a zinc element. The curable composition (S) may contain one type of zinc compound (B) or two or more types of zinc compounds (B).
作為鋅化合物(B)例如可舉出以下者。 Examples of the zinc compound (B) include the following.
a)無機鋅鹽 a) inorganic zinc salt
氟化鋅、氯化鋅、溴化鋅、碘化鋅等鹵化鋅；硫酸鋅、碳酸鋅、硼酸鋅、硝酸鋅、磷酸鋅、氫氧化鋅、氯化鋅銨、硫酸鋅鋁、硫酸鋅鉀、鉻酸鋅、錫酸鋅等 Zinc halide, zinc chloride, zinc bromide, zinc iodide, etc.; zinc sulfate, zinc carbonate, zinc borate, zinc nitrate, zinc phosphate, zinc hydroxide, zinc ammonium chloride, zinc aluminum sulfate, zinc potassium sulfate , zinc chromate, zinc stannate, etc.
b)其它無機鋅化合物 b) other inorganic zinc compounds
鋅的氧化物(氧化鋅)；無機系鋅錯合物 Zinc oxide (zinc oxide); inorganic zinc complex
c)有機鋅鹽 c) organic zinc salt
甲酸鋅、乙酸鋅、丙酸鋅、硬脂酸鋅、月桂酸鋅、十二院酸鋅、油酸鋅、己二酸鋅、葡萄糖酸鋅、檸檬酸鋅、羥基乙酸鋅、苯甲酸鋅、磷酸酯鋅鹽等有機酸鋅鹽 Zinc formate, zinc acetate, zinc propionate, zinc stearate, zinc laurate, zinc zirconate, zinc oleate, zinc adipate, zinc gluconate, zinc citrate, zinc glycolate, zinc benzoate, Organic acid zinc salt such as zinc phosphate salt
d)其它有機鋅化合物 d) other organozinc compounds
二甲基鋅、二乙基鋅、二苯基鋅等； 有機系鋅錯合物。 Dimethylzinc, diethylzinc, diphenylzinc, etc.; organic zinc complex.
從提高光學積層體的耐熱性的觀點而言，鋅化合物(B)的含量係相對於含唑啉基的聚合物(A)100質量份，通常為1質量份以上且300質量份以下，以2質量份以上且250質量份以下為佳，較佳為5質量份以上且200質量份以下，更佳為10質量份以上且150質量份以下。 From the viewpoint of improving the heat resistance of the optical laminate, the content of the zinc compound (B) is relative to 100 parts by mass of the oxazoline group-containing polymer (A) is usually 1 part by mass or more and 300 parts by mass or less, preferably 2 parts by mass or more and 250 parts by mass or less, preferably 5 parts by mass or more and 200 parts by mass or less. More preferably, it is 10 mass parts or more and 150 mass parts or less.
在一實施形態中，鋅化合物(B)的含量係相對於含唑啉基的聚合物(A)100質量份，為10質量份以上且140質量份以下或10質量份以上且120質量份以下。 In one embodiment, the content of the zinc compound (B) is relative to 100 parts by mass of the oxazoline group polymer (A) is 10 parts by mass or more and 140 parts by mass or less or 10 parts by mass or more and 120 parts by mass or less.
鋅化合物(B)的含量太少時，不容易藉由含有鋅化合物(B)而得到提高光學積層體的耐熱性之效果。又，鋅化合物(B)的含量太多時，在光學積層體中光學膜與第1硬化物層之間的密著性、及第1硬化物層與第1熱塑性樹脂膜之間的密著性的至少任一者有容易低落之傾向。 When the content of the zinc compound (B) is too small, it is not easy to obtain an effect of improving the heat resistance of the optical layered body by containing the zinc compound (B). When the content of the zinc compound (B) is too large, the adhesion between the optical film and the first cured layer in the optical laminate and the adhesion between the first cured layer and the first thermoplastic resin film At least one of the sexes tends to be low.
硬化性組成物(S)係能夠更含有選自由具有羧基的化合物(C)及化合物(C)的酸酐之至少1種。以下，將具有羧基的化合物(C)亦稱為「化合物(C)」。 The curable composition (S) can further contain at least one selected from the group consisting of the compound (C) having a carboxyl group and the acid anhydride of the compound (C). Hereinafter, the compound (C) having a carboxyl group is also referred to as "compound (C)".
化合物(C)係具有能夠與含唑啉基的聚合物(A)的唑啉基反應的羧基之化合物。在此，所謂羧基亦包含羧基的衍生物，但是不包含化合物(C)的酸酐。 Compound (C) has the ability to contain Oxazolinyl polymer (A) A compound of a carboxyl group reacted with an oxazoline group. Here, the carboxyl group also contains a derivative of a carboxyl group, but does not contain an acid anhydride of the compound (C).
作為羧基的衍生物可舉出羧酸鹽陰離子基。作為羧酸鹽陰離子基的相對離子之陽離子可舉出：鋰離子、 鈉離子、鉀離子等金屬離子；銨離子、鋶離子、鏻離子等有機陽離子等。 The carboxylate derivative may, for example, be a carboxylate anion group. Examples of the cation of the relative ion of the carboxylate anion group include metal ions such as lithium ion, sodium ion, and potassium ion; and organic cations such as ammonium ion, cesium ion, and cesium ion.
硬化性組成物(S)可含有1種化合物(C)，亦可含有2種以上的化合物(C)。硬化性組成物(S)可含有1種化合物(C)的酸酐，亦可含有2種以上的化合物(C)的酸酐。硬化性組成物(S)亦可含有1種以上的化合物(C)、及1種以上的化合物(C)的酸酐。 The curable composition (S) may contain one type of compound (C), or may contain two or more types of compound (C). The curable composition (S) may contain an acid anhydride of one kind of the compound (C), or may contain two or more kinds of acid anhydrides of the compound (C). The curable composition (S) may contain one or more compounds (C) and one or more acid anhydrides of the compound (C).
尤其是從提高光學積層體的耐熱性、在光學積層體中光學膜與第1硬化物層之間的密著性、第1硬化物層與第1熱塑性樹脂膜之間的密著性、以及第1硬化物層的耐水性之觀點而言，化合物(C)係以在分子內具有2個以上的羧基(或其衍生物)之化合物(多官能羧酸化合物)為佳。 In particular, the heat resistance of the optical laminate, the adhesion between the optical film and the first cured layer in the optical laminate, the adhesion between the first cured layer and the first thermoplastic resin film, and From the viewpoint of water resistance of the first cured layer, the compound (C) is preferably a compound (polyfunctional carboxylic acid compound) having two or more carboxyl groups (or derivatives thereof) in the molecule.
多官能羧酸化合物的一個例子為二羧酸化合物。作為二羧酸化合物可舉出草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、酒石酸、麩胺酸(glutamic acid)、蘋果酸、順丁烯二酸、反丁烯二酸、伊康酸、己二烯二酸(muconic acid)、1,4-環己烷二羧酸、1,4-萘二羧酸、2,6-萘二羧酸、2,7-萘二羧酸、4,4’-聯苯基二羧酸、2,5-吡啶二羧酸、3,5-吡啶二羧酸、二苯基碸二羧酸、二苯基甲烷二羧酸、草乙酸、甲基反丁烯二酸、2,6-吡啶二羧酸等。 An example of a polyfunctional carboxylic acid compound is a dicarboxylic acid compound. Examples of the dicarboxylic acid compound include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, sebacic acid, phthalic acid, and isophthalic acid. , terephthalic acid, tartaric acid, glutamic acid, malic acid, maleic acid, fumaric acid, itaconic acid, muconic acid, 1,4-ring Hexanedicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 2,5-pyridine Dicarboxylic acid, 3,5-pyridinedicarboxylic acid, diphenylphosphonium dicarboxylic acid, diphenylmethanedicarboxylic acid, oxalic acid, methyl fumaric acid, 2,6-pyridinedicarboxylic acid, and the like.
多官能羧酸化合物的另一個例子為三羧酸化合物。作為三羧酸化合物可舉出檸檬酸、烏頭酸、丙烷- 1,2,3-三羧酸、偏苯三甲酸、1,3,5-苯三甲酸、1,2,3-苯三甲酸(hemimellitic acid)、聯苯基-3,4’,5-三羧酸、1,3,5-環己烷三羧酸等。 Another example of a polyfunctional carboxylic acid compound is a tricarboxylic acid compound. Examples of the tricarboxylic acid compound include citric acid, aconitic acid, propane-1,2,3-tricarboxylic acid, trimellitic acid, 1,3,5-benzenetricarboxylic acid, and 1,2,3-benzenetricarboxylic acid. (hemimellitic acid), biphenyl-3,4',5-tricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, and the like.
多官能羧酸化合物的又另一個例子為四羧酸化合物。作為四羧酸化合物可舉出焦蜜石酸酸、二苯基碸四羧酸、聯苯基四羧酸、二苯基酮四羧酸、萘四羧酸、噻吩四羧酸、丁烷四羧酸、1,2,4,5-肆(4-羧苯基)苯等。 Yet another example of a polyfunctional carboxylic acid compound is a tetracarboxylic acid compound. Examples of the tetracarboxylic acid compound include pyruvic acid, diphenylphosphonium tetracarboxylic acid, biphenyltetracarboxylic acid, diphenylketonetetracarboxylic acid, naphthalenetetracarboxylic acid, thiophene tetracarboxylic acid, butane tetra Carboxylic acid, 1,2,4,5-anthracene (4-carboxyphenyl)benzene, and the like.
在以上例示之多官能羧酸化合物中，至少1個羧基亦可為其衍生物。 In the polyfunctional carboxylic acid compound exemplified above, at least one carboxyl group may be a derivative thereof.
化合物(C)亦可具有羧基以外的其它官能基。其它官能基的一個例子為羥基。 The compound (C) may have a functional group other than a carboxyl group. An example of other functional groups is a hydroxyl group.
從光學積層體的耐熱性之觀點而言，化合物(C)所具有之羧基的數目係較佳為2或3。 The number of carboxyl groups which the compound (C) has is preferably 2 or 3 from the viewpoint of heat resistance of the optical laminate.
多官能羧酸化合物亦可為在分子內具有2個以上的羧基(或其衍生物)之聚合物。該聚合物的一個例子為羧基改性聚合物。羧基改性聚合物的一個例子為羧基改性聚乙烯醇系聚合物。 The polyfunctional carboxylic acid compound may also be a polymer having two or more carboxyl groups (or derivatives thereof) in the molecule. An example of such a polymer is a carboxyl modified polymer. An example of the carboxyl group-modified polymer is a carboxyl group-modified polyvinyl alcohol-based polymer.
羧基改性聚乙烯醇系聚合物係藉由將羧基或其衍生物導入至側鏈而受到改性之聚乙烯醇系聚合物。 The carboxyl group-modified polyvinyl alcohol polymer is a polyvinyl alcohol polymer modified by introducing a carboxyl group or a derivative thereof into a side chain.
作為羧基的衍生物可舉出羧酸鹽陰離子基。羧酸鹽陰離子基的相對離子之陽離子的例子係如上述。較佳陽離子的一個例子為鈉離子。 The carboxylate derivative may, for example, be a carboxylate anion group. Examples of the cation of the relative ion of the carboxylate anion group are as described above. An example of a preferred cation is sodium ion.
構成羧基改性聚乙烯醇系聚合物的主鏈之聚乙烯醇系聚合物，可為將屬旖乙酸乙烯酯的同元聚合物之 聚乙酸乙烯酯進行皂化處理而得到之乙烯醇同元聚合物(完全皂化聚乙烯醇或部分皂化聚乙烯醇)，亦可為將乙酸乙烯酯和能夠與其共聚合的其它單體之共聚物進行皂化處理而得到之聚乙烯醇系共聚物。 The polyvinyl alcohol-based polymer constituting the main chain of the carboxyl group-modified polyvinyl alcohol-based polymer may be a homopolymer of vinyl alcohol obtained by saponifying a polyvinyl acetate of a homopolymer of vinyl acetate. The material (completely saponified polyvinyl alcohol or partially saponified polyvinyl alcohol) may be a polyvinyl alcohol-based copolymer obtained by saponifying a copolymer of vinyl acetate and another monomer copolymerizable therewith.
作為能夠與乙酸乙烯酯共聚合的其它單體可舉出不飽和羧酸類、烯烴類、乙烯醚類、不飽和磺酸類、及具有銨基之(甲基)丙烯醯胺類等。 Examples of the other monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and (meth) acrylamides having an ammonium group.
羧基改性聚乙烯醇系聚合物的皂化度通常為80莫耳%以上且100莫耳%以下，較佳為85莫耳%以上(例如88莫耳%以上)。 The degree of saponification of the carboxyl group-modified polyvinyl alcohol polymer is usually 80 mol% or more and 100 mol% or less, preferably 85 mol% or more (for example, 88 mol% or more).
羧基改性聚乙烯醇系聚合物的皂化度係能夠依據JIS K 6726：1994而測定。 The degree of saponification of the carboxyl group-modified polyvinyl alcohol polymer can be measured in accordance with JIS K 6726:1994.
羧基改性聚乙烯醇系聚合物之藉由羧基(或其衍生物)的改性度(改性量)通常為0.1莫耳%以上。從提高光學積層體的耐熱性、在光學積層體中光學膜與第1硬化物層之間的密著性、第1硬化物層與第1熱塑性樹脂膜之間的密著性、以及第1硬化物層的耐水性之觀點而言，羧基改性聚乙烯醇系聚合物的改性度係以0.5莫耳%以上且40莫耳%以下為佳，較佳為1莫耳%以上且20莫耳%以下。改性度係例如能夠藉由1H-NMR而測定。 The degree of modification (modified amount) of the carboxyl group-modified polyvinyl alcohol-based polymer by a carboxyl group (or a derivative thereof) is usually 0.1 mol% or more. The heat resistance of the optical laminate, the adhesion between the optical film and the first cured layer in the optical laminate, the adhesion between the first cured layer and the first thermoplastic resin film, and the first The degree of modification of the carboxyl group-modified polyvinyl alcohol-based polymer is preferably 0.5 mol% or more and 40 mol% or less, and preferably 1 mol% or more and 20 or less, from the viewpoint of water resistance of the cured layer. Mole% or less. The degree of modification can be measured, for example, by 1 H-NMR.
羧基改性聚乙烯醇系聚合物的平均聚合度通常為100以上且3000以下。 The average degree of polymerization of the carboxyl group-modified polyvinyl alcohol-based polymer is usually 100 or more and 3,000 or less.
羧基改性聚乙烯醇系聚合物的平均聚合度係能夠依據JIS K 6726：1994而測定。 The average degree of polymerization of the carboxyl group-modified polyvinyl alcohol-based polymer can be measured in accordance with JIS K 6726:1994.
在一較佳實施形態中，化合物(C)之分子量為1000以下。該分子量係從化學結構式算出之分子量，但在化合物(C)為聚合物時，亦可為以使用凝膠滲透層析法(GPC)而得到的標準聚苯乙烯換算值之方式測定之數量平均分子量。 In a preferred embodiment, the compound (C) has a molecular weight of 1,000 or less. The molecular weight is a molecular weight calculated from a chemical structural formula. However, when the compound (C) is a polymer, the amount may be measured by a standard polystyrene equivalent value obtained by gel permeation chromatography (GPC). Average molecular weight.
就提高光學積層體的耐熱性而言，使用分子量為1000以下之化合物(C)為有利。從光學積層體的耐熱性之觀點而言，化合物(C)的分子量係以800以下為佳，較佳為500以下。 In order to improve the heat resistance of the optical layered body, it is advantageous to use the compound (C) having a molecular weight of 1,000 or less. The molecular weight of the compound (C) is preferably 800 or less, and preferably 500 or less, from the viewpoint of heat resistance of the optical layered product.
又，從光學積層體的耐熱性、在光學積層體中光學膜與第1硬化物層之間的密著性、以及第1硬化物層與第1熱塑性樹脂膜之間的密著性的觀點而言，化合物(C)的分子量係以90以上為佳，較佳為100以上。 Moreover, the heat resistance of the optical laminate, the adhesion between the optical film and the first cured layer in the optical laminate, and the adhesion between the first cured layer and the first thermoplastic resin film The molecular weight of the compound (C) is preferably 90 or more, and more preferably 100 or more.
化合物(C)的較佳例為檸檬酸、蘋果酸、順丁烯二酸、酒石酸。 Preferred examples of the compound (C) are citric acid, malic acid, maleic acid, and tartaric acid.
作為化合物(C)的酸酐可舉出羧酸酐。羧酸酐可舉出乙酸酐、丙酸酐、草酸酐、琥珀酸酐、順丁烯二酸酐、鄰苯二甲酸酐、苯甲酸酐等。 The acid anhydride of the compound (C) is exemplified by a carboxylic acid anhydride. Examples of the carboxylic acid anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, and benzoic anhydride.
從提高光學積層體的耐熱性之觀點而言，選自化合物(C)及化合物(C)的酸酐之至少1種的含量係相對於含唑啉基的聚合物(A)100質量份，以0.01質量份以上且30質量份為佳，較佳為0.1質量份以上且25質量份以下，更佳為0.2質量份以上且20質量份以下，又更佳為0.2質量份以上且15質量份以下。 From the viewpoint of improving the heat resistance of the optical layered body, the content of at least one selected from the group consisting of the compound (C) and the compound (C) is relative to the content 100 parts by mass of the oxazoline group-containing polymer (A) is preferably 0.01 parts by mass or more and 30 parts by mass, more preferably 0.1 part by mass or more and 25 parts by mass or less, still more preferably 0.2 part by mass or more and 20 parts by mass or less. More preferably, it is 0.2 mass part or more and 15 mass parts or less.
在一實施形態中，選自化合物(C)及化合物(C)的酸酐之至少1種的含量係相對於含唑啉基的聚合物(A)100質量份，為0.3質量份以上且10質量份以下，或為0.5質量份以上且10質量份以下，或為0.5質量份以上且8質量份以下，或為1質量份以上且8質量份以下。 In one embodiment, the content of at least one selected from the group consisting of the compound (C) and the compound (C) is relative to 100 parts by mass of the oxazoline group polymer (A) is 0.3 parts by mass or more and 10 parts by mass or less, or 0.5 parts by mass or more and 10 parts by mass or less, or 0.5 parts by mass or more and 8 parts by mass or less or 1 part by mass or more and 8 parts by mass or less.
選自化合物(C)及化合物(C)的酸酐之至少1種的含量太少時，難以藉由含有選自化合物(C)及化合物(C)的酸酐之至少1種，而得到提高光學積層體的耐熱性之效果。又，選自化合物(C)及化合物(C)的酸酐之至少1種的含量太多時，提高光學積層體的耐熱性之效果有容易低落之傾向。 When the content of at least one of the acid anhydrides selected from the compound (C) and the compound (C) is too small, it is difficult to obtain an optical laminate by containing at least one of the acid anhydrides selected from the compound (C) and the compound (C). The effect of heat resistance of the body. In addition, when the content of at least one of the acid anhydrides selected from the compound (C) and the compound (C) is too large, the effect of improving the heat resistance of the optical layered product tends to be low.
硬化性組成物(S)可更含有：促進含唑啉基的聚合物(A)之唑啉基與具有羧基的化合物(C)的羧基反應之化合物(D)。以下，將該化合物亦稱為「化合物(D)」。在此所稱之促進亦包含使該反應開始之情況。 The curable composition (S) may further contain: promoted inclusion Oxazolinyl polymer (A) Compound (D) wherein an oxazoline group reacts with a carboxyl group of a compound (C) having a carboxyl group. Hereinafter, this compound is also referred to as "compound (D)". The term "promotion" as used herein also encompasses the circumstances in which the reaction begins.
硬化性組成物(S)含有化合物(C)的酸酐時，化合物(D)係與在化合物(C)的酸酐的至少一部分因水解而產生的羧酸中之羧基開始反應開始或促進反應。 When the curable composition (S) contains the acid anhydride of the compound (C), the compound (D) starts or accelerates the reaction with the carboxyl group in the carboxylic acid produced by hydrolysis of at least a part of the acid anhydride of the compound (C).
作為化合物(D)之較佳例子可舉出酸化合物。酸化合物亦可以是作為含唑啉基的聚合物(A)的唑啉基、與化合物(C)的羧基及/或化合物(C)的酸酐因水解而產 生的羧基反應之觸媒的功能之化合物。 A preferred example of the compound (D) is an acid compound. Acid compounds can also be included Oxazolinyl polymer (A) A compound having a function as a catalyst for reacting an oxazoline group with a carboxyl group of the compound (C) and/or an acid anhydride of the compound (C) by hydrolysis.
作為上述酸化合物可舉出：硫酸、氯化氫、硝酸、磷酸、亞磷酸、硼酸等無機酸；對甲苯磺酸、十二烷基苯磺酸、萘磺酸、甲磺酸、苯磺酸、苯基磷酸、對胺苯磺酸(sulfanilic acid)、苯基膦酸、乙酸、丙酸等有機酸。 Examples of the acid compound include inorganic acids such as sulfuric acid, hydrogen chloride, nitric acid, phosphoric acid, phosphorous acid, and boric acid; p-toluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, methanesulfonic acid, benzenesulfonic acid, and benzene. An organic acid such as phosphatidyl acid, sulfanilic acid, phenylphosphonic acid, acetic acid or propionic acid.
硬化性組成物(S)可含有1種化合物(D)，亦可含有2種以上的化合物(D)。 The curable composition (S) may contain one type of compound (D) or two or more types of compound (D).
化合物(D)亦可以含有化合物(D)的溶液(例如水溶液)之方式被調配在硬化性組成物(S)。 The compound (D) may be formulated in the curable composition (S) in such a manner as to contain a solution (for example, an aqueous solution) of the compound (D).
尤其是從提高光學積層體的耐熱性、在光學積層體中光學膜與第1硬化物層之間的密著性、第1硬化物層與第1熱塑性樹脂膜之間的密著性的觀點而言，化合物(D)係以較強的酸為佳，作為此種酸化合物可舉出硫酸、氯化氫(鹽酸)、硝酸、對甲苯磺酸等。 In particular, from the viewpoint of improving the heat resistance of the optical laminate, the adhesion between the optical film and the first cured layer in the optical laminate, and the adhesion between the first cured layer and the first thermoplastic resin film The compound (D) is preferably a strong acid, and examples of such an acid compound include sulfuric acid, hydrogen chloride (hydrochloric acid), nitric acid, and p-toluenesulfonic acid.
使用如上述的強酸作為化合物(D)時，尤其是具有容易提升在光學積層體中光學膜與第1硬化物層之間的密著性、第1硬化物層與第1熱塑性樹脂膜之間的密著性之傾向。 When the strong acid as described above is used as the compound (D), in particular, it is easy to improve the adhesion between the optical film and the first cured layer in the optical laminate, and between the first cured layer and the first thermoplastic resin film. The tendency of closeness.
硬化性組成物(S)之化合物(D)的含量，係相對於含唑啉基的聚合物(A)100質量份，通常為1質量份以上且150質量份以下，從提高光學積層體的耐熱性、在光學積層體中光學膜與第1硬化物層之間的密著性、第1硬化物層與第1熱塑性樹脂膜之間的密著性之觀點而言，係以3質量份以上且100質量份以下為佳，較佳為5質量份 以上且100質量份以下，更佳為10質量份以上且100質量份以下。 The content of the compound (D) of the curable composition (S) is relative to 100 parts by mass of the oxazoline group-containing polymer (A) is usually 1 part by mass or more and 150 parts by mass or less, and the heat resistance of the optical layered body is improved, and between the optical film and the first cured layer in the optical layered body. The adhesion, the adhesion between the first cured layer and the first thermoplastic resin film is preferably 3 parts by mass or more and 100 parts by mass or less, more preferably 5 parts by mass or more and 100% by mass. The amount is preferably 10 parts by mass or more and 100 parts by mass or less.
在一較佳實施形態中，從提高光學積層體的耐熱性之觀點而言，化合物(D)的含量係相對於含唑啉基的聚合物(A)100質量份，為10質量份以上且80質量份以下或10質量份以上且50質量份以下。 In a preferred embodiment, the content of the compound (D) is relative to the content from the viewpoint of improving the heat resistance of the optical laminate. 100 parts by mass of the oxazoline group polymer (A) is 10 parts by mass or more and 80 parts by mass or less or 10 parts by mass or more and 50 parts by mass or less.
化合物(D)的含量太少時，難以藉由含有化合物(D)而得到提高光學積層體的耐熱性之效果。而且化合物(D)的含量太少時，難以藉由含有化合物(D)而得到提高在光學積層體之光學膜與第1硬化物層之間的密著性之效果、以及提高第1硬化物層與第1熱塑性樹脂膜之間的密著性之效果。 When the content of the compound (D) is too small, it is difficult to obtain an effect of improving the heat resistance of the optical layered body by containing the compound (D). Further, when the content of the compound (D) is too small, it is difficult to obtain an effect of improving the adhesion between the optical film of the optical laminate and the first cured layer by containing the compound (D), and improving the first cured product. The effect of the adhesion between the layer and the first thermoplastic resin film.
化合物(D)的含量太多時，在光學積層體中光學膜與第1硬化物層之間的密著性、及第1硬化物層與第1熱塑性樹脂膜之間的密著性的至少任一者有容易低落之傾向。 When the content of the compound (D) is too large, the adhesion between the optical film and the first cured layer in the optical laminate and at least the adhesion between the first cured layer and the first thermoplastic resin film are at least Either one has a tendency to be low.
硬化性組成物(S)係能夠含有含唑啉基的聚合物(A)、鋅化合物(B)、化合物(C)、化合物(C)的酸酐及化合物(D)以外之其它成分。 The curable composition (S) can contain The oxazoline group polymer (A), the zinc compound (B), the compound (C), the acid anhydride of the compound (C), and other components other than the compound (D).
作為其它成分可舉出：多元醛、三聚氰胺系化合物、氧化鋯化合物、鋅化合物、氮丙啶化合物、乙二醛、乙二醛衍生物、水溶性環氧樹脂等硬化性成分和交聯 劑；羧基改性聚乙烯醇系聚合物以外的改性聚乙烯醇系聚合物；偶合劑、黏著賦予劑、抗氧化劑、紫外線吸收劑、熱安定劑、抗水解劑等添加劑。 Examples of the other component include a curable component such as a polyvalent aldehyde, a melamine compound, a zirconia compound, a zinc compound, an aziridine compound, glyoxal, a glyoxal derivative, and a water-soluble epoxy resin; and a crosslinking agent; A modified polyvinyl alcohol polymer other than a carboxyl group-modified polyvinyl alcohol polymer; an additive such as a coupling agent, an adhesion-imparting agent, an antioxidant, an ultraviolet absorber, a heat stabilizer, or a hydrolysis inhibitor.
硬化性組成物(S)係能夠含有1種或2種以上的其它成分。 The curable composition (S) can contain one or two or more other components.
硬化性組成物(S)係以含有溶劑為佳。作為溶劑可舉出水、有機溶劑、或該等的混合物。溶劑係較佳是含有水，但是亦可併用水與水溶性的有機溶劑。作為有機溶劑可舉出乙醇、1-甲氧基-2-丙醇等醇溶劑。 The curable composition (S) is preferably a solvent. The solvent may, for example, be water, an organic solvent or a mixture thereof. The solvent is preferably water, but may be combined with water and a water-soluble organic solvent. The organic solvent may, for example, be an alcohol solvent such as ethanol or 1-methoxy-2-propanol.
溶劑的主成分係以水為佳。所謂主成分係意味著佔有全溶劑的50質量%以上。 The main component of the solvent is preferably water. The main component system means that 50% by mass or more of the total solvent is contained.
硬化性組成物(S)的固形物濃度通常為0.5質量%以上且20質量%以下，較佳為1質量%以上且15質量%以下。 The solid content concentration of the curable composition (S) is usually 0.5% by mass or more and 20% by mass or less, preferably 1% by mass or more and 15% by mass or less.
硬化性組成物(S)係能夠使用作為用以在基材上形成塗膜(塗佈層)之塗佈液。例如能夠藉由將硬化性組成物(S)塗佈在基材上且使塗佈層硬化而形成塗膜。基材係較佳為光學膜。針對光學膜係如後述。此時，光學積層體係包含光學膜、及由硬化性組成物(S)的硬化物所構成之第1硬化物層。 The curable composition (S) can be used as a coating liquid for forming a coating film (coating layer) on a substrate. For example, a coating film can be formed by applying a curable composition (S) onto a substrate and curing the coating layer. The substrate is preferably an optical film. The optical film system will be described later. In this case, the optical layering system includes an optical film and a first cured layer composed of a cured product of the curable composition (S).
硬化性組成物(S)亦能夠使用作為接著劑組成物。在一實施形態中，硬化性組成物(S)係用以將光學膜與第1熱塑性樹脂膜貼合之接著劑組成物。此時，光學積層體係依序包含光學膜、由硬化性組成物(S)的硬化物所構成 之第1硬化物層(接著劑層)、及第1熱塑性樹脂膜。藉由將硬化性組成物(S)塗佈在光學膜及第1熱塑性樹脂膜之至少任一者的貼合面，而且隔著塗佈層而層積光學膜與第1熱塑性樹脂膜而得到積層體之後，使塗佈層硬化，能夠製造該光學積層體。 The curable composition (S) can also be used as an adhesive composition. In one embodiment, the curable composition (S) is an adhesive composition for bonding an optical film and a first thermoplastic resin film. In this case, the optical layering system sequentially includes an optical film, a first cured layer (adhesive layer) composed of a cured product of the curable composition (S), and a first thermoplastic resin film. The curable composition (S) is applied to the bonding surface of at least one of the optical film and the first thermoplastic resin film, and the optical film and the first thermoplastic resin film are laminated via the coating layer. After the laminate is formed, the coating layer is cured, and the optical laminate can be produced.
光學積層體係以光學膜為偏光片之偏光板為佳。所謂偏光板係包含偏光片、及層積在其至少一面的第1硬化物層(由硬化性組成物(S)的硬化物所構成之硬化物層)之光學積層體。 The optical layering system is preferably a polarizing plate in which an optical film is a polarizer. The polarizing plate is an optical layered body including a polarizer and a first cured layer (a cured layer composed of a cured product of the curable composition (S)) laminated on at least one surface thereof.
接著劑組成物之硬化性組成物(S)係以偏光板用接著劑組成物，亦即用以製造偏光板的接著劑組成物為佳。此時，硬化性組成物(S)係例如用以將偏光片與第1熱塑性樹脂膜貼合。 The curable composition (S) of the composition of the second embodiment is preferably an adhesive composition for a polarizing plate, that is, an adhesive composition for producing a polarizing plate. In this case, the curable composition (S) is used, for example, to bond the polarizer to the first thermoplastic resin film.
硬化性組成物(S)較佳為水系組成物。亦即，硬化性組成物(S)係以使調配成分溶解在含有水的溶劑而成之溶液、或使調配成分分散在含有水的溶劑而成之分散體(例如乳化液)為佳。 The curable composition (S) is preferably a water-based composition. In other words, the curable composition (S) is preferably a solution obtained by dissolving a formulation component in a solvent containing water or a dispersion (for example, an emulsion) in which a formulation component is dispersed in a solvent containing water.
硬化性組成物(S)之在25℃之黏度係以50mPa．sec以下為佳，以1mPa．sec以上且30mPa．sec以下為較佳，以2mPa．sec以上且20mPa．sec以下為更佳。在25℃之黏度大於50mPa．sec時，難以均勻地塗佈而有產生塗佈不均之可能性，而且有配管產生孔洞堵塞等不良狀況之可能性。 The viscosity of the hardening composition (S) at 25 ° C is 50 mPa. The following is better than sec, at 1mPa. Above sec and 30mPa. The following is preferred for sec, at 2mPa. Above sec and 20mPa. The following sec is better. The viscosity at 25 ° C is greater than 50 mPa. In the case of sec, it is difficult to apply uniformly, and there is a possibility that coating unevenness may occur, and there is a possibility that a pipe may cause a problem such as clogging of a hole.
硬化性組成物(S)之在25℃之黏度，係能夠使 用E型黏度計而測定。 The viscosity of the curable composition (S) at 25 ° C can be measured using an E-type viscometer.
<光學積層體> <Optical laminate>
本發明之光學積層體係包含光學膜、及層積在其至少一面之第1硬化物層(由硬化性組成物(S)的硬化物所構成之硬化物層)。 The optical layering system of the present invention comprises an optical film and a first cured layer (a cured layer composed of a cured product of the curable composition (S)) laminated on at least one surface thereof.
依照本發明，因為在光學積層體所含有的硬化物層係由硬化性組成物(S)的硬化物所構成，所以能夠使光學積層體的耐熱性成為良好。 According to the invention, since the cured layer contained in the optical layered body is composed of a cured product of the curable composition (S), the heat resistance of the optical layered body can be improved.
將光學積層體的層結構的例子顯示在第1圖至第5圖。 An example of the layer structure of the optical laminate is shown in Figs. 1 to 5.
第1圖顯示之光學積層體係包含光學膜30、及層積在其一面之第1硬化物層15。第1硬化物層15係能夠發揮作為被覆光學膜30的表面而予以保護之保護層，及作為對光學膜30追加賦予光學功能的光學功能層等之功能。 The optical layering system shown in Fig. 1 includes an optical film 30 and a first cured layer 15 laminated on one surface thereof. The first cured layer 15 functions as a protective layer that protects the surface of the coated optical film 30 and an optical functional layer that imparts an optical function to the optical film 30.
光學膜30與第1硬化物層15係以直接接觸為佳。 It is preferable that the optical film 30 and the first cured material layer 15 are in direct contact.
第2圖顯示之光學積層體係包含光學膜30、及隔著第1硬化物層15而積層貼合在該光學膜30的一面之第1熱塑性樹脂膜10。第1硬化物層15係能夠發揮作為將光學膜30與第1熱塑性樹脂膜10接著的接著劑層之功能。 The optical layering system shown in Fig. 2 includes an optical film 30 and a first thermoplastic resin film 10 laminated on one surface of the optical film 30 via the first cured layer 15. The first cured material layer 15 functions as an adhesive layer that connects the optical film 30 and the first thermoplastic resin film 10 .
第1硬化物層15與第1熱塑性樹脂膜10係 以直接接觸為佳。 The first cured product layer 15 and the first thermoplastic resin film 10 are preferably in direct contact.
光學膜30與第1硬化物層15係以直接接觸為佳。 It is preferable that the optical film 30 and the first cured material layer 15 are in direct contact.
第3圖顯示之光學積層體係包含光學膜30、隔著第1硬化物層15而積層貼合在該光學膜30的一面之第1熱塑性樹脂膜10、及隔著第2硬化物層25而積層貼合在光學膜30的另一面之第2熱塑性樹脂膜20。亦即，本發明之光學積層體亦可依序包含第2熱塑性樹脂膜20、第2硬化物層25、光學膜30、第1硬化物層15、及第1熱塑性樹脂膜10。第1硬化物層15及第2硬化物層25係能夠分別發揮作為將光學膜30與第1熱塑性樹脂膜10接著的接著劑層、及作為將光學膜30與第2熱塑性樹脂膜20接著的接著劑層之功能。 The optical layering system shown in FIG. 3 includes the optical film 30, the first thermoplastic resin film 10 laminated on one surface of the optical film 30 via the first cured material layer 15, and the second cured material layer 25 interposed therebetween. The second thermoplastic resin film 20 is laminated on the other surface of the optical film 30. In other words, the optical laminate of the present invention may include the second thermoplastic resin film 20, the second cured material layer 25, the optical film 30, the first cured material layer 15, and the first thermoplastic resin film 10 in this order. The first cured material layer 15 and the second cured material layer 25 can respectively serve as an adhesive layer that connects the optical film 30 and the first thermoplastic resin film 10, and as the optical film 30 and the second thermoplastic resin film 20, respectively. The function of the layer of the agent.
第1硬化物層15與第1熱塑性樹脂膜10係以直接接觸為佳。 The first cured product layer 15 and the first thermoplastic resin film 10 are preferably in direct contact.
光學膜30與第1硬化物層15係以直接接觸為佳。 It is preferable that the optical film 30 and the first cured material layer 15 are in direct contact.
第2硬化物層25與第2熱塑性樹脂膜20係以直接接觸為佳。 The second cured product layer 25 and the second thermoplastic resin film 20 are preferably in direct contact.
光學膜30與第2硬化物層25係以直接接觸為佳。 It is preferable that the optical film 30 and the second cured layer 25 are in direct contact.
第4圖顯示之光學積層體係包含光學膜30、層積在其一面之第1硬化物層15、及隔著第2硬化物層25而積層貼合在光學膜30的另一面之第2熱塑性樹脂膜20。第1 硬化物層15係能夠發揮作為被覆光學膜30的表面而予以保護之保護層，及作為對光學膜30追加賦予性光學功能的光學功能層等之功能。第2硬化物層25係能夠作為將光學膜30與第2熱塑性樹脂膜20接著的接著劑層之功能。 The optical layering system shown in Fig. 4 includes an optical film 30, a first cured layer 15 laminated on one surface thereof, and a second thermoplastic layer laminated on the other surface of the optical film 30 via the second cured layer 25. Resin film 20. The first cured layer 15 functions as a protective layer that protects the surface of the coated optical film 30 and an optical functional layer that adds an imparting optical function to the optical film 30. The second cured layer 25 can function as an adhesive layer that connects the optical film 30 and the second thermoplastic resin film 20 .
光學膜30與第1硬化物層15係以直接接觸為佳。 It is preferable that the optical film 30 and the first cured material layer 15 are in direct contact.
第2硬化物層25與第2熱塑性樹脂膜20係以直接接觸為佳。 The second cured product layer 25 and the second thermoplastic resin film 20 are preferably in direct contact.
光學膜30與第2硬化物層25係以直接接觸為佳。 It is preferable that the optical film 30 and the second cured layer 25 are in direct contact.
第5圖顯示之光學積層體係包含光學膜30、層積在其一面之第1硬化物層15、及層積在光學膜30的另一面之第2硬化物層25。第1硬化物層15及第2硬化物層25係能夠發揮作為被覆光學膜30的表面而予以保護之保護層，及作為對光學膜30追加賦予光學功能的光學功能層等之功能。 The optical layering system shown in Fig. 5 includes an optical film 30, a first cured layer 15 laminated on one surface thereof, and a second cured layer 25 laminated on the other surface of the optical film 30. The first cured layer 15 and the second cured layer 25 can function as a protective layer that protects the surface of the coated optical film 30, and an optical functional layer that adds an optical function to the optical film 30.
光學膜30與第1硬化物層15係以直接接觸為佳。 It is preferable that the optical film 30 and the first cured material layer 15 are in direct contact.
光學膜30與第2硬化物層25係以直接接觸為佳。 It is preferable that the optical film 30 and the second cured layer 25 are in direct contact.
光學膜30亦可為能夠被組裝於液晶顯示裝置等畫像顯示裝置之各種光學膜(具有光學特性之薄膜)。作為光學膜30例如可舉出偏光片、相位差膜、亮度提升膜、防眩膜、抗反射膜、擴散膜、聚光膜等。 The optical film 30 may be various optical films (films having optical characteristics) that can be incorporated in an image display device such as a liquid crystal display device. Examples of the optical film 30 include a polarizer, a retardation film, a brightness enhancement film, an anti-glare film, an anti-reflection film, a diffusion film, and a light-concentrating film.
光學積層體係能夠包含上述以外的其它層(或 薄膜)。作為其它層例如可舉出：層積在第1熱塑性樹脂膜10、第2熱塑性樹脂膜20、第1硬化物層15、第2硬化物層25及/或光學膜30的外表面之黏著劑層；層積在該黏著劑層的外表面之隔離膜(亦稱為「剝離膜」)；層積在第1熱塑性樹脂膜10、第2熱塑性樹脂膜20、第1硬化物層15、第2硬化物層25及/或光學膜30的外表面之保護膜(亦稱為「表面保護膜」)；隔著接著劑層和黏著劑層而層積在第1熱塑性樹脂膜10、第2熱塑性樹脂膜20、第1硬化物層15、第2硬化物層25及/或光學膜30的外表面之光學功能性膜(或層)等。 The optical layering system can comprise other layers (or films) than those described above. Examples of the other layer include an adhesive laminated on the outer surfaces of the first thermoplastic resin film 10, the second thermoplastic resin film 20, the first cured material layer 15, the second cured material layer 25, and/or the optical film 30. a separator (also referred to as a "peeling film") laminated on the outer surface of the adhesive layer; laminated on the first thermoplastic resin film 10, the second thermoplastic resin film 20, the first cured layer 15, and the first 2 a protective film (also referred to as a "surface protective film") on the outer surface of the cured layer 25 and/or the optical film 30; laminated on the first thermoplastic resin film 10 and the second via the adhesive layer and the adhesive layer An optical functional film (or layer) of the outer surface of the thermoplastic resin film 20, the first cured material layer 15, the second cured material layer 25, and/or the optical film 30.
偏光片係具有使來自自然光之某一方向的直線偏光選擇性地穿透的功能之層或薄膜。 The polarizer has a function of a layer or film that selectively penetrates linearly polarized light from a certain direction of natural light.
作為偏光片例如可舉出使二色性色素吸附/配向在聚乙烯醇系樹脂膜而成之薄膜。作為二色性色素可舉出碘、二色性有機染料等。 The polarizing plate is, for example, a film obtained by adsorbing/aligning a dichroic dye to a polyvinyl alcohol-based resin film. Examples of the dichroic dye include iodine and a dichroic organic dye.
又，偏光片亦可為將溶致液晶(lyotropic liquid crystal)狀態的二色性染料塗佈在基材薄膜且予以配向/固定化而成之塗佈型偏光膜。 Further, the polarizer may be a coating type polarizing film obtained by applying a dicophilic dye in a lyotropic liquid crystal state to a base film and aligning/fixing it.
以上的偏光片，由於使來自自然光之某一方向的直線偏光選擇性地穿透，且將另一方向的直線偏光吸收，故被稱為吸收型偏光片。 The above polarizer is referred to as an absorptive polarizer because it selectively permeates linearly polarized light from a certain direction of natural light and absorbs linearly polarized light in the other direction.
偏光片不限定於吸收型偏光片，亦可為將來 自自然光之某一方向的直線偏光選擇性地穿透且將另一方向的直線偏光反射之反射型偏光片、或是將另一方向的直線偏光散射之散射型偏光片，但就具有優異的觀視性而言，係以吸收型偏光片為佳。尤其是以由聚乙烯醇系樹脂膜所構成之聚乙烯醇系偏光膜為較佳，以使碘、二色性染料等二色性色素吸附/配向在聚乙烯醇系樹脂膜而成之聚乙烯醇系偏光膜為更佳，以使碘吸附/配向在聚乙烯醇系樹脂膜而成之聚乙烯醇系偏光膜為特佳。 The polarizer is not limited to the absorptive polarizer, and may be a reflective polarizer that selectively penetrates linearly polarized light from one direction of natural light and polarized light in the other direction, or in another direction. A linear polarized light scattering type polarizer, but in terms of excellent visibility, an absorptive polarizer is preferred. In particular, a polyvinyl alcohol-based polarizing film comprising a polyvinyl alcohol-based resin film is preferably used to adsorb/align a dichroic dye such as iodine or a dichroic dye to a polyvinyl alcohol-based resin film. A vinyl alcohol-based polarizing film is more preferable, and a polyvinyl alcohol-based polarizing film in which iodine is adsorbed/aligned to a polyvinyl alcohol-based resin film is particularly preferable.
作為聚乙烯醇系樹脂係能夠使用將聚乙酸乙烯系樹脂皂化而成者。就聚乙酸乙烯系樹脂而言，係除了屬旖乙酸乙烯酯的同元聚合物之聚乙酸乙烯酯以外，亦可舉出乙酸乙烯酯和能夠與該乙酸乙烯酯共聚合的其它單體之共聚物等。作為能夠與乙酸乙烯酯共聚合的其它單體可舉出不飽和羧酸類、烯烴類、乙烯醚類、不飽和磺酸類、及具有銨基之(甲基)丙烯醯胺類等。 As the polyvinyl alcohol-based resin, a polyvinyl acetate-based resin can be used for saponification. In the case of a polyvinyl acetate-based resin, in addition to a polyvinyl acetate which is a homopolymer of vinyl acetate, a copolymerization of vinyl acetate and other monomers copolymerizable with the vinyl acetate may be mentioned. Things and so on. Examples of the other monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and (meth) acrylamides having an ammonium group.
聚乙烯醇系樹脂的皂化度通常為85莫耳%以上且100莫耳%以下，以98莫耳%以上為佳。聚乙烯醇系樹脂亦可經改性，例如亦能夠使用經醛類改性聚乙烯甲醛或聚乙烯縮醛等。聚乙烯醇系樹脂的平均聚合度通常為1000以上且10000以下，以1500以上且5000以下為佳。 The degree of saponification of the polyvinyl alcohol-based resin is usually 85 mol% or more and 100 mol% or less, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, and for example, an aldehyde-modified polyethylene formaldehyde or a polyvinyl acetal may also be used. The average degree of polymerization of the polyvinyl alcohol-based resin is usually 1,000 or more and 10,000 or less, and more preferably 1,500 or more and 5,000 or less.
聚乙烯醇系樹脂的平均聚合度係能夠依據JIS K 6726：1994而求取。 The average degree of polymerization of the polyvinyl alcohol-based resin can be determined in accordance with JIS K 6726:1994.
將此種聚乙烯醇系樹脂製膜而成者，係被使用作為由聚乙烯醇系樹脂膜所構成之偏光膜的坯膜。將聚 乙烯醇系樹脂製膜之方法係沒有特別限定，能夠採用眾所周知的方法。聚乙烯醇系坯膜的厚度係例如150μm以下，較佳為100μm以下(例如50μm以下)且5μm以上。 A film made of such a polyvinyl alcohol-based resin is used as a green film of a polarizing film made of a polyvinyl alcohol-based resin film. The method for forming a film of a polyvinyl alcohol-based resin is not particularly limited, and a known method can be employed. The thickness of the polyvinyl alcohol-based green film is, for example, 150 μm or less, preferably 100 μm or less (for example, 50 μm or less) and 5 μm or more.
由聚乙烯醇系樹脂膜所構成之偏光膜係能夠藉由眾所周知的方法而製造。具體而言，係能夠藉由包含下列步驟之方法而製造：將聚乙烯醇系樹脂膜進行單軸延伸之步驟；藉由使用二色性色素將聚乙烯醇系樹脂膜染色而使其吸附二色性色素之步驟；使用硼酸水溶液對已吸附二色性色素的聚乙烯醇系樹脂膜進行處理(交聯處理)之步驟；以及，在處理後藉由硼酸水溶液進行水洗之步驟。 The polarizing film composed of a polyvinyl alcohol-based resin film can be produced by a known method. Specifically, it can be produced by a method comprising the steps of: uniaxially stretching a polyvinyl alcohol-based resin film; and dyeing the polyvinyl alcohol-based resin film by using a dichroic dye to adsorb the second a step of treating a coloring dye; a step of treating (cross-linking) the polyvinyl alcohol-based resin film to which the dichroic dye has been adsorbed using an aqueous solution of boric acid; and a step of washing with water by a boric acid aqueous solution after the treatment.
偏光片的厚度係能夠設為40μm以下，以30μm以下(例如20μm以下，更佳為15μm以下，又更佳為10μm以下或8μm以下)為佳。藉由日本特開2000-338329號公報或日本特開2012-159778號公報記載之方法時，能夠更容易地製造薄膜的偏光片，且更容易地使偏光片的厚度成為例如20μm以下，更佳為15μm以下，又更佳為10μm以下或8μm以下。偏光片的厚度通常為2μm以上。減少偏光片的厚度，係對光學積層體(偏光板)、及包含該光學積層體之畫像顯示裝置的薄型化為有利。 The thickness of the polarizer can be 40 μm or less, preferably 30 μm or less (for example, 20 μm or less, more preferably 15 μm or less, still more preferably 10 μm or less or 8 μm or less). When the method described in JP-A-2000-338778 or JP-A-2012-159778, the polarizer of the film can be more easily produced, and the thickness of the polarizer can be more easily made, for example, 20 μm or less, more preferably It is 15 μm or less, and more preferably 10 μm or less or 8 μm or less. The thickness of the polarizer is usually 2 μm or more. It is advantageous to reduce the thickness of the polarizer to reduce the thickness of the optical layered body (polarizing plate) and the image display device including the optical layered body.
作為相位差膜可舉出：將具有透光性之熱塑性樹脂進行單軸延伸或雙軸延伸而成之延伸膜；將碟狀液晶或向列型液晶等液晶性化合物配向固定而成之薄膜；及在基材薄 膜上形成有上述液晶層者等。又，在本說明書中，相位差膜亦包含零遲滯值薄膜。 The retardation film is a stretched film obtained by uniaxially stretching or biaxially stretching a light-transmitting thermoplastic resin, and a film obtained by disposing a liquid crystal compound such as a discotic liquid crystal or a nematic liquid crystal; And the liquid crystal layer formed on the base film. Further, in the present specification, the retardation film also includes a film having a zero hysteresis value.
基材薄膜通常係由熱塑性樹脂所構成之薄膜，熱塑性樹脂的一個例子為三乙酸纖維素等纖維素酯系樹脂。 The base film is usually a film made of a thermoplastic resin, and an example of the thermoplastic resin is a cellulose ester resin such as cellulose triacetate.
作為具有透光性之熱塑性樹脂可舉出構成後述第1熱塑性樹脂膜10之樹脂等。 The thermoplastic resin which is translucent is exemplified by a resin constituting the first thermoplastic resin film 10 to be described later.
所謂零遲滯值薄膜係指面內相位差值Re及厚度方向相位差值Rth均為-15至15nm之薄膜。該相位差膜適合使用在IPS模式的液晶顯示裝置。面內相位差值Re及厚度方向相位差值Rth係以均為-10至10nm為佳，較佳是均為-5至5nm。在此所謂面內相位差值Re及厚度方向相位差值Rth為在波長590nm之值。 The zero hysteresis value film refers to a film in which the in-plane phase difference value R e and the thickness direction phase difference value R th are both -15 to 15 nm. This retardation film is suitable for use in a liquid crystal display device of the IPS mode. The in-plane phase difference value R e and the thickness direction phase difference value R th are preferably from -10 to 10 nm, preferably from -5 to 5 nm. Here, the in-plane phase difference value R e and the thickness direction phase difference value R th are values at a wavelength of 590 nm.
面內相位差值Re及厚度方向相位差值Rth各由下述式定義：Re=(nx-ny)×d The in-plane phase difference value R e and the thickness direction phase difference value R th are each defined by the following formula: R e =(n x -n y )×d
Rth=[(nx+ny)/2-nz]×d R th =[(n x +n y )/2-n z ]×d
式中，nx為薄膜面內的慢軸方向(x軸方向)之折射率，ny為薄膜面內的快軸方向(在面內與x軸正交之y軸方向)之折射率，nz為薄膜厚度方向(與薄膜面垂直的z軸方向)之折射率，d為薄膜厚度。 Where n x is the refractive index in the slow axis direction (x-axis direction) in the plane of the film, and n y is the refractive index in the fast axis direction (the y-axis direction orthogonal to the x-axis in the plane) in the plane of the film, n z is the refractive index of the film thickness direction (z-axis direction perpendicular to the film surface), and d is the film thickness.
零遲滯值薄膜係例如能夠使用由纖維素系樹脂、鏈狀聚烯烴系樹脂及環狀聚烯烴系樹脂等聚烯烴系樹脂、聚對苯二甲酸乙二酯系樹脂或(甲基)丙烯酸系樹脂所構成之樹脂膜。特別是因為容易控制相位差值且亦容易取 得，故適合使用纖維素系樹脂、聚烯烴系樹脂或(甲基)丙烯酸系樹脂。 For the film having a zero hysteresis value, for example, a polyolefin resin such as a cellulose resin, a chain polyolefin resin or a cyclic polyolefin resin, a polyethylene terephthalate resin or a (meth)acrylic acid can be used. A resin film composed of a resin. In particular, since it is easy to control the phase difference and is also easily obtained, a cellulose resin, a polyolefin resin or a (meth)acrylic resin is suitably used.
作為藉由液晶性化合物的塗佈/配向而顯現光學異向性之薄膜，可舉出下列薄膜：第一形態：棒狀液晶化合物朝與支撐基材水平的方向配向之相位差膜，第二形態：棒狀液晶化合物朝與支撐基材垂直的方向配向之相位差膜，第三形態：棒狀液晶化合物在面內沿螺旋狀改變配向方向之相位差膜，第四形態：圓盤狀液晶化合物傾斜配向之相位差膜、第五形態：圓盤狀液晶化合物朝與支撐基材垂直的方向配向之雙軸性相位差膜。 A film which exhibits optical anisotropy by application/alignment of a liquid crystal compound includes the following film: a first form: a retardation film in which a rod-like liquid crystal compound is aligned in a direction horizontal to a support substrate, and a second Form: a retardation film in which a rod-like liquid crystal compound is aligned in a direction perpendicular to a support substrate, and a third aspect: a retardation film in which a rod-like liquid crystal compound changes a direction of alignment in a spiral shape in a plane, and a fourth form: discotic liquid crystal A retardation film in which the compound is obliquely aligned, and a fifth aspect: a biaxial retardation film in which the discotic liquid crystal compound is aligned in a direction perpendicular to the support substrate.
例如作為使用在有機電致發光顯示器之光學膜，適合使用第一形態、第二形態、第五形態。或者亦可將該等層積而使用。 For example, as the optical film used in the organic electroluminescence display, the first form, the second form, and the fifth form are suitably used. Alternatively, the layers may be used in combination.
相位差膜為由聚合性液晶化合物之處在配向狀態的聚合物所構成之層(以下，有時稱為「光學異向性層」)時，相位差膜係以具有逆波長分散性為佳。所謂逆波長分散性，係相較於在長波長的液晶配向面內相位差值，在短波長的液晶配向面內相位差值為較小之光學特性，較佳係相位差膜滿足下述式(1)及式(2)。又，Re(λ)係表示相對於波長λnm的光線之面內相位差值。 When the retardation film is a layer composed of a polymer in a state of being aligned with a polymerizable liquid crystal compound (hereinafter referred to as an "optical anisotropic layer"), the retardation film preferably has a reverse wavelength dispersion property. . The reverse wavelength dispersion is an optical characteristic in which the phase difference value in the short-wavelength liquid crystal alignment plane is small compared to the phase difference in the liquid crystal alignment direction of the long wavelength, and the phase difference film preferably satisfies the following formula. (1) and formula (2). Further, R e (λ) represents the in-plane retardation value of the light with respect to the wavelength λ nm.
Re(450)/Re(550)≦1 (1) R e (450)/R e (550)≦1 (1)
1≦Re(630)/Re(550) (2) 1≦R e (630)/R e (550) (2)
在相位差膜為第一形態且具有逆波長分散性時，在顯示裝置之黑畫面時的著色得到減低，因而較佳，在式(1)中為0.82≦Re(450)/Re(550)≦0.93時為較佳。以120≦Re(550)≦150為更佳。 When the retardation film has the first form and has reverse wavelength dispersion, the coloring at the black screen of the display device is reduced, so that it is preferably 0.82 ≦R e (450)/R e (in the formula (1)). 550) ≦ 0.93 is preferred. It is better to use 120 ≦R e (550) ≦ 150.
作為在相位差膜為具有光學異向性層之薄膜時的聚合性液晶化合物，可舉出在液晶手冊(液晶手冊編集委員會編，丸善(股)平成12年10月30日發行)的「3.8.6網狀(完全交聯型)」、「6.5.1液晶材料b.聚合性向列型液晶材料」記載之化合物中具有聚合性基之化合物、以及在日本特開2010-31223號公報、日本特開2010-270108號公報、日本特開2011-6360號公報、日本特開2011-207765號公報、日本特開2016-81035號公報、國際公開第2017/043438號及日本特表2011-207765號公報記載之聚合性液晶化合物。 The polymerizable liquid crystal compound in the case where the retardation film is a film having an optically anisotropic layer is 3.8 in the liquid crystal handbook (edited by the Liquid Crystal Handbook Compilation Committee, Maruzen Co., Ltd., issued on October 30, 2009). a compound having a polymerizable group in the compound described in the "6. 1 network material (completely crosslinked type)", "6.5.1 liquid crystal material b. polymerizable nematic liquid crystal material", and Japanese Laid-Open Patent Publication No. 2010-31223, Japan Japanese Laid-Open Patent Publication No. 2010-270108, Japanese Laid-Open Patent Publication No. 2011-6360, Japanese Laid-Open Patent Publication No. 2011-207765, Japanese Laid-Open Patent Publication No. Hei. No. 2016-81035, International Publication No. 2017/043438, and Japanese Patent Publication No. 2011-207765 A polymerizable liquid crystal compound described in the publication.
從聚合性液晶化合物之處在配向狀態之聚合物製造相位差膜之方法，例如可舉出在日本特開2010-31223號公報記載的方法。 A method of producing a retardation film from a polymer in an alignment state from a polymerizable liquid crystal compound, for example, a method described in JP-A-2010-31223.
為第2形態時，面內相位差值Re(550)係調整在0至10nm的範圍、較佳為0至5nm的範圍即可，厚度方向的相位差值Rth係調整在-10至-300nm的範圍、較佳為-20至-200nm的範圍即可。 In the second embodiment, the in-plane phase difference value R e (550) is adjusted in the range of 0 to 10 nm, preferably in the range of 0 to 5 nm, and the phase difference R th in the thickness direction is adjusted to -10 to The range of -300 nm, preferably in the range of -20 to -200 nm, may be sufficient.
意指厚度方向的折射率異向性之厚度方向的 相位差值Rth，係能夠從將面內的快軸傾斜50度成傾斜軸而測定之相位差值R50及面內相位差值Re算出。亦即，厚度方向的相位差值Rth係能夠從面內的相位差值Re、將進相軸傾斜50度成傾斜軸而測定之相位差值R50、相位差膜的厚度d、及相位差膜的平均折射率n0，依照以下的式(4)至(6)求取nx、ny及nz，而且將該等nx、ny及nz代入至式(3)而算出。 The phase difference R th in the thickness direction of the refractive index anisotropy in the thickness direction is a phase difference R 50 and an in-plane phase difference R which can be measured by inclining the in-plane fast axis by 50 degrees into an inclined axis. e calculated. That is, the thickness retardation value R th lines from the direction retardation value R e can be in the plane, the fast axis is inclined 50 degrees to the axis of the retardation value measured inclination 50 R & lt retardation film thickness d, and The average refractive index n 0 of the retardation film is obtained by taking n x , n y and n z according to the following formulas (4) to (6), and substituting the n x , n y and n z into the formula (3) And calculate.
Rth=[(nx+ny)/2-nz]×d (3) R th =[(n x +n y )/2-n z ]×d (3)
Re=(nx-ny)×d (4) R e =(n x -n y )×d (4)
R50=(nx-ny’)×d/cos(φ) (5) R 50 =(n x -n y ')×d/cos(φ) (5)
(nx+ny+nz)/3=n0 (6) (n x +n y +n z )/3=n 0 (6)
在此， here,
φ=sin-1〔sin(40°)/n0〕 φ=sin -1 [sin(40°)/n 0 ]
ny’=ny×nz/〔ny 2×sin2(φ)+nz 2×cos2(φ)〕1/2 n y '=n y ×n z /[n y 2 ×sin 2 (φ)+n z 2 ×cos 2 (φ)] 1/2
相位差膜亦可為具有二個以上的層之多層膜。例如可舉出：將保護膜層積在相位差膜的一面或兩面而成者；及隔著黏著劑或接著劑將二個以上的相位差膜層積而成者。 The retardation film may also be a multilayer film having two or more layers. For example, a protective film may be laminated on one surface or both surfaces of a retardation film; and two or more retardation films may be laminated via an adhesive or an adhesive.
第1硬化物層15係由硬化性組成物(S)的硬化物所構成之硬化物層。針對硬化性組成物(S)係如上述。硬化性組成物(S)係例如能夠藉由熱而使其硬化。 The first cured layer 15 is a cured layer composed of a cured product of the curable composition (S). The curable composition (S) is as described above. The curable composition (S) can be cured, for example, by heat.
第1熱塑性樹脂膜10及第2熱塑性樹脂膜20可分別為由下述者所構成之薄膜：具有透光性之(較佳為光學上為透明的)熱塑性樹脂，例如鏈狀聚烯烴系樹脂(聚丙烯系樹脂等)、環狀聚烯烴系樹脂(降莰烯系樹脂等)等聚烯烴系樹脂；三乙酸纖維素、二乙酸纖維素等纖維素酯系樹脂；聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯等聚酯系樹脂；聚碳酸酯系樹脂；(甲基)丙烯酸系樹脂；聚苯乙烯系樹脂；或該等樹脂的混合物、共聚物等。 Each of the first thermoplastic resin film 10 and the second thermoplastic resin film 20 may be a film composed of a light transmissive (preferably optically transparent) thermoplastic resin such as a chain polyolefin resin. (polypropylene resin, etc.), polyolefin resin such as cyclic polyolefin resin (northene based resin); cellulose ester resin such as cellulose triacetate or cellulose diacetate; polyethylene terephthalate a polyester resin such as a diester, polyethylene naphthalate or polybutylene terephthalate; a polycarbonate resin; a (meth)acrylic resin; a polystyrene resin; or a resin Mixtures, copolymers, and the like.
第1熱塑性樹脂膜10及第2熱塑性樹脂膜20係各自可為未經延伸之薄膜、或經單軸或是雙軸延伸之薄膜之任一者。雙軸延伸可為同時朝2個延伸方向延伸之同時雙軸延伸，亦可為在朝第1方向延伸之後再朝不同之第2方向延伸之逐次雙軸延伸。 Each of the first thermoplastic resin film 10 and the second thermoplastic resin film 20 may be either an unstretched film or a film that is uniaxially or biaxially stretched. The biaxial extension may be a biaxial extension while extending in two extending directions at the same time, or may be a sequential biaxial extension extending in the second direction after extending in the first direction.
第1熱塑性樹脂膜10及/或第2熱塑性樹脂膜20亦可為承擔保護光學膜30的作用之保護膜，且亦可為兼具相位差膜等的光學功能之保護膜。 The first thermoplastic resin film 10 and/or the second thermoplastic resin film 20 may be a protective film that functions to protect the optical film 30, or may be a protective film that has an optical function such as a retardation film.
針對相位差膜係引用上述[4]的記載。 The description of the above [4] is cited for the retardation film system.
作為鏈狀聚烯烴系樹脂能夠舉出聚乙烯樹脂、聚丙烯樹脂等鏈狀烯烴的同元聚合物、以及由2種以上的鏈狀烯烴所構成之共聚物。 Examples of the chain-like polyolefin resin include a homopolymer of a chain olefin such as a polyethylene resin or a polypropylene resin, and a copolymer composed of two or more kinds of chain olefins.
環狀聚烯烴系樹脂係含有以降莰烯、四環十二烯(別名：二甲橋八氫萘；dimethano octahydronaphthalene)或該等的衍生物作為代表例之環狀烯烴作為聚合單元之樹 脂的總稱。就環狀聚烯烴系樹脂而言，可舉出環狀烯烴的開環(共)聚合物及其氫化物、環狀烯烴的加成聚合物、環狀烯烴與乙烯、丙烯等鏈狀烯烴或具有乙烯基之芳香族化合物的共聚物、以及該等聚合物經用不飽和羧酸或其衍生物改性之改性(共)聚合物等。 The cyclic polyolefin-based resin is a general term for a resin containing a terpene, tetracyclododecene (alias: dimethano octahydronaphthalene) or a derivative of such a cyclic olefin as a polymerized unit. . Examples of the cyclic polyolefin-based resin include a ring-opened (co)polymer of a cyclic olefin, a hydrogenated product thereof, an addition polymer of a cyclic olefin, a cyclic olefin, and a chain olefin such as ethylene or propylene. A copolymer having a vinyl aromatic compound, and a modified (co)polymer or the like modified with an unsaturated carboxylic acid or a derivative thereof.
尤其適合使用將降莰烯、多環降莰烯系單體等降莰烯系單體作為環狀烯烴之降莰烯系樹脂。 In particular, a norbornene-based resin having a norbornene-based monomer such as a norbornene or a polycyclic norbornene-based monomer as a cyclic olefin is preferably used.
纖維素酯系樹脂係纖維素中之羥基的至少一部分經乙酸酯化之樹脂，亦可為一部分經乙酸酯化且一部分經其它酸酯化之混合酯。纖維素酯系樹脂較佳為乙酸纖維素系樹脂。 The cellulose esterified resin of at least a part of the hydroxyl group in the cellulose ester-based cellulose may be a partially mixed ester which is acetated and partially esterified. The cellulose ester-based resin is preferably a cellulose acetate-based resin.
作為乙酸纖維素系樹脂可舉出三乙酸纖維素、二乙酸纖維素、纖維素乙酸酯丙酸酯、纖維素乙酸酯丁酸酯等。 Examples of the cellulose acetate-based resin include cellulose triacetate, cellulose diacetate, cellulose acetate propionate, and cellulose acetate butyrate.
聚酯系樹脂係具有酯鍵之上述纖維素酯系樹脂以外的樹脂，通常為由多元羧酸或其衍生物與多元醇的聚縮合物所構成者。 The polyester-based resin is a resin other than the cellulose ester-based resin having an ester bond, and is usually composed of a polycondensate of a polyvalent carboxylic acid or a derivative thereof and a polyhydric alcohol.
作為聚酯系樹脂可舉出聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯、聚萘二甲酸丁二酯、聚對苯二甲酸丙二酯、聚萘二甲酸丙二酯、聚對苯二甲酸環己烷二甲酯、聚萘二甲酸環己烷二甲酯等。 Examples of the polyester-based resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polytrimethylene terephthalate. , propylene naphthalate, dimethyl dimethyl terephthalate, cyclohexane dimethyl phthalate, and the like.
尤其是從機械性質、耐溶劑性、耐刮傷性、成本等的觀點而言，係能夠適合使用聚對苯二甲酸乙二酯。所謂聚對苯二甲酸乙二酯係指重複單元的80莫耳%以上 係由對苯二甲酸乙二酯所構成之樹脂，亦可含有源自其它共聚合成分(間苯二甲酸等二羧酸成分；丙二醇等二醇成分等)之結構單元。 In particular, from the viewpoints of mechanical properties, solvent resistance, scratch resistance, cost, and the like, polyethylene terephthalate can be suitably used. The term "polyethylene terephthalate" means that 80 mol% or more of the repeating unit is a resin composed of ethylene terephthalate, and may also contain other copolymerized components (dicarboxylic acid such as isophthalic acid). A structural unit such as an acid component or a diol component such as propylene glycol.
聚碳酸酯系樹脂係由碳酸與二醇或雙酚所形成之聚酯。從耐熱性、耐候性及耐酸性的觀點而言，尤其是適合使用在分子鏈具有二苯基烷之芳香族聚碳酸酯。 The polycarbonate resin is a polyester formed of carbonic acid and a diol or bisphenol. From the viewpoints of heat resistance, weather resistance, and acid resistance, an aromatic polycarbonate having a diphenyl alkane in a molecular chain is particularly preferably used.
作為聚碳酸酯可舉出由2,2-雙(4-羥苯基)丙烷(別名雙酚A)、2,2-雙(4-羥苯基)丁烷、1,1-雙(4-羥苯基)環己烷、1,1-雙(4-羥苯基)異丁烷、1,1-雙(4-羥苯基)乙烷等雙酚所衍生之聚碳酸酯。 The polycarbonate may be exemplified by 2,2-bis(4-hydroxyphenyl)propane (alias bisphenol A), 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis (4). A polycarbonate derived from a bisphenol such as -hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)isobutane or 1,1-bis(4-hydroxyphenyl)ethane.
(甲基)丙烯酸系樹脂係含有源自(甲基)丙烯酸系單體的結構單元之聚合物，作為(甲基)丙烯酸系單體可舉出甲基丙烯酸酯及丙烯酸酯。 The (meth)acrylic resin contains a polymer derived from a structural unit of a (meth)acrylic monomer, and examples of the (meth)acrylic monomer include methacrylate and acrylate.
作為甲基丙烯酸酯可舉出甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正、異或第三丁酯、甲基丙烯酸環己酯、甲基丙烯酸苯酯、甲基丙烯酸苯甲酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸2-羥基乙酯等。 Examples of the methacrylate include methyl methacrylate, ethyl methacrylate, methacrylic acid, n- or tert-butyl ester, cyclohexyl methacrylate, phenyl methacrylate, and methacrylic acid benzoate. Ester, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, and the like.
作為丙烯酸酯可舉出丙烯酸乙酯、丙烯酸正、異或第三丁酯、丙烯酸環己酯、丙烯酸苯酯、丙烯酸苯甲酯、丙烯酸2-乙基己酯、丙烯酸2-羥基乙酯等。 Examples of the acrylate include ethyl acrylate, n-butyl acrylate, iso- or tert-butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and the like.
(甲基)丙烯酸系樹脂可為只由源自(甲基)丙烯酸單體的結構單元所構成之聚合物，亦可含有其它結構單元。 The (meth)acrylic resin may be a polymer composed only of a structural unit derived from a (meth)acrylic monomer, and may contain other structural units.
在一較佳實施形態中，(甲基)丙烯酸系樹脂係 含有甲基丙烯酸甲酯作為共聚合成分，或含有甲基丙烯酸甲酯及丙烯酸甲酯作為共聚合成分。 In a preferred embodiment, the (meth)acrylic resin contains methyl methacrylate as a copolymerization component or methyl methacrylate and methyl acrylate as a copolymerization component.
在一較佳實施形態中，(甲基)丙烯酸系樹脂能夠為將甲基丙烯酸酯作為主要單體(含有50質量%以上)之聚合物，以將甲基丙烯酸酯與其它共聚合成分共聚合而成之共聚物為佳。 In a preferred embodiment, the (meth)acrylic resin can be a polymer having methacrylate as a main monomer (containing 50% by mass or more) to copolymerize methacrylate with other copolymerization components. The resulting copolymer is preferred.
(甲基)丙烯酸系樹脂的玻璃轉移溫度較佳為80℃以上且160℃以下。玻璃轉移溫度係能夠藉由調整甲基丙烯酸酯系單體與丙烯酸酯系單體之聚合比、各自的酯基的碳鏈長度及該等單體所具有的官能基種類、以及多官能單體相對於單體全體之聚合比而得到控制。 The glass transition temperature of the (meth)acrylic resin is preferably 80° C. or higher and 160° C. or lower. The glass transition temperature can be adjusted by adjusting the polymerization ratio of the methacrylate monomer and the acrylate monomer, the carbon chain length of each ester group, the functional group types of the monomers, and the polyfunctional monomer. It is controlled with respect to the polymerization ratio of the entire monomer.
作為用以提高(甲基)丙烯酸系樹脂的玻璃轉移溫度之手段，將環結構導入至高分子的主鏈亦為有效。環結構係以環狀酸酐結構、環狀醯亞胺結構及內酯結構等雜環結構為佳。具體而言，可舉出：戊二酸酐結構、琥珀酸酐結構等環狀酸酐結構；戊二醯亞胺(Glutarimide)結構、琥珀醯亞胺結構等環狀醯亞胺結構；丁內酯、戊內酯等內酯環結構。 As means for increasing the glass transition temperature of the (meth)acrylic resin, it is also effective to introduce a ring structure into the main chain of the polymer. The ring structure is preferably a heterocyclic structure such as a cyclic acid anhydride structure, a cyclic quinone imine structure or a lactone structure. Specific examples thereof include a cyclic acid anhydride structure such as a glutaric anhydride structure or a succinic anhydride structure; a cyclic quinone imine structure such as a Glutarimide structure or an amber quinone structure; butyrolactone and pentane a lactone ring structure such as a lactone.
主鏈中的環結構含量越增加時，有越能夠提高(甲基)丙烯酸系樹脂的玻璃轉移溫度之傾向。 When the content of the ring structure in the main chain increases, the glass transition temperature of the (meth)acrylic resin tends to increase.
環狀酸酐結構、環狀醯亞胺結構係能夠藉由下列方法而導入：藉由使順丁烯二酸酐、順丁烯二醯亞胺等具有環狀構造之單體共聚合而導入之方法；藉由聚合後脫水/脫甲醇縮合反應而導入環狀酸酐結構之方法；及使胺 基化合物反應而導入環狀醯亞胺結構之方法等。 The cyclic acid anhydride structure and the cyclic quinone imine structure system can be introduced by a method in which a monomer having a cyclic structure such as maleic anhydride or maleimide is copolymerized and introduced. A method of introducing a cyclic acid anhydride structure by a dehydration/de-methanol condensation reaction after polymerization; a method of introducing an amine group compound into a cyclic quinone imine structure, and the like.
具有內酯環結構之樹脂(聚合物)係能夠藉由下列方法而得到：調製在高分子鏈具有羥基及酯基之聚合物後，藉由加熱且視需要在有機磷化合物等觸媒的存在下，使在所得到的聚合物中之羥基及酯基進行環化縮合而形成內酯環結構之方法。 A resin (polymer) having a lactone ring structure can be obtained by disposing a polymer having a hydroxyl group and an ester group in a polymer chain, and heating, and optionally, a catalyst such as an organic phosphorus compound. Next, a method of forming a lactone ring structure by cyclizing and condensing a hydroxyl group and an ester group in the obtained polymer.
(甲基)丙烯酸系樹脂及由該(甲基)丙烯酸系樹脂所形成之熱塑性樹脂膜，亦可視需要而含有添加劑。作為添加劑例如能夠舉出潤滑劑、抗結塊劑、熱安定劑、抗氧化劑、抗靜電劑、耐光劑、耐衝撃性改良劑、界面活性劑等。 The (meth)acrylic resin and the thermoplastic resin film formed of the (meth)acrylic resin may contain an additive as needed. Examples of the additive include a lubricant, an anti-caking agent, a thermal stabilizer, an antioxidant, an antistatic agent, a light stabilizer, a pressurization improving agent, and a surfactant.
該等添加劑亦可在使用(甲基)丙烯酸系樹脂以外的其它熱塑性樹脂之情況時被作為構成熱塑性樹脂膜之熱塑性樹脂使用。 These additives may be used as a thermoplastic resin constituting the thermoplastic resin film when a thermoplastic resin other than the (meth)acrylic resin is used.
從對薄膜的製膜性、薄膜的耐衝撃性等之觀點而言，(甲基)丙烯酸系樹脂亦可含有衝撃性改良劑之丙烯酸系橡膠粒子。所謂丙烯酸系橡膠粒子係將以丙烯酸酯作為主體之彈性聚合物作為必要成分之粒子，可舉出實質上只由該彈性聚合物所構成的單層結構者、及將該彈性聚合物作為1層之多層結構者。 The (meth)acrylic resin may contain acrylic rubber particles of a rinsing agent, from the viewpoints of the film-forming property of the film, the squeezing resistance of the film, and the like. The acrylic rubber particles are particles in which an elastic polymer mainly composed of acrylate is used as an essential component, and a single layer structure consisting essentially of only the elastic polymer and a layer of the elastic polymer are used. The multi-layer structure.
作為上述彈性聚合物的例子可舉出將丙烯酸烷酯作為主成分且和能夠與該丙烯酸烷酯共聚合的其它乙烯系單體及交聯性單體共聚合而成之交聯彈性共聚物。 An example of the above-mentioned elastic polymer is a crosslinked elastic copolymer obtained by copolymerizing an alkyl acrylate as a main component and another vinyl monomer and a crosslinkable monomer copolymerizable with the alkyl acrylate.
作為彈性聚合物的主成分之丙烯酸烷酯例如 可舉出丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯等烷基的碳數為1以上且8以下左右者，適合使用具有碳數4以上的烷基之丙烯酸烷酯。 Examples of the alkyl acrylate which is a main component of the elastic polymer include those having an alkyl group such as methyl acrylate, ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate having a carbon number of 1 or more and 8 or less. An alkyl acrylate having an alkyl group having 4 or more carbon atoms is used.
作為能夠與上述丙烯酸烷酯共聚合之其它乙烯系單體能夠舉出在分子內具有1個聚合性碳-碳雙鍵之化合物，更具體地，可舉出：甲基丙烯酸甲酯等甲基丙烯酸酯；苯乙烯等芳香族乙烯系化合物；丙烯腈等乙烯基氰化合物等。 The other vinyl monomer which can be copolymerized with the above-mentioned alkyl acrylate can be a compound having one polymerizable carbon-carbon double bond in the molecule, and more specifically, a methyl group such as methyl methacrylate Acrylate; an aromatic vinyl compound such as styrene; a vinyl cyanide compound such as acrylonitrile.
作為上述交聯性單體能夠舉出在分子內具有至少2個聚合性碳-碳雙鍵之交聯性化合物，更具體地可舉出：乙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯等多元醇的(甲基)丙烯酸酯類；(甲基)丙烯酸烯丙酯等(甲基)丙烯酸的烯酯；二乙烯苯等。 The crosslinkable monomer may be a crosslinkable compound having at least two polymerizable carbon-carbon double bonds in the molecule, and more specifically, ethylene glycol di(meth)acrylate or dibutyl a (meth) acrylate of a polyhydric alcohol such as an alcohol di(meth) acrylate; an enester of (meth)acrylic acid such as allyl (meth) acrylate; divinyl benzene or the like.
亦能夠將不含有橡膠粒子且由(甲基)丙烯酸系樹脂所構成的薄膜與含有橡膠粒子且由(甲基)丙烯酸系樹脂所構成的薄膜之積層體，設為要貼合在光學膜30之熱塑性樹脂膜。又，亦能夠將在由與(甲基)丙烯酸樹脂不同的樹脂所構成之相位差顯現層的一面或兩面形成有(甲基)丙烯酸系樹脂層且顯現相位差者，設為要貼合在光學膜30之熱塑性樹脂膜。 A laminate of a film composed of a (meth)acrylic resin and a film containing a rubber particle and comprising a (meth)acrylic resin, which is not contained in rubber particles, can be bonded to the optical film 30. A thermoplastic resin film. In addition, a (meth)acrylic resin layer may be formed on one surface or both surfaces of a phase difference display layer composed of a resin different from the (meth)acrylic resin, and a phase difference may be exhibited. A thermoplastic resin film of the optical film 30.
第1熱塑性樹脂膜10及第2熱塑性樹脂膜20係各自以含有選自由纖維素酯系樹脂、聚酯系樹脂、(甲基)丙烯酸系樹脂及環狀聚烯烴系樹脂所組成群組之1種以上的熱塑性樹脂之薄膜為佳，以纖維素酯系樹脂膜、聚 酯系樹脂膜、(甲基)丙烯酸系樹脂膜、或環狀聚烯烴系樹脂膜為較佳。 Each of the first thermoplastic resin film 10 and the second thermoplastic resin film 20 contains one selected from the group consisting of a cellulose ester resin, a polyester resin, a (meth)acrylic resin, and a cyclic polyolefin resin. A film of the above thermoplastic resin is preferable, and a cellulose ester resin film, a polyester resin film, a (meth)acrylic resin film, or a cyclic polyolefin resin film is preferable.
第1熱塑性樹脂膜10及/或第2熱塑性樹脂膜20亦可含有紫外線吸收劑、紅外線吸收劑、有機系染料、顏料、無機色素、抗氧化劑、抗靜電劑、界面活性劑、潤滑劑、分散劑、熱安定化劑等。將光學積層體應用在畫像顯示裝置時，藉由將含有紫外線吸收劑之熱塑性樹脂膜配置在畫像顯示元件(例如液晶單元、有機EL顯示元件等)的觀視側，能夠抑制畫像顯示元件因紫外線而劣化。 The first thermoplastic resin film 10 and/or the second thermoplastic resin film 20 may contain an ultraviolet absorber, an infrared ray absorbing agent, an organic dye, a pigment, an inorganic dye, an antioxidant, an antistatic agent, a surfactant, a lubricant, and a dispersion. Agent, heat stabilizer, etc. When the optical layered product is applied to the image display device, the thermoplastic resin film containing the ultraviolet absorber is disposed on the viewing side of the image display element (for example, a liquid crystal cell or an organic EL display device), thereby suppressing the ultraviolet light of the image display device. And deteriorated.
作為紫外線吸收劑可舉出水楊酸酯系化合物、二苯基酮系化合物、苯并***系化合物、氰基丙烯酸酯系化合物、鎳錯鹽系化合物等。 Examples of the ultraviolet absorber include a salicylate-based compound, a diphenylketone-based compound, a benzotriazole-based compound, a cyanoacrylate-based compound, and a nickel-salted salt-based compound.
第1熱塑性樹脂膜10及第2熱塑性樹脂膜20可為由相同的熱塑性樹脂所構成之薄膜，亦可為由互相不同的熱塑性樹脂所構成之薄膜。第1熱塑性樹脂膜10及第2熱塑性樹脂膜20可在厚度、有無添加劑和其種類、相位差特性等方面為相同亦不同。 The first thermoplastic resin film 10 and the second thermoplastic resin film 20 may be a film composed of the same thermoplastic resin, or may be a film composed of thermoplastic resins different from each other. The first thermoplastic resin film 10 and the second thermoplastic resin film 20 may be the same in terms of thickness, presence or absence of additives, types thereof, phase difference characteristics, and the like.
第1熱塑性樹脂膜10及/或第2熱塑性樹脂膜20亦可在其外表面(與光學膜30相反側的表面)具備硬塗層、防眩層、抗反射層、光擴散層、抗靜電層、防污層、導電層等表面處理層(塗佈層)。 The first thermoplastic resin film 10 and/or the second thermoplastic resin film 20 may have a hard coat layer, an antiglare layer, an antireflection layer, a light diffusion layer, and an antistatic layer on the outer surface (the surface opposite to the optical film 30). A surface treatment layer (coating layer) such as a layer, an antifouling layer, or a conductive layer.
第1熱塑性樹脂膜10及第2熱塑性樹脂膜20的厚度各自通常為5μm以上且200μm以下，以10μm以上且120μm以下為佳，較佳為10μm以上且85μm以下， 更佳為15μm以上65μm以下。第1熱塑性樹脂膜10及第2熱塑性樹脂膜20的厚度各自可為50μm以下，亦可為40μm以下。將第1熱塑性樹脂膜10及第2熱塑性樹脂膜20的厚度減小，對光學積層體(偏光板)、及包含該光學積層體之畫像顯示裝置之薄型化為有利。 The thickness of each of the first thermoplastic resin film 10 and the second thermoplastic resin film 20 is usually 5 μm or more and 200 μm or less, preferably 10 μm or more and 120 μm or less, preferably 10 μm or more and 85 μm or less, and more preferably 15 μm or more and 65 μm or less. The thickness of each of the first thermoplastic resin film 10 and the second thermoplastic resin film 20 may be 50 μm or less, or may be 40 μm or less. The thickness of the first thermoplastic resin film 10 and the second thermoplastic resin film 20 is reduced, and it is advantageous to reduce the thickness of the optical layered body (polarizing plate) and the image display device including the optical layered body.
從提升密著性之觀點，對於第1熱塑性樹脂膜10及第2熱塑性樹脂膜20之要塗佈硬化性組成物之面可進行皂化處理、電漿處理、電暈處理、底漆處理等表面改質處理，從步驟簡單化的觀點，亦可實施表面改質處理。亦可對光學膜30的貼合面進行表面改質處理以取代熱塑性樹脂膜的貼合面，或是對熱塑性樹脂膜的貼合面與光學膜30的貼合面一起進行表面改質處理。 From the viewpoint of improving the adhesion, the surface of the first thermoplastic resin film 10 and the second thermoplastic resin film 20 to which the curable composition is applied can be subjected to saponification treatment, plasma treatment, corona treatment, primer treatment, and the like. The modification process can also be carried out from the viewpoint of simplification of the steps. The bonding surface of the optical film 30 may be subjected to surface modification treatment in place of the bonding surface of the thermoplastic resin film, or the surface of the bonding surface of the thermoplastic resin film and the bonding surface of the optical film 30 may be subjected to surface modification treatment.
第1熱塑性樹脂膜10或第2熱塑性樹脂膜20為纖維素酯系樹脂膜時，從提升密著性之觀點而言，係以進行皂化處理為佳。作為皂化處理可舉出浸漬在如氫氧化鈉和氫氧化鉀的鹼水溶液中之方法。 When the first thermoplastic resin film 10 or the second thermoplastic resin film 20 is a cellulose ester-based resin film, it is preferable to carry out saponification treatment from the viewpoint of improving adhesion. As the saponification treatment, a method of immersing in an aqueous alkali solution such as sodium hydroxide and potassium hydroxide can be mentioned.
形成第2硬化物層25之硬化性組成物可為上述硬化性組成物(S)，亦可為與其不同之其它硬化性組成物。從光學積層體的耐熱性等的觀點而言，第2硬化物層25係以硬化性組成物(S)的硬化物層為佳。 The curable composition forming the second cured layer 25 may be the curable composition (S) or another curable composition different therefrom. The second cured material layer 25 is preferably a cured layer of the curable composition (S) from the viewpoint of heat resistance of the optical laminate or the like.
第1硬化物層15及第2硬化物層25係由硬化性組成物(S)形成時，該等硬化性組成物可為相同的組成， 亦可為不同的組成。 When the first cured layer 15 and the second cured layer 25 are formed of a curable composition (S), the curable compositions may have the same composition or different compositions.
作為其它硬化性組成物可舉出含有已使硬化性樹脂成分溶解或分散在水中而成之眾所周知的水系組成物(含有水系接著劑)及活性能量線硬化性化合物之眾所周知的活性能量線硬化性組成物(含有活性能量線硬化性接著)等。 The other curable composition is a well-known active energy ray curability including a water-based composition (including a water-based adhesive) and an active energy ray-curable compound which are known to dissolve or disperse a curable resin component in water. The composition (including active energy ray hardenability) and the like.
作為在水系組成物所含有的樹脂成分可舉出聚乙烯醇系樹脂、胺甲酸酯樹脂等。 The resin component contained in the water-based composition may, for example, be a polyvinyl alcohol-based resin or a urethane resin.
為了提升密著性和接著性，含有聚乙烯醇系樹脂的水系組成物係能夠更含有多元醛、三聚氰胺系化合物、氧化鋯化合物、鋅化合物、乙二醛、乙二醛衍生物、水溶性環氧樹脂等硬化性成分或交聯劑。 In order to improve adhesion and adhesion, the aqueous composition containing a polyvinyl alcohol-based resin can further contain a polyvalent aldehyde, a melamine-based compound, a zirconia compound, a zinc compound, glyoxal, a glyoxal derivative, and a water-soluble ring. A curable component such as an oxygen resin or a crosslinking agent.
作為含有胺甲酸酯樹脂之水系組成物可舉出含有聚酯系離子聚合物型胺甲酸酯樹脂及具有環氧丙氧基的化合物之水系組成物。所謂聚酯系離子聚合物型胺甲酸酯樹脂係具有聚酯骨架之胺甲酸酯樹脂且其中導入有少量離子性成分(親水成分)者。 The water-based composition containing a urethane resin includes a water-based composition containing a polyester-based ionic polymer-type urethane resin and a compound having a glycidoxy group. The polyester-based ionic polymer type urethane resin is a urethane resin having a polyester skeleton and in which a small amount of an ionic component (hydrophilic component) is introduced.
活性能量線硬化性組成物係會藉由照射紫外線、可見光、電子射線、X射線等活性能量線而硬化之組成物。使用活性能量線硬化性組成物時，第2硬化物層25為該組成物的硬化物層。 The active energy ray-curable composition is a composition which is cured by irradiation with active energy rays such as ultraviolet rays, visible rays, electron rays, and X-rays. When the active energy ray-curable composition is used, the second cured layer 25 is a cured layer of the composition.
活性能量線硬化性組成物能夠為含有會藉由陽離子聚合而硬化之環氧系化合物作為硬化性成分之組成物，較佳是含有此種環氧系化合物作為硬化性成分之紫外 線硬化性組成物。所謂環氧系化合物係意味著在分子內具有平均1個以上、較佳為2個以上的環氧基之化合物。環氧系化合物可只有使用1種亦可併用2種以上。 The active energy ray-curable composition can be a composition containing an epoxy compound which is cured by cationic polymerization as a curable component, and is preferably an ultraviolet curable composition containing such an epoxy compound as a curable component. . The epoxy compound means a compound having an average of one or more, preferably two or more epoxy groups in the molecule. The epoxy compound may be used alone or in combination of two or more.
作為環氧系化合物可舉出：藉由使對芳香族多元醇的芳香環進行氫化反應而得到的脂環式多元醇，與表氯醇反應而得到之氫化環氧系化合物(具有脂環式環之多元醇的環氧丙基醚)；脂肪族多元醇或其環氧烷加成物的聚環氧丙基醚等脂肪族環氧系化合物；及在分子內具有1個以上之鍵結在脂環式環的環氧基之環氧系化合物亦即脂環式環氧系化合物等。 The epoxy-based compound is an alicyclic polyol obtained by hydrogenating an aromatic ring of an aromatic polyol, and a hydrogenated epoxy compound obtained by reacting with epichlorohydrin (having an alicyclic formula) a cyclopropyl ether of a cyclic polyol; an aliphatic epoxy compound such as a polyepoxypropyl ether of an aliphatic polyol or an alkylene oxide adduct thereof; and one or more bonds in a molecule An epoxy compound which is an epoxy group of an alicyclic ring, that is, an alicyclic epoxy compound.
活性能量線硬化性組成物係可含有自由基聚合性之(甲基)丙烯酸系化合物作為硬化性成分以代替上述環氧系化合物，或是含有該環氧系化合物與自由基聚合性之(甲基)丙烯酸系化合物作為硬化性成分。作為(甲基)丙烯酸系化合物能夠舉出：在分子內具有1個以上的(甲基)丙烯醯氧基之(甲基)丙烯酸酯單體；及能夠使2種以上的含官能基之化合物反應而得到之在分子內具有至少2個(甲基)丙烯醯氧基之(甲基)丙烯酸酯寡聚物等含(甲基)丙烯醯氧基之化合物。 The active energy ray-curable composition may contain a radically polymerizable (meth)acrylic compound as a curable component instead of the above epoxy compound, or may contain the epoxy compound and radical polymerizable (A) The acrylic compound is used as a curable component. Examples of the (meth)acrylic compound include a (meth) acrylate monomer having one or more (meth) acryloxy groups in the molecule; and two or more functional group-containing compounds. A (meth)acryloxy group-containing compound such as a (meth) acrylate oligomer having at least two (meth) acryloxy groups in the molecule obtained by the reaction.
活性能量線硬化性組成物係含有會藉由陽離子聚合而硬化之環氧系化合物作為硬化性成分時，以含有光陽離子聚合起始劑為佳。作為光陽離子聚合起始劑例如能夠舉出：芳香族重氮鎓鹽；芳香族碘鎓鹽、芳香族鋶鹽等的鎓鹽；鐵-芳烴錯合物等。 When the active energy ray-curable composition contains an epoxy compound which is cured by cationic polymerization as a curable component, it is preferred to contain a photocationic polymerization initiator. Examples of the photocationic polymerization initiator include aromatic diazonium salts; sulfonium salts such as aromatic iodonium salts and aromatic sulfonium salts; and iron-aromatic hydrocarbon complexes.
活性能量線硬化性組成物含有(甲基)丙烯酸系化合物等自由基聚合性成分時，以含有光自由基聚合起始劑為佳。作為光自由基聚合起始劑例如能夠舉出苯乙酮系起始劑、二苯基酮系起始劑、苯偶姻醚系起始劑、硫雜蒽酮系起始劑、氧雜蒽酮、茀酮、樟腦醌、苯甲醛、蒽醌等。 When the active energy ray-curable composition contains a radically polymerizable component such as a (meth)acrylic compound, it is preferred to contain a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include an acetophenone-based initiator, a diphenylketone-based initiator, a benzoin-ether initiator, a thioxanthone-based initiator, and xanthene. Ketone, fluorenone, camphorquinone, benzaldehyde, hydrazine and the like.
光學積層體亦可含有黏著劑層來代替第2硬化物層25。亦即，亦可隔著黏著劑層而將光學膜30貼合在第2熱塑性樹脂膜20。針對該黏著劑層係引用後述黏著劑層之記載。 The optical laminate may also contain an adhesive layer instead of the second cured layer 25. In other words, the optical film 30 may be bonded to the second thermoplastic resin film 20 via the adhesive layer. The description of the adhesive layer described later is cited for the adhesive layer.
藉由隔著第1硬化物層15而將第1熱塑性樹脂膜10層積接著在光學膜30的一面，而能夠得到第2圖顯示的構成之光學積層體，而且藉由隔著第2硬化物層25而將第2熱塑性樹脂膜20進一步層積接著在光學膜30的另一面，而能夠得到第3圖顯示的構成之光學積層體。 By laminating the first thermoplastic resin film 10 on one surface of the optical film 30 via the first cured material layer 15, the optical layered body having the structure shown in Fig. 2 can be obtained, and the second hardening layer can be obtained. In the object layer 25, the second thermoplastic resin film 20 is further laminated on the other surface of the optical film 30, whereby the optical layered body having the structure shown in Fig. 3 can be obtained.
製造具有第1熱塑性樹脂膜10及第2熱塑性樹脂膜20雙方之光學積層體時，該等薄膜可階段性地每次層積接著一面，亦可同時層積接著兩面的薄膜。 When an optical layered body having both the first thermoplastic resin film 10 and the second thermoplastic resin film 20 is produced, the films may be laminated one step at a time, or a film may be laminated on both sides.
作為使光學膜30與第1熱塑性樹脂膜10接著之方法，可舉出將硬化性組成物(S)塗佈在光學膜30及第1熱塑性樹脂膜10的貼合面之任一方或其雙方，將其層積在另一方的貼合面且使用例如貼合輥等從上下按壓而 貼合之方法。 As a method of adhering the optical film 30 and the first thermoplastic resin film 10, one or both of the bonding surfaces of the optical film 30 and the first thermoplastic resin film 10 may be applied to the curable composition (S). This method is laminated on the other bonding surface and pressed by pressing up and down using, for example, a bonding roller.
硬化性組成物(S)的塗佈係例如能夠利用刮刀片、線棒、模縫塗佈機、缺角輪塗佈機、凹版塗佈機等各種的塗佈方式。又，亦可為將光學膜30及第1熱塑性樹脂膜10以兩者的貼合面成為內側之方式連續地供給的情況下，使硬化性組成物(S)流延至其之間的方式。 The coating of the curable composition (S) can be carried out, for example, by various coating methods such as a doctor blade, a wire bar, a die coater, a notch coater, and a gravure coater. In addition, when the optical film 30 and the first thermoplastic resin film 10 are continuously supplied so that the bonding surfaces of both of them are inward, the curable composition (S) may be cast between them.
將光學膜30與第1熱塑性樹脂膜10貼合之後，係以對包含光學膜30、第1硬化物層15及第1熱塑性樹脂膜10之積層體施行加熱處理為佳。加熱處理的溫度係例如40℃以上且100℃以下，較佳為50℃以上且90℃以下。藉由加熱處理而能夠將在硬化性組成物層所含有的溶劑除去。而且，藉由該加熱處理而能夠使硬化性組成物進行硬化/交聯反應。 After the optical film 30 and the first thermoplastic resin film 10 are bonded together, it is preferable to heat-treat the layered body including the optical film 30, the first cured material layer 15, and the first thermoplastic resin film 10. The temperature of the heat treatment is, for example, 40 ° C or more and 100 ° C or less, preferably 50 ° C or more and 90 ° C or less. The solvent contained in the curable composition layer can be removed by heat treatment. Further, the curing composition can be subjected to a curing/crosslinking reaction by the heat treatment.
以上接著方法亦能夠應用在光學膜30與第2熱塑性樹脂膜20之接著。 The above method can also be applied to the optical film 30 and the second thermoplastic resin film 20.
使用活性能量線硬化性組成物作為構成第2硬化物層之硬化性組成物時，係視需要進行硬化性組成物層的乾燥後，照射活性能量線而使硬化性組成物層硬化。 When the active energy ray-curable composition is used as the curable composition constituting the second cured layer, the curable composition layer is dried, and then the active energy ray is irradiated to cure the curable composition layer.
照射活性能量線時所使用之光源只要是能夠產生紫外線、電子射線、X射線等者即可。特別適合使用在波長400nm以下具有發光分布之例如低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、化學燈、黑光燈、微波激發水銀燈、鹵化金屬燈等。 The light source used when the active energy ray is irradiated may be any one that can generate ultraviolet rays, electron rays, X-rays, or the like. Particularly suitable for use in a light-emitting distribution having a wavelength of 400 nm or less, for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, a black lamp, a microwave-excited mercury lamp, a halogenated metal lamp, or the like.
如第1圖顯示的在第1硬化物層15上不具 有第1熱塑性樹脂膜之光學積層體，係能夠藉由將硬化性組成物(S)塗佈在光學膜30的表面，而且對所得到的積層體例如使用熱風乾燥機施行80℃、300秒鐘的加熱處理而製造。又，製造由隔離膜/硬化性組成物(S)/光學膜30所構成之積層體製造之後，藉由將隔離膜剝離，隨後施行加熱處理亦能夠製造第1圖顯示之光學積層體。 The optical layered body having no first thermoplastic resin film on the first cured product layer 15 as shown in Fig. 1 can be applied to the surface of the optical film 30 by applying the curable composition (S). The obtained laminated body is produced, for example, by a heat treatment at 80 ° C for 300 seconds using a hot air dryer. Further, after the production of the laminate including the separator/curable composition (S)/optical film 30, the optical layered body shown in Fig. 1 can be produced by peeling off the separator and then performing heat treatment.
由硬化性組成物(S)所形成之第1硬化物層15的厚度係例如1nm以上且20μm以下，以5nm以上且10μm以下為佳，較佳為10nm以上且5μm以下，更佳為20nm以上且1μm以下。由上述眾所周知的水系組成物所形成的硬化物層亦能夠具有與此相同程度的厚度。 The thickness of the first cured material layer 15 formed of the curable composition (S) is, for example, 1 nm or more and 20 μm or less, preferably 5 nm or more and 10 μm or less, preferably 10 nm or more and 5 μm or less, and more preferably 20 nm or more. And 1 μm or less. The cured layer formed of the well-known water-based composition described above can also have the same thickness.
由活性能量線硬化性組成物所形成的硬化物層之厚度係例如10nm以上且20μm以下，以100nm以上且10μm以下為佳，較佳為500nm以上且5μm以下。 The thickness of the cured material layer formed of the active energy ray-curable composition is, for example, 10 nm or more and 20 μm or less, preferably 100 nm or more and 10 μm or less, and more preferably 500 nm or more and 5 μm or less.
第1硬化物層15與第2硬化物層25之厚度可為相同亦可為不同。 The thickness of the first cured layer 15 and the second cured layer 25 may be the same or different.
光學積層體係除了用以賦予需要的光學功能之光學膜30(例如偏光片)以外，亦能夠具備其它的光學功能性膜，其較佳的一個例子為相位差膜。 The optical layering system can have other optical functional films in addition to the optical film 30 (for example, a polarizer) for imparting a desired optical function, and a preferred example thereof is a retardation film.
如上述，第1熱塑性樹脂膜10及/或第2熱塑性樹脂膜20亦能夠充當相位差膜，但是該等薄膜亦能 夠另外地層積相位差膜。在後者的情況，相位差膜係能夠隔著黏著劑層或接著劑層而層積在第1熱塑性樹脂膜10、第2熱塑性樹脂膜20、第1硬化物層15及/或第2硬化物層25的外表面。針對相位差膜係引用上述[4]的記載。 As described above, the first thermoplastic resin film 10 and/or the second thermoplastic resin film 20 can also function as a retardation film, but these films can also additionally laminate a retardation film. In the latter case, the retardation film can be laminated on the first thermoplastic resin film 10, the second thermoplastic resin film 20, the first cured material layer 15, and/or the second cured product via the adhesive layer or the adhesive layer. The outer surface of layer 25. The description of the above [4] is cited for the retardation film system.
在偏光板等光學積層體所能夠含有之其它光學功能性膜(光學構件)的例子為聚光板、亮度提升膜、反射層(反射薄膜)、半穿透反射層(半穿透反射膜)、光擴散層(光擴散膜)等。 Examples of other optical functional films (optical members) that can be contained in an optical laminate such as a polarizing plate are a concentrating plate, a brightness enhancement film, a reflective layer (reflective film), and a semi-transmissive reflective layer (semi-transflective film). Light diffusion layer (light diffusion film) or the like.
聚光板係以光程控制等為目的而使用者，能夠為稜鏡陣列薄片、透鏡陣列薄片、附設斑點的薄片等。 The concentrating plate is intended for the purpose of optical path control or the like, and can be a 稜鏡 array sheet, a lens array sheet, a speckle-attached sheet, or the like.
亮度提升膜係以使應用偏光板等光學積層體的畫像顯示裝置之亮度提升為目的而使用者。具體而言，可舉出：將複數片之折射率的異向性互相不同之薄膜層積而設計成反射率產生異向性之反射型偏光分離薄片；及在基材薄膜上支撐膽固醇型液晶聚合物的配向薄膜或其配向液晶層而成之圓偏光分離薄片等。 The brightness enhancement film is intended to be used for the purpose of improving the brightness of an image display device using an optical layered body such as a polarizing plate. Specifically, a reflective polarizing separation sheet in which an anisotropy of reflectance is formed by laminating thin films in which the refractive indices of the plurality of sheets are different from each other is laminated, and cholesteric liquid crystal is supported on the base film. An alignment film of a polymer or a circularly polarizing separation sheet obtained by aligning the liquid crystal layer.
反射層、半穿透反射層、光擴散層係各自用以將偏光板設為反射型、半穿透型、擴散型光學構件而設置者。反射型偏光板係使用在使來自觀視側的入射光反射而顯示之類型的液晶顯示裝置，因為能夠省略背光板等的光源，所以容易使液晶顯示裝置薄型化。半穿透型偏光板係使用在亮處被作為反射型且在暗處使用來自背光板的光線顯示之類型的液晶顯示裝置。又，擴散型偏光板係使用在賦予光擴散性而抑制波紋(moire)等的顯示不良之液晶 顯示裝置。反射層、半穿透反射層及光擴散層係能夠使用眾所周知的方法而形成。 Each of the reflective layer, the semi-transmissive reflective layer, and the light-diffusing layer is provided to provide a polarizing plate as a reflective, semi-transmissive, or diffusing optical member. In the reflective polarizing plate, a liquid crystal display device of a type that reflects and reflects incident light from the viewing side is used. Since the light source such as a backlight can be omitted, the liquid crystal display device can be easily made thinner. The semi-transmissive polarizing plate is a liquid crystal display device of a type that is used as a reflection type in a bright place and a light display from a backlight in a dark place. Further, the diffusing type polarizing plate is a liquid crystal display device which is provided with light diffusion resistance and suppresses display defects such as moire. The reflective layer, the semi-transmissive reflective layer, and the light diffusing layer can be formed using well-known methods.
光學積層體係能夠含有黏著劑層。作為黏著劑層可舉出用以將光學積層體貼合在液晶單元、有機EL顯示元件等畫像顯示元件、或其它光學構件之黏著劑層。該黏著劑層係在第1圖及2顯示之構成的光學積層體中能夠層積在光學膜30的外表面，在第3圖顯示構成之光學積層體中能夠層積在第1熱塑性樹脂膜10或第2熱塑性樹脂膜20的外表面，在第4圖顯示構成之光學積層體中能夠層積在第1硬化物層15或第2熱塑性樹脂膜20的外表面，在第5圖顯示構成之光學積層體中能夠層積在第1硬化物層15或第2硬化物層25的外表面。 The optical laminate system can contain an adhesive layer. An adhesive layer for bonding an optical layered body to an image display element such as a liquid crystal cell or an organic EL display element or another optical member is exemplified as the pressure-sensitive adhesive layer. The adhesive layer can be laminated on the outer surface of the optical film 30 in the optical layered body having the structure shown in Figs. 1 and 2, and can be laminated on the first thermoplastic resin film in the optical layered body having the structure shown in Fig. 3 10 or the outer surface of the second thermoplastic resin film 20 can be laminated on the outer surface of the first cured material layer 15 or the second thermoplastic resin film 20 in the optical layered body shown in Fig. 4, and is shown in Fig. 5 The optical laminate can be laminated on the outer surface of the first cured layer 15 or the second cured layer 25.
將黏著劑層40層積在第3圖顯示構成之光學積層體的第2熱塑性樹脂膜20的外表面之例子，係顯示在第6圖。 The example in which the adhesive layer 40 is laminated on the outer surface of the second thermoplastic resin film 20 of the optical laminate which is shown in Fig. 3 is shown in Fig. 6.
作為在黏著劑層所使用的黏著劑能夠使用將(甲基)丙烯酸系樹脂、聚矽氧系樹脂、聚酯系樹脂、聚胺甲酸酯系樹脂、聚醚系樹脂等作為基質聚合物者。尤其是從透明性、黏著力、可靠性、耐候性、耐熱性、再加工性等的觀點而言，係以(甲基)丙烯酸系黏著劑為佳。 As the adhesive used for the adhesive layer, a (meth)acrylic resin, a polyoxynated resin, a polyester resin, a polyurethane resin, a polyether resin, or the like can be used as the matrix polymer. . In particular, a (meth)acrylic adhesive is preferred from the viewpoints of transparency, adhesion, reliability, weather resistance, heat resistance, reworkability and the like.
在(甲基)丙烯酸系黏著劑中，將具有甲基、乙基、正、異或第三丁基等碳數為20以下的烷基之(甲基)丙 烯酸烷酯、及(甲基)丙烯酸、(甲基)丙烯酸羥基乙酯等含官能基的(甲基)丙烯酸系單體，以使玻璃轉移溫度較佳成為25℃以下、更佳成為0℃以下之方式調配而成之重量平均分子量為10萬以上的(甲基)丙烯酸系樹脂適合用作為基質聚合物。 In the (meth)acrylic adhesive, an alkyl (meth)acrylate having an alkyl group having a carbon number of 20 or less, such as a methyl group, an ethyl group, a normal group, an iso- or a third butyl group, and (meth) A functional group-containing (meth)acrylic monomer such as acrylic acid or hydroxyethyl (meth)acrylate, which has a glass transition temperature of preferably 25 ° C or less, more preferably 0 ° C or less. A (meth)acrylic resin having a molecular weight of 100,000 or more is suitably used as a matrix polymer.
將黏著劑層形成在光學積層體係能夠藉由下列方式而進行：例如使黏著劑組成物溶解或分散在甲苯、乙酸乙酯等有機溶劑而調製黏著劑液，而且將該黏著劑液直接塗佈在光學積層體的對象面而形成黏著劑層之方式；及在已施行脫模處理之隔離膜上預先將黏著劑層形成為薄片狀，並將其轉移至光學積層體的對象面之方式等。 The formation of the adhesive layer in the optical layering system can be carried out by, for example, dissolving or dispersing the adhesive composition in an organic solvent such as toluene or ethyl acetate to prepare an adhesive liquid, and directly coating the adhesive liquid. a method of forming an adhesive layer on a target surface of an optical layered body; and a method of forming an adhesive layer into a sheet shape on the release film subjected to the release treatment and transferring the same to a target surface of the optical layered body; .
黏著劑層的厚度係按照其接著力等而決定，以1μm以上且50μm以下的範圍為佳，較佳為2μm以上且40μm以下。 The thickness of the pressure-sensitive adhesive layer is determined according to the adhesion force or the like, and is preferably 1 μm or more and 50 μm or less, and more preferably 2 μm or more and 40 μm or less.
光學積層體係能夠包含上述隔離膜。隔離膜能夠為由聚乙烯等聚乙烯系樹脂、聚丙烯等聚丙烯系樹脂、聚對苯二甲酸乙二酯等聚酯系樹脂等所構成之薄膜。尤其是以聚對苯二甲酸乙二酯的延伸膜為佳。 The optical layering system can include the above separator. The separator may be a film made of a polyethylene resin such as polyethylene, a polypropylene resin such as polypropylene, or a polyester resin such as polyethylene terephthalate. In particular, a stretch film of polyethylene terephthalate is preferred.
黏著劑層可視需要而含有由玻璃纖維、玻璃珠粒、樹脂珠粒、金屬粉、其它無機粉末所構成之填充劑、顏料、著色劑、抗氧化劑、紫外線吸收劑、抗靜電劑等。 The adhesive layer may contain a filler composed of glass fibers, glass beads, resin beads, metal powder, and other inorganic powders, a pigment, a colorant, an antioxidant, an ultraviolet absorber, an antistatic agent, and the like, as needed.
光學積層體係能夠含有用以保護其表面(典型上為第1 熱塑性樹脂膜10、第2熱塑性樹脂膜20、第1硬化物層15及/或第2硬化物層25的表面)的防護膜(protect film)。防護膜係例如將光學積層體貼合在畫像顯示元件或其它光學構件之後，連同其所具有的黏著劑層一起被剝離除去。 The optical layering system can include a protective film for protecting the surface (typically the surfaces of the first thermoplastic resin film 10, the second thermoplastic resin film 20, the first cured material layer 15, and/or the second cured layer 25). Protect film). The pellicle film is peeled off, for example, after the optical laminate is attached to the image display element or other optical member, together with the adhesive layer it has.
防護膜係例如由基材薄膜及層積在該基材薄上之黏著劑層所構成。針對黏著劑層係引用上述的記載。 The pellicle film is composed of, for example, a base film and an adhesive layer laminated on the base material. The above description is cited for the adhesive layer.
構成基材薄膜之樹脂係例如如聚乙烯的聚乙烯系樹脂、如聚丙烯的聚丙烯系樹脂、如聚對苯二甲酸乙二酯或聚萘二甲酸乙二酯的聚酯系樹脂、聚碳酸酯系樹脂等熱塑性樹脂。較佳為聚對苯二甲酸乙二酯等聚酯系樹脂。 The resin constituting the base film is, for example, a polyethylene-based resin such as polyethylene, a polypropylene-based resin such as polypropylene, a polyester-based resin such as polyethylene terephthalate or polyethylene naphthalate, and a poly A thermoplastic resin such as a carbonate resin. A polyester resin such as polyethylene terephthalate is preferred.
<畫像顯示裝置> <Portrait display device>
本發明之光學積層體係能夠應用在畫像顯示裝置。此時，畫像顯示裝置係包含光學積層體及畫像顯示元件。作為畫像顯示元件可舉出液晶單元、有機EL顯示元件等。就該等畫像顯示元件而言，能夠使用先前眾所周知者。 The optical layering system of the present invention can be applied to an image display device. In this case, the image display device includes an optical layered body and an image display element. Examples of the image display element include a liquid crystal cell, an organic EL display device, and the like. As for the image display elements, those previously known can be used.
將偏光板之光學積層體應用在液晶顯示裝置時，光學積層體可配置在液晶單元的背光側(背面側)，亦可配置在觀視側，亦可配置在該等背面側及觀視側雙方。將偏光板之光學積層體應用在有機EL顯示裝置時，光學積層體通常係配置在有機EL顯示元件的觀視側。 When the optical layered body of the polarizing plate is applied to a liquid crystal display device, the optical layered body may be disposed on the backlight side (back side) of the liquid crystal cell, or may be disposed on the viewing side, or may be disposed on the back side and the viewing side. both sides. When the optical layered body of the polarizing plate is applied to an organic EL display device, the optical layered body is usually disposed on the viewing side of the organic EL display element.
以下，揭示實施例而更具體地說明本發明，但是本發明係不被該等例限定。例中，表示含量或使用量 之%及份係只要未特別記載，就為質量基準。 Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited by the examples. In the examples, the % and the parts indicating the content or the amount used are based on mass unless otherwise specified.
在表1中，含唑啉基的聚合物(A)、鋅化合物(B)、具有羧基的化合物(C)、及促進含唑啉基的聚合物(A)的唑啉基與化合物(C)的羧基反應之化合物(D)，係各自簡記為(A)、(B)、(C)、(D)。 In Table 1, Oxazoline group polymer (A), zinc compound (B), compound having a carboxyl group (C), and promoting Oxazolinyl polymer (A) The compound (D) in which the oxazoline group reacts with the carboxyl group of the compound (C) is simply referred to as (A), (B), (C), and (D).
(製造例：偏光片的製造) (Manufacturing example: manufacture of polarizer)
將厚度60μm的聚乙烯醇薄膜(平均聚合度：約2,400、皂化度：99.9莫耳%以上)浸漬在30℃的純水之後，浸漬在碘/碘化鉀/水的質量比為0.02/2/100之30℃的水溶液中。隨後，浸漬在碘化鉀/硼酸/水的質量比為12/5/100之56.5℃的水溶液中。接著，使用8℃的純水洗淨之後，在65℃進行乾燥而得到碘吸附配向在聚乙烯醇薄膜之厚度23μm的偏光片。延伸主要是在碘染色及硼酸處理的步驟中進行，總延伸倍率為5.5倍。 A polyvinyl alcohol film having a thickness of 60 μm (average degree of polymerization: about 2,400, degree of saponification: 99.9 mol% or more) was immersed in pure water at 30° C., and the mass ratio of immersion in iodine/potassium iodide/water was 0.02/2/100. In an aqueous solution at 30 °C. Subsequently, it was immersed in an aqueous solution of potassium iodide/boric acid/water at a mass ratio of 5/5/100 of 56.5 °C. Subsequently, the mixture was washed with pure water at 8 ° C, and then dried at 65 ° C to obtain a polarizer having an iodine adsorption alignment of 23 μm in thickness of the polyvinyl alcohol film. The extension is mainly carried out in the steps of iodine dyeing and boric acid treatment, and the total stretching ratio is 5.5 times.
<實施例1至5、比較例1> <Examples 1 to 5, Comparative Example 1>
(1)硬化性組成物的調製 (1) Modulation of hardenable composition
將表1顯示之成分以表1顯示之調配量與作為溶劑的純水一起混合而調製硬化性組成物(接著劑水溶液)。表1顯示之各成分的調配量之單位為質量份，各成分的調配量為經固形物換算之量。在實施例1及實施例2中，所得到的硬化性組成物之(A)的濃度係設為7.0質量%，實施例3的硬化性組成物之(A)的濃度係設為6.0質量%，實施例4 的硬化性組成物之(A)的濃度係設為5.0質量%，實施例5的硬化性組成物之(A)的濃度係設為4.0質量%。在比較例1中，硬化性組成物之(X)的濃度係設為3.0質量%。 The components shown in Table 1 were mixed with pure water as a solvent in the amount shown in Table 1, and a curable composition (aqueous solution of an adhesive) was prepared. The unit of the amount of each component shown in Table 1 is a part by mass, and the amount of each component is an amount converted by solid matter. In Example 1 and Example 2, the concentration of (A) of the curable composition obtained was 7.0% by mass, and the concentration of (A) of the curable composition of Example 3 was 6.0% by mass. The concentration of the (A) of the curable composition of Example 4 was 5.0% by mass, and the concentration of (A) of the curable composition of Example 5 was 4.0% by mass. In Comparative Example 1, the concentration of (X) of the curable composition was 3.0% by mass.
(2)偏光板的製造 (2) Manufacturing of polarizing plate
對三乙酸纖維素(TAC)薄膜[Konica Minolta Opto(股)製的商品名「KC4UAW」、厚度：40μm]之一面施行皂化處理之後，將上述(1)調製的硬化性組成物使用棒式塗佈機而塗佈在該皂化處理面，同時對由環狀聚烯烴系樹脂所構成的零相位差膜[日本ZEON(股)製的商品名「ZEONOR」、厚度：23μm]之一面施行電暈處理，而且將上述(1)調製的硬化性組成物使用棒塗佈機而塗佈在該電暈處理面。以使硬化性組成物成為偏光片側之方式，將皂化處理完畢的TAC薄膜層積在偏光片的一面且將電暈處理完畢的零相位差膜層積在另一面，而得到具有零相位差膜/硬化性組成物層/偏光片/硬化性組成物層/TAC薄膜的層結構之積層體。藉由使用熱風乾燥機對該積層體進行80℃、300秒鐘的加熱處理，而製造具有零相位差膜/硬化物層/偏光片/硬化物層/TAC薄膜的層結構之偏光板。所製造的偏光板中之硬化物層厚度中每一層為20至60nm。 After saponification treatment was performed on one side of a cellulose triacetate (TAC) film [Konica Minolta Opto Co., Ltd., trade name "KC4UAW", thickness: 40 μm], the curable composition prepared in the above (1) was coated with a bar. A corona-treated surface is applied to the saponified surface, and a corona film made of a cyclic polyolefin resin (trade name "ZEONOR" manufactured by ZEON Co., Ltd., thickness: 23 μm] is used for corona. The curable composition prepared in the above (1) was applied to the corona-treated surface using a bar coater. The saponified TAC film was laminated on one surface of the polarizer and the corona-treated zero retardation film was laminated on the other side so that the curable composition became the polarizer side, thereby obtaining a film having a zero retardation film. / Laminate composition layer / polarizer / hardenable composition layer / layer structure of TAC film layer structure. The laminate was subjected to heat treatment at 80 ° C for 300 seconds by using a hot air dryer to produce a polarizing plate having a layer structure of a zero retardation film/cured layer/polarizer/cured layer/TAC film. Each of the layers of the cured layer in the manufactured polarizing plate has a thickness of 20 to 60 nm.
(3)光學耐久性(耐熱性)的評價 (3) Evaluation of optical durability (heat resistance)
(3-1)△Ty變化率的測定 (3-1) Determination of ΔTy change rate
將所得到的偏光板裁斷成為30mm×30mm的大小之後， 將零相位差膜側隔著(甲基)丙烯酸系黏著劑貼合在玻璃基板而得到測定試樣。測定試樣的層結構為玻璃基板/(甲基)丙烯酸系黏著劑層/零相位差膜/硬化物層/偏光片/硬化物層/TAC薄膜。玻璃基板係使用無鹼玻璃基板[Corning公司製的商品名「Eagle XG」]。 After the obtained polarizing plate was cut into a size of 30 mm × 30 mm, the zero retardation film was bonded to the glass substrate via a (meth)acrylic adhesive to obtain a measurement sample. The layer structure of the measurement sample was a glass substrate / (meth)acrylic adhesive layer / zero retardation film / cured layer / polarizer / cured layer / TAC film. As the glass substrate, an alkali-free glass substrate [trade name "Eagle XG" manufactured by Corning Co., Ltd.] was used.
針對所得到的測定試樣使用附積分球的分光光度計[日本分光(股)製的製品名「V7100」]而測定在波長380至780nm的範圍之MD穿透率與TD穿透率且算出在各波長之單體穿透率。針對所算出的單體穿透率，藉由JIS Z 8701：1999「顏色的表示方法-XYZ表色系及X10Y10Z10表色系」的2度區域(C光源)來進行發光因數校正且求取耐熱試驗前的發光因數校正單體穿透率Ty。又，測定試樣係將偏光板的TAC薄膜側作為偵測側且以使光從玻璃基板側入射之方式安裝在附積分球的分光光度計。 For the measurement sample to be obtained, the MD transmittance and the TD transmittance in the range of 380 to 780 nm were measured using a spectrophotometer with a integrating sphere [product name "V7100" manufactured by JASCO Corporation]. Monomer penetration at each wavelength. For the calculated monomer transmittance, the luminescence factor is performed by a 2 degree region (C light source) of JIS Z 8701:1999 "Color representation method - XYZ color system and X 10 Y 10 Z 10 color system" The luminescence factor before the heat resistance test was corrected and the monomer transmittance Ty was corrected. In addition, the measurement sample was attached to a spectrophotometer with an integrating sphere so that the TAC film side of the polarizing plate was used as the detection side and light was incident from the glass substrate side.
單體穿透率(%)係以下述式定義： 單體穿透率(λ)=(Tp(λ)+Tc(λ))/2。 The monomer permeability (%) is defined by the following formula: Monomer transmittance (λ) = (Tp(λ) + Tc(λ))/2.
Tp(λ)係在入射波長λ(nm)的直線偏光與平行偏光的關係下測定之測定試樣的穿透率(%)。 Tp (λ) is a transmittance (%) of a measurement sample measured in the relationship between linear polarization and parallel polarization at an incident wavelength λ (nm).
Tc(λ)係在入射波長λ(nm)的直線偏光與正交偏光的關係下測定之測定試樣的穿透率(%)。 Tc (λ) is a transmittance (%) of a measurement sample measured under the relationship between linear polarization of incident wavelength λ (nm) and orthogonal polarization.
其次，將該測定試樣在溫度105℃的乾燥環境下放置750小時之後，在溫度23℃、相對濕度50%RH的環境下放置24小時而提供耐熱試驗。耐熱試驗後，藉由與耐熱試驗前同樣的方法而求取發光因數校正單體穿透率 Ty。 Next, the measurement sample was allowed to stand in a dry environment at a temperature of 105 ° C for 750 hours, and then allowed to stand in an environment of a temperature of 23 ° C and a relative humidity of 50% RH for 24 hours to provide a heat resistance test. After the heat resistance test, the luminosity correction monomer transmittance Ty was determined by the same method as before the heat resistance test.
算出耐熱試驗後的發光因數校正單體穿透率Ty與耐熱試驗前的發光因數校正單體穿透率Ty之差的絕對值(|△Ty|)。 The absolute value (|ΔTy|) of the difference between the luminescence factor corrected monomer transmittance Ty after the heat resistance test and the luminescence factor corrected monomer transmittance Ty before the heat resistance test was calculated.
其次，從所得到的|△Ty|之值，根據下述式而求取以比較例1的|△Ty|為基準之各例的「△Ty變化率」(%)。將△Ty變化率的算出值顯示在表1。△Ty變化率越大時，具有越優異的耐熱性。 Then, from the value of |ΔTy| obtained, the "ΔTy change rate" (%) of each example based on |ΔTy| of Comparative Example 1 was obtained by the following formula. The calculated value of the ΔTy change rate is shown in Table 1. When the ΔTy change rate is larger, the heat resistance is more excellent.
各例的△Ty變化率(%)=|{(各例的|△Ty|)-(比較例1的|△Ty|)}|/(比較例1的|△Ty|) ΔTy change rate (%) of each example=|{(|ΔTy| of each example)-(|ΔTy| of Comparative Example 1)||/(|ΔTy| of Comparative Example 1)
又，在任一實施例及比較例中，△Ty均顯示負值。 Further, in any of the examples and the comparative examples, ΔTy showed a negative value.
(3-2)△ab變化率的測定 (3-2) Determination of Δab change rate
將所得到的偏光板裁斷成為30mm×30mm的大小之後，將零相位差膜側隔著(甲基)丙烯酸系黏著劑而貼合在玻璃基板以得到測定試樣。測定試樣的層結構為玻璃基板/(甲基)丙烯酸系黏著劑層/零相位差膜/硬化物層/偏光片/硬化物層/TAC薄膜。玻璃基板係使用無鹼玻璃基板[Corning公司製的商品名「Eagle XG」]。 After the obtained polarizing plate was cut into a size of 30 mm × 30 mm, the zero retardation film was bonded to the glass substrate via a (meth)acrylic adhesive to obtain a measurement sample. The layer structure of the measurement sample was a glass substrate / (meth)acrylic adhesive layer / zero retardation film / cured layer / polarizer / cured layer / TAC film. As the glass substrate, an alkali-free glass substrate [trade name "Eagle XG" manufactured by Corning Co., Ltd.] was used.
針對所得到的測定試樣，使用附積分球的分光光度計[日本分光(股)製的製品名「V7100」]而測定在波長380至780nm的範圍之MD穿透率及TD穿透率且算出 在各波長之單體穿透率。使用所算出的單體穿透率，針對穿透色相的a值及b值算出根據CIE(國際照明委員會)所規定的Lab表色系的穿透色相的a值及b值。 With respect to the obtained measurement sample, the MD transmittance and the TD transmittance in the range of 380 to 780 nm were measured using a spectrophotometer with an integrating sphere [product name "V7100" manufactured by JASCO Corporation]. The monomer transmittance at each wavelength was calculated. Using the calculated monomer transmittance, the a value and the b value of the penetrating hue of the Lab color system defined by CIE (International Commission on Illumination) were calculated for the a value and the b value of the penetrating hue.
其次，將該測定試樣在溫度105℃的乾燥環境下放置750小時後，在溫度23℃、相對濕度50%RH的環境下放置24小時而提供耐熱試驗。耐熱試驗後，係使用與耐熱試驗前同樣的方法而求取穿透色相的a值及b值。使用所測得之耐久前後的a值及b值且依照下述式而計算藉由耐熱試驗得到之色相變化的指標之△ab值的絕對值(|△ab|)。 Next, the measurement sample was allowed to stand in a dry environment at a temperature of 105 ° C for 750 hours, and then allowed to stand in an environment of a temperature of 23 ° C and a relative humidity of 50% RH for 24 hours to provide a heat resistance test. After the heat resistance test, the a value and the b value of the penetrating hue were obtained by the same method as before the heat resistance test. The absolute value (|Δab|) of the Δab value of the index of the hue change obtained by the heat resistance test was calculated using the measured a value and the b value before and after the endurance.
|△ab|=|{(a(耐久試驗後)-a(耐久試驗前))2+(b(耐久試驗後)-b(耐久試驗前))2}1/2| |△ab|=|{(a (after endurance test)-a (before endurance test)) 2 + (b (after endurance test)-b (before endurance test)) 2 } 1/2 |
其次，從所得到的|△ab|之值，根據下述式而求取以比較例1的|△ab為基準之各例的「△ab變化率」(%)。將△ab變化率的算出值顯示在表1。△ab變化率越大時，具有越優異的耐熱性。 Next, from the value of |Δab| obtained, the "Δab change rate" (%) of each example based on |Δab of Comparative Example 1 was obtained from the following formula. The calculated value of the Δab change rate is shown in Table 1. When the rate of change of Δab is larger, the heat resistance is more excellent.
各例的△ab變化率(%)=100×|{(各例的|△ab|)-(比較例1的|△ab|)}|/(比較例1的|△ab|) Δab change rate (%) of each example = 100 × | { (|Δab| of each case) - (|Δab| of Comparative Example 1)|/(|Δab| of Comparative Example 1)
又，在任一實施例及比較例中，△ab均顯示正值。 Further, in any of the examples and comparative examples, Δab showed a positive value.
表1顯示之各成分的詳細資料係如以下。 The details of each component shown in Table 1 are as follows.
a1：日本觸媒股份有限公司製的商品名「EPOCROSS WS-300」[具有2-唑啉基作為側鏈之含唑啉基的丙烯酸系聚合物的水溶液、固形物濃度：10質量%、唑啉價(理論值)：130g solid/eq.、唑啉基量(理論值)：7.7mmol/g,solid、數量平均分子量：4×104、重量平均分子量：12×104)] A1: The product name "EPOCROSS WS-300" manufactured by Nippon Shokubai Co., Ltd. [with 2- Oxazolinyl as a side chain Aqueous solution and solid content of the oxazoline-based acrylic polymer: 10% by mass, Oxazoline valence (theoretical value): 130 g solid/eq., Amount of oxazoline group (theoretical value): 7.7 mmol/g, solid, number average molecular weight: 4 × 10 4 , weight average molecular weight: 12 × 10 4 )]
b1：氯化鋅(ZnCl2) B1: zinc chloride (ZnCl 2 )
b2：碘化鋅(ZnI2) B2: zinc iodide (ZnI 2 )
c1：檸檬酸 C1: citric acid
d1：硫酸 D1: sulfuric acid
x1：日本合成化學工業股份公司製之商品名「Gohsefimer Z-200」[乙醯乙醯基改性聚乙烯醇、平均聚合度：1100、皂化度：98.5莫耳%以上] X1: The product name "Gohsefimer Z-200" manufactured by Nippon Synthetic Chemical Industry Co., Ltd. [Ethyl acetate-modified polyvinyl alcohol, average polymerization degree: 1100, saponification degree: 98.5 mol% or more]
y1：乙二醛 Y1: glyoxal
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