TWI672338B - Active energy ray-curable composition and laminate using the same - Google Patents
Active energy ray-curable composition and laminate using the same Download PDFInfo
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- TWI672338B TWI672338B TW107116506A TW107116506A TWI672338B TW I672338 B TWI672338 B TW I672338B TW 107116506 A TW107116506 A TW 107116506A TW 107116506 A TW107116506 A TW 107116506A TW I672338 B TWI672338 B TW I672338B
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Abstract
本發明提供一種用以形成折射率匹配層的活性能量線硬化性組成物,所述折射率匹配層即便過量地照射活性能量線,透明性與耐擦傷性也良好,且可保持相對於基材及透明導電層的黏接性。一種活性能量線硬化性組成物,其包含金屬氧化物,且用以形成在基材上具有折射率匹配層及透明導電層的層疊體中的折射率匹配層,所述活性能量線硬化性組成物的特徵在於滿足以下(1)~(4)。The present invention provides an active energy ray-curable composition for forming a refractive index matching layer. Even if the refractive index matching layer is excessively irradiated with active energy rays, the transparency and scratch resistance are good, and it can be maintained relative to the substrate. And the adhesion of the transparent conductive layer. An active energy ray hardening composition comprising a metal oxide and used to form a refractive index matching layer in a laminate having a refractive index matching layer and a transparent conductive layer on a substrate, the active energy ray hardening composition Objects are characterized by satisfying the following (1) to (4).
Description
本發明是有關於一種活性能量線硬化性組成物及使用其的層疊體。The present invention relates to an active energy ray-curable composition and a laminate using the same.
以前,在觸控螢幕(touch panel)用途等中使用在聚酯等基材上設置有透明導電層的透明導電性的層疊體。透明導電層通常使用銦錫氧化物(Indium Tin Oxide,ITO)等金屬氧化物的薄膜,利用濺鍍法或真空蒸鍍法而層疊於基材上。 作為觸控螢幕的動作方式,電阻膜式為主流,但近年來,靜電電容式急速擴大。電阻膜式觸控螢幕中使用的具有透明導電性的層疊體通常包括未經圖案化的透明導電層。另一方面,靜電電容式觸控螢幕中通常使用層疊有經圖案化的透明導電層的透明導電性的層疊體。Conventionally, a transparent conductive laminate in which a transparent conductive layer is provided on a substrate such as polyester is used for touch panel applications and the like. The transparent conductive layer is generally a thin film of a metal oxide such as indium tin oxide (ITO), and is laminated on a substrate by a sputtering method or a vacuum evaporation method. As the operation method of the touch screen, the resistance film type is the mainstream, but in recent years, the capacitance type has been rapidly expanded. A transparent conductive laminate used in a resistive film touch screen usually includes an unpatterned transparent conductive layer. On the other hand, in a capacitive touch screen, a transparent conductive laminate in which a patterned transparent conductive layer is laminated is generally used.
靜電電容式觸控螢幕中使用的具有透明導電性的層疊體通常利用照相平版蝕刻(photolithoetching)等對透明導電層進行圖案化,俯視時存在透明導電層的圖案部與非圖案部。在如上所述的使用透明導電層經圖案化的具有透明導電性的層疊體的靜電電容式觸控螢幕中,透明導電層的圖案部可見的所謂「透視」的現象成為問題,使作為顯示裝置的品質下降。 例如專利文獻1、專利文獻2等中提出了抑制透明導電層圖案的透視。另外,專利文獻3中提出了一種當製造大量的具有透明導電性的層疊體時具有透明性及相對於大量的活性能量線照射也可耐受的黏接性、與透明導電性的層疊體。進而,專利文獻4中提出了一種內部應力及硬化收縮得到改善的折射率匹配(index matching)層疊體。A transparent conductive laminate used in an electrostatic capacitance type touch screen is usually patterned by photolithoetching or the like. There are patterned portions and non-patterned portions of the transparent conductive layer in a plan view. In a capacitive touch screen using a transparent conductive layered patterned transparent conductive layered body as described above, the phenomenon of so-called "see-through" in which the pattern portion of the transparent conductive layer is visible becomes a problem, making it a display device. The quality is degraded. For example, Patent Literature 1, Patent Literature 2, and the like propose to suppress the see-through of the transparent conductive layer pattern. In addition, Patent Document 3 proposes a laminated body that has transparency and adhesiveness that is resistant to a large amount of active energy ray irradiation and transparent conductivity when a large number of laminated bodies having transparent conductivity are produced. Furthermore, Patent Document 4 proposes an index matching laminated body having improved internal stress and hardening shrinkage.
近年來,根據層疊體的用途而有時在基材的單面或兩面上施以多層化,在所述各層的形成時或透明導電層的圖案化時會照射大量的活性能量線。所述情況下,在專利文獻1或專利文獻2的技術中,雖顯現出抑制透明導電層圖案的透視的效果,但在折射率匹配層接受到大量的活性能量線的情況下,存在與基材的黏接性下降的課題。另外,如果為了確保基材與折射率匹配層的黏接性而欲以活性能量線的累計光量不成為大量的方式設計層構成,則產生層疊體的層構成受到限定的問題。再者,在專利文獻3的技術中,公開了一種當製造具有透明導電性的層疊體時具有透明性及相對於大量的活性能量線照射也可耐受的黏接性、與透明導電性的層疊體。但要求黏接性的進一步提高。 [現有技術文獻]In recent years, depending on the application of the laminate, multilayering may be performed on one or both sides of the substrate, and a large amount of active energy rays may be irradiated during the formation of the respective layers or the patterning of the transparent conductive layer. In this case, although the technology of Patent Document 1 or Patent Document 2 exhibits the effect of suppressing the see-through of the transparent conductive layer pattern, when the refractive index matching layer receives a large amount of active energy rays, there is a problem with the base. The problem of lowering the adhesiveness of wood. In addition, if the layer structure is designed so that the accumulated light amount of the active energy rays does not become large in order to ensure the adhesion between the substrate and the refractive index matching layer, a problem arises that the layer structure of the laminate is limited. In addition, the technology of Patent Document 3 discloses a transparent conductive material and a transparent conductive material which has transparency and resistance to a large amount of active energy ray irradiation when it is produced, Laminated body. However, further improvement in adhesion is required. [Prior Art Literature]
[專利文獻] [專利文獻1] 日本專利特開2011-084075號公報 [專利文獻2]:國際公開WO2012/176481號公報 [專利文獻3]:日本專利特開2017-35816號公報 [專利文獻4]:日本專利特開2014-209333號公報[Patent Literature] [Patent Literature 1] Japanese Patent Laid-Open No. 2011-084075 [Patent Literature 2]: International Publication WO2012 / 176481 [Patent Literature 3]: Japanese Patent Laid-Open Publication No. 2017-35816 [Patent Literature 4] ]: Japanese Patent Laid-Open No. 2014-209333
[發明所要解決的問題] 本發明提供一種用以形成折射率匹配層的活性能量線硬化性組成物,無論活性能量線的照射量如何,所述折射率匹配層的透明性及耐擦傷性均良好,且可保持相對於基材及透明導電層的黏接性。 [解決問題的技術手段][Problems to be Solved by the Invention] The present invention provides an active energy ray-curable composition for forming a refractive index matching layer. Regardless of the amount of active energy ray exposure, the transparency and scratch resistance of the refractive index matching layer are both. Good, and can maintain the adhesion to the substrate and the transparent conductive layer. [Technical means to solve the problem]
本發明者對上述課題反覆進行了努力研究,結果發現通過使用以下所記載的活性能量線硬化性組成物來解決所述課題,從而完成了本發明。The present inventors have intensively studied the above problems, and as a result, have found that the problems are solved by using an active energy ray-curable composition described below, and the present invention has been completed.
即,本發明的一實施形態是有關於一種活性能量線硬化性組成物,其包含金屬氧化物,且用以形成在基材上依序具有折射率匹配層及透明導電層的層疊體中的折射率匹配層,所述活性能量線硬化性組成物的特徵在於滿足以下(1)~(4)。 (1)金屬氧化物的平均粒徑為4 nm~200 nm,且以95/5~40/60的質量比含有氧化鋯與氧化鈦及/或氧化鋅。 (2)在活性能量線硬化性組成物的固體成分100質量%中,含有10質量%~80質量%的分子量未滿700的季戊四醇丙烯酸酯系化合物。 (3)含有具有6個以上的(甲基)丙烯醯基且質量平均分子量為700~10000的丙烯酸酯樹脂,且所述丙烯酸酯樹脂為聚酯丙烯酸酯及/或胺基甲酸酯丙烯酸酯; (4)所述丙烯酸酯樹脂與所述季戊四醇丙烯酸酯系化合物的質量比為80/20~50/50。That is, one embodiment of the present invention relates to an active energy ray-curable composition that includes a metal oxide and is used to form a laminate having a refractive index matching layer and a transparent conductive layer in this order on a substrate. The refractive index matching layer is characterized in that the active energy ray-curable composition satisfies the following (1) to (4). (1) The average particle diameter of the metal oxide is 4 nm to 200 nm, and zirconium oxide and titanium oxide and / or zinc oxide are contained in a mass ratio of 95/5 to 40/60. (2) 100% by mass of the solid content of the active energy ray-curable composition contains 10 to 80% by mass of a pentaerythritol acrylate-based compound having a molecular weight of less than 700. (3) an acrylate resin containing 6 or more (meth) acryl fluorene groups and a mass average molecular weight of 700 to 10,000, and the acrylate resin is a polyester acrylate and / or a urethane acrylate (4) A mass ratio of the acrylate resin to the pentaerythritol acrylate compound is 80/20 to 50/50.
另外,在本發明的一實施形態中,氧化鈦及/或氧化鋅的比表面積可為20 m2 /g~160 m2 /g。Moreover, in one embodiment of the present invention, the specific surface area of the titanium oxide and / or zinc oxide may be 20 m 2 / g to 160 m 2 / g.
另外,在本發明的一實施形態中,照射6500 mJ/cm2 的活性能量線後的所述層疊體的利用依據日本工業標準(Japanese Industrial Standards,JIS)K5600-5-6的黏接試驗而測定的所述折射率匹配層相對於所述基材的黏接性可為剝離面積未滿15%。In addition, in an embodiment of the present invention, the use of the laminated body after irradiating an active energy ray of 6500 mJ / cm 2 is used in accordance with an adhesion test according to Japanese Industrial Standards (JIS) K5600-5-6. The measured adhesion of the refractive index matching layer to the substrate may be less than 15% of a peeling area.
另外,本發明的一實施形態還可含有具有6個以上的(甲基)丙烯醯基且質量平均分子量為700~10000的丙烯酸酯樹脂(其中所述季戊四醇丙烯酸酯系化合物除外)。An embodiment of the present invention may further include an acrylate resin (excluding the pentaerythritol acrylate-based compound) having 6 or more (meth) acrylfluorenyl groups and having a mass average molecular weight of 700 to 10,000.
另外,本發明的另一實施形態是有關於一種層疊體,其在基材上依序具有作為所述活性能量線硬化性組成物的硬化物的折射率匹配層、及透明導電層。 [發明的效果]Moreover, another embodiment of this invention is related with the laminated body which has a refractive index matching layer as a hardened | cured material of the said active-energy-ray-curable composition, and a transparent conductive layer in order on a base material. [Effect of the invention]
根據本發明,可提供一種用以形成折射率匹配層的活性能量線硬化性組成物,無論活性能量線的照射量如何,所述折射率匹配層的透明性及耐擦傷性均良好,且可保持相對於基材及透明導電層的黏接性。According to the present invention, there can be provided an active energy ray-curable composition for forming a refractive index matching layer. Regardless of the amount of active energy ray exposure, the refractive index matching layer has good transparency and scratch resistance, and can Maintains adhesion to the substrate and transparent conductive layer.
以下對本發明的實施形態進行詳細說明,但以下所記載的構成要件的說明為本發明的實施方式的一例(代表例),本發明只要不超出其主旨則不限定於這些內容。Hereinafter, the embodiment of the present invention will be described in detail. However, the description of the constituent elements described below is an example (representative example) of the embodiment of the present invention, and the present invention is not limited to these contents as long as it does not exceed the gist thereof.
以下,對構成本發明的各要素進行詳細說明。Hereinafter, each element which comprises this invention is demonstrated in detail.
本發明的一實施形態為一種活性能量線硬化性組成物,其包含金屬氧化物,且用以形成在基材上依序具有折射率匹配層及透明導電層的層疊體中的折射率匹配層,所述活性能量線硬化性組成物的特徵在於滿足以下(1)及(2)。 (1)金屬氧化物的平均粒徑為4 nm~200 nm,且以99/1~30/70的質量比含有氧化鋯與氧化鈦及/或氧化鋅。 (2)在活性能量線硬化性組成物的固體成分100質量%中,含有10質量%~80質量%的季戊四醇丙烯酸酯系化合物。An embodiment of the present invention is an active energy ray-curable composition that includes a metal oxide and is used to form a refractive index matching layer in a laminate having a refractive index matching layer and a transparent conductive layer in this order on a substrate. The active energy ray-curable composition is characterized by satisfying the following (1) and (2). (1) The average particle diameter of the metal oxide is 4 nm to 200 nm, and zirconium oxide and titanium oxide and / or zinc oxide are contained in a mass ratio of 99/1 to 30/70. (2) A pentaerythritol acrylate-based compound is contained in 100% by mass of the solid content of the active energy ray-curable composition, in an amount of 10% by mass to 80% by mass.
<基材> 作為本發明的基材,可列舉但並不限定於:聚酯膜、三乙醯基纖維素膜、聚烯烴膜、環烯烴系膜、丙烯酸系膜、聚碳酸酯系膜等。特別較佳為使用聚酯膜、其中的聚對苯二甲酸乙二酯(polyethylene terephthalate,PET)膜。所述基材的厚度根據所期望的用途適宜地選擇即可,適當為20 μm至300 μm的範圍,較佳為50 μm至250 μm的範圍,更較佳為50 μm至200 μm的範圍。<Substrate> Examples of the substrate of the present invention include, but are not limited to, polyester films, triethylfluorene-based cellulose films, polyolefin films, cycloolefin-based films, acrylic films, polycarbonate-based films, and the like. . It is particularly preferable to use a polyester film and a polyethylene terephthalate (PET) film among them. The thickness of the substrate may be appropriately selected according to the intended use, and is suitably in a range of 20 μm to 300 μm, preferably in a range of 50 μm to 250 μm, and more preferably in a range of 50 μm to 200 μm.
另外,就大大有助於依序具有基材、折射率匹配層、透明導電層的層疊體全體中的可見性的方面而言,基材的折射率較佳為1.45~1.75,更較佳為1.45~1.70。The refractive index of the base material is preferably from 1.45 to 1.75, and more preferably from the viewpoint of greatly contributing to the visibility of the entire laminated body having the base material, the refractive index matching layer, and the transparent conductive layer in this order. 1.45 to 1.70.
所述基材可在其表面進一步具有包含有機物及/或無機物的層,作為其具體例,可列舉用以提高與其他層的黏接性的易黏接層,但並不限定於此。作為易黏接層,可列舉電暈放電處理、紫外線(UV)-臭氧處理、電漿處理、底塗(primer)處理等所形成的各種層,也可經組合處理。其中,特別較佳為經底塗處理或電暈放電處理的基材,更較佳為經底塗處理的基材。The substrate may further include a layer including an organic substance and / or an inorganic substance on a surface thereof. As a specific example thereof, an easily-adhesive layer for improving adhesion with other layers may be mentioned, but is not limited thereto. Examples of the easily-adhesive layer include various layers formed by a corona discharge treatment, an ultraviolet (UV) -ozone treatment, a plasma treatment, a primer treatment, or the like, or a combination treatment. Among them, a substrate treated with a primer or a corona discharge is particularly preferred, and a substrate treated with a primer is more preferred.
<折射率匹配層> 本發明中,所謂「折射率匹配層」是指形成觸控螢幕等顯示裝置中所使用的層疊體的層,且是為了減小基材上的具有透明導電層的部分與不具有透明導電層的部分的光學特性的差而設置於PET膜等基材與透明導電層之間的層。再者,雖並不限定於以下所述,但折射率匹配層的膜厚較佳為0.02 μm~30 μm,折射率較佳為1.4~2.0。<Refractive index matching layer> In the present invention, the "refractive index matching layer" refers to a layer that forms a laminate used in a display device such as a touch screen, and is intended to reduce a portion having a transparent conductive layer on a substrate. A layer provided between a base material such as a PET film and the transparent conductive layer with a difference in optical characteristics from a portion having no transparent conductive layer. Although not limited to the following, the film thickness of the refractive index matching layer is preferably 0.02 μm to 30 μm, and the refractive index is preferably 1.4 to 2.0.
<活性能量線硬化性組成物> 另外,以下對本發明的用以形成折射率匹配層的活性能量線硬化性組成物進行說明。<Active-energy-ray-curable composition> Hereinafter, the active-energy-ray-curable composition of the present invention for forming a refractive index matching layer will be described.
所謂活性能量線硬化性組成物,是指含有通過紫外線或電子束等活性能量線的照射而經由交聯反應等進行硬化的樹脂成分的組成物。在活性能量線硬化性組成物的塗敷後,通過照射活性能量線來加以硬化而形成折射率匹配層。作為所述樹脂,可列舉紫外線硬化性樹脂或電子束硬化性樹脂等作為代表物,就機械膜強度(耐擦傷性、鉛筆硬度)優異的方面而言,較佳為通過紫外線照射而硬化的樹脂,例如可列舉季戊四醇丙烯酸酯系化合物等具有丙烯酸酯基的化合物,但並不限定於此。The active energy ray-curable composition refers to a composition containing a resin component that is hardened by irradiation of an active energy ray such as ultraviolet rays or electron beams through a crosslinking reaction or the like. After the application of the active energy ray-curable composition, the active energy ray is irradiated to harden to form a refractive index matching layer. Examples of the resin include ultraviolet curable resins and electron beam curable resins. Representative resins are preferable in terms of excellent mechanical film strength (scratch resistance, pencil hardness), and are cured by ultraviolet radiation. Examples include compounds having an acrylate group, such as pentaerythritol acrylate-based compounds, but are not limited thereto.
<金屬氧化物> 本發明的活性能量線硬化性組成物中所含的金屬氧化物的平均粒徑為4 nm~200 nm,如果為所述範圍,則折射率匹配層的透明性優異。更較佳為10 nm~100 nm。本說明書中,所謂金屬氧化物的平均粒徑,表示分散於組成物中的狀態下的平均粒徑,且為利用動態光散射法而測定的粒度分佈中的D50值。動態光散射測定例如可使用日機裝(股)公司製造的「納奇克(Nanotrac)UPA」等來測定。<Metal Oxide> The average particle diameter of the metal oxide contained in the active energy ray-curable composition of the present invention is 4 nm to 200 nm, and if it is within the above range, the transparency of the refractive index matching layer is excellent. It is more preferably 10 nm to 100 nm. In this specification, the average particle diameter of a metal oxide means the average particle diameter in the state dispersed in a composition, and is a D50 value in the particle size distribution measured by the dynamic light scattering method. The dynamic light scattering measurement can be performed using, for example, "Nanotrac UPA" manufactured by Nikkiso Co., Ltd. and the like.
另外,氧化鋯與氧化鈦及/或氧化鋅的平均粒徑的比例較佳為1.0:0.3~1.0:1.8,更較佳為1.0:0.5~1.0:1.5。在使用氧化鈦與氧化鋅兩者的情況下,較佳為各自的平均粒徑與氧化鋯的平均粒徑的比例為所述範圍內。The ratio of the average particle diameter of zirconia to titanium oxide and / or zinc oxide is preferably 1.0: 0.3 to 1.0: 1.8, and more preferably 1.0: 0.5 to 1.0: 1.5. When both titanium oxide and zinc oxide are used, it is preferable that the ratio of each average particle diameter to the average particle diameter of a zirconia is in the said range.
關於氧化鋯與氧化鈦及/或氧化鋅的質量比,為了有效地遮斷紫外線等活性能量線,較佳為以99/1~30/70的質量比而含有氧化鋯/氧化鈦・氧化鋅。更較佳為95/5~40/60。另外,在活性能量線硬化性組成物的固體成分100質量%中,較佳為含有合計為10質量%~80質量%的氧化鋯與氧化鈦及/或氧化鋅。Regarding the mass ratio of zirconia to titanium oxide and / or zinc oxide, in order to effectively block active energy rays such as ultraviolet rays, it is preferable to contain zirconia / titanium oxide / zinc oxide at a mass ratio of 99/1 to 30/70. . It is more preferably 95/5 to 40/60. In addition, the solid content of the active energy ray-curable composition is preferably 100% by mass, and preferably contains zirconia, titanium oxide, and / or zinc oxide in a total amount of 10% to 80% by mass.
另外,所述金屬氧化物的一次粒徑較佳為4 nm~200 nm。如果為所述範圍,則可更有效地遮斷紫外線等活性能量線。氧化鋯與氧化鈦及/或氧化鋅的一次粒徑的比例較佳為1.0:10~1.0:0.3,更較佳為1.0:5~1.0:0.4。在使用氧化鈦與氧化鋅兩者的情況下,較佳為各自的一次粒徑與氧化鋯的一次粒徑的比例為所述範圍內。The primary particle diameter of the metal oxide is preferably 4 nm to 200 nm. Within this range, active energy rays such as ultraviolet rays can be blocked more effectively. The ratio of the primary particle diameter of zirconia to titanium oxide and / or zinc oxide is preferably 1.0: 10 to 1.0: 0.3, and more preferably 1.0: 5 to 1.0: 0.4. When both titanium oxide and zinc oxide are used, it is preferable that the ratio of each primary particle diameter to the primary particle diameter of a zirconia is in the said range.
本說明書中,所謂金屬氧化物的一次粒徑,是指通過使用穿透型電子顯微鏡進行測定而獲得的值,且較佳為取5點以上的測定值的平均值。In the present specification, the primary particle diameter of the metal oxide refers to a value obtained by measurement using a transmission electron microscope, and it is preferable to take an average of the measured values of 5 points or more.
也可利用有機物或無機物對所述金屬氧化物的表面進行處理。氧化鈦較佳為金紅石(rutile)型結晶,氧化鋅較佳為六方晶。 再者,金屬氧化物的粒子形狀並無特別限定,例如為球狀、中空狀、多孔質狀、棒狀、板狀、纖維狀或無規形狀,較佳為球狀。The surface of the metal oxide may be treated with an organic substance or an inorganic substance. Titanium oxide is preferably a rutile crystal, and zinc oxide is preferably a hexagonal crystal. The particle shape of the metal oxide is not particularly limited, and is, for example, spherical, hollow, porous, rod-like, plate-like, fibrous, or random, and preferably spherical.
所述氧化鈦及氧化鋅的比表面積較佳為20 m2 /g~160 m2 /g,更較佳為30 m2 /g~150 m2 /g。比表面積可利用JIS Z 8830:2001中記載的測定方法來測定。如果比表面積為所述範圍,則折射率匹配層的透明性變得良好,進而,即便在以累計光量計而大量照射活性能量線的情況下,也可良好地維持與基材的黏接性。The specific surface area of the titanium oxide and zinc oxide is preferably 20 m 2 / g to 160 m 2 / g, and more preferably 30 m 2 / g to 150 m 2 / g. The specific surface area can be measured by a measurement method described in JIS Z 8830: 2001. When the specific surface area is within the above range, the transparency of the refractive index matching layer becomes good, and even when the active energy ray is irradiated in a large amount as a cumulative light amount, the adhesion to the substrate can be maintained well. .
本發明中,金屬氧化物較佳為氧化鋯與氧化鈦的組合。In the present invention, the metal oxide is preferably a combination of zirconia and titanium oxide.
所述氧化鈦及氧化鋅的真密度較佳為3~6.5。另外,體積密度較佳為0.20 g/cm3 ~0.40 g/cm3 。The true density of the titanium oxide and zinc oxide is preferably 3 to 6.5. The bulk density is preferably 0.20 g / cm 3 to 0.40 g / cm 3 .
在以下的說明中,所謂(甲基)丙烯酸酯是指甲基丙烯酸酯與丙烯酸酯的合稱,所謂(甲基)丙烯酸是指甲基丙烯酸與丙烯酸的合稱。In the following description, (meth) acrylate refers to a collective name of methacrylate and acrylate, and (meth) acrylic acid refers to a collective name of methacrylic acid and acrylic acid.
<季戊四醇丙烯酸酯系化合物> 本發明的活性能量線硬化性組成物在固體成分100質量%中含有10質量%~80質量%的季戊四醇丙烯酸酯系化合物。較佳為20質量%~70質量%。另外,較佳為以所述金屬氧化物的合計與季戊四醇丙烯酸酯系化合物的質量比(金屬氧化物/季戊四醇丙烯酸酯系化合物)為90/10~15/85而含有。<Pentaerythritol acrylate compound> The active-energy-ray-curable composition of this invention contains 10 mass%-80 mass% of pentaerythritol acrylate compounds in 100 mass% of solid content. It is preferably 20% by mass to 70% by mass. The mass ratio of the total of the metal oxides to the pentaerythritol acrylate-based compound (metal oxide / pentaerythritol acrylate-based compound) is preferably contained at 90/10 to 15/85.
本說明書中,所謂季戊四醇丙烯酸酯系化合物,是指季戊四醇三丙烯酸酯(分子量298)、季戊四醇三甲基丙烯酸酯(分子量340)、季戊四醇四丙烯酸酯(分子量352)、季戊四醇四甲基丙烯酸酯(分子量408)、二季戊四醇五丙烯酸酯(分子量524)、二季戊四醇五甲基丙烯酸酯(分子量594)、二季戊四醇六丙烯酸酯(分子量578)、二季戊四醇六甲基丙烯酸酯(分子量662)等具有季戊四醇結構與(甲基)丙烯酸酯結構的化合物,以及進而在這些化合物的季戊四醇結構與(甲基)丙烯酸酯結構之間具有聚環氧乙烷、聚環氧丙烷等聚醚結構的化合物,且為分子量未滿700的化合物。再者,這些季戊四醇(甲基)丙烯酸酯系化合物可單獨使用,也可併用兩種以上。 上述中,較佳為季戊四醇三丙烯酸酯(分子量298)、季戊四醇四丙烯酸酯(分子量352)、二季戊四醇五丙烯酸酯(分子量524)及二季戊四醇六丙烯酸酯(分子量578)。In this specification, the pentaerythritol acrylate compound refers to pentaerythritol triacrylate (molecular weight 298), pentaerythritol trimethacrylate (molecular weight 340), pentaerythritol tetraacrylate (molecular weight 352), pentaerythritol tetramethacrylate (molecular weight) 408), dipentaerythritol pentaacrylate (molecular weight 524), dipentaerythritol pentamethacrylate (molecular weight 594), dipentaerythritol hexaacrylate (molecular weight 578), dipentaerythritol hexamethacrylate (molecular weight 662), etc. have pentaerythritol structure Compounds having a (meth) acrylate structure and compounds having a polyether structure such as polyethylene oxide and polypropylene oxide between the pentaerythritol structure and the (meth) acrylate structure of these compounds, and having a molecular weight Less than 700 compounds. These pentaerythritol (meth) acrylate compounds may be used alone or in combination of two or more. Among the above, pentaerythritol triacrylate (molecular weight 298), pentaerythritol tetraacrylate (molecular weight 352), dipentaerythritol pentaacrylate (molecular weight 524), and dipentaerythritol hexaacrylate (molecular weight 578) are preferred.
另外,季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等不具有羥基的季戊四醇丙烯酸酯系化合物包含於後述的用作用以獲得丙烯酸酯樹脂的原料的季戊四醇三丙烯酸酯、二季戊四醇五丙烯酸酯等的製品中。因此,所獲得的樹脂組成物成為丙烯酸酯樹脂與季戊四醇丙烯酸酯系化合物的混合物。In addition, pentaerythritol acrylate compounds having no hydroxyl group, such as pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate, are contained in pentaerythritol triacrylate, dipentaerythritol, diamine, and other raw materials that are used to obtain acrylic resin. In products such as pentaerythritol pentaacrylate. Therefore, the obtained resin composition becomes a mixture of an acrylate resin and a pentaerythritol acrylate-based compound.
<丙烯酸酯樹脂> 在所述活性能量線硬化性組成物中,還可含有具有6個以上的(甲基)丙烯醯基且質量平均分子量為700~10000的丙烯酸酯樹脂(其中所述季戊四醇(甲基)丙烯酸酯系化合物除外)。關於所述丙烯酸酯樹脂的含量,在組成物固體成分100質量%中較佳為5質量%~45質量%,更較佳為10質量%~40質量%。另外,就塗敷性的觀點而言,質量平均分子量更較佳為1000~8000。另外,作為黏度,利用B型黏度計,在60℃下較佳為500 mPa・s~30000 mPa・s。 作為所述樹脂,就塗膜強度、耐摩擦(擦傷)性的觀點而言,可較佳為使用胺基甲酸酯丙烯酸酯、聚環氧丙烯酸酯、聚酯丙烯酸酯等多官能的(甲基)丙烯酸酯樹脂。其中,較佳為聚酯丙烯酸酯及/或胺基甲酸酯丙烯酸酯。<Acrylic Resin> The active energy ray-curable composition may further contain an acrylate resin (where the pentaerythritol (the pentaerythritol ( Except for meth) acrylates). The content of the acrylate resin is preferably 5 to 45% by mass, and more preferably 10 to 40% by mass, based on 100% by mass of the solid content of the composition. From the viewpoint of coating properties, the mass average molecular weight is more preferably 1,000 to 8,000. In addition, as the viscosity, a B-type viscometer is used, and preferably 500 mPa ・ s to 30,000 mPa ・ s at 60 ° C. As the resin, a polyfunctional (formaldehyde) such as a urethane acrylate, a polyepoxy acrylate, and a polyester acrylate can be preferably used from the viewpoints of coating film strength and abrasion (scratch) resistance. Based) acrylic resin. Among these, polyester acrylate and / or urethane acrylate is preferable.
再者,在含有所述丙烯酸酯樹脂的情況下,與季戊四醇丙烯酸酯系化合物的質量比(丙烯酸酯樹脂/季戊四醇丙烯酸酯系化合物)較佳為90/10~10/90,更較佳為80/20~50/50。When the acrylate resin is contained, the mass ratio to the pentaerythritol acrylate compound (acrylate resin / pentaerythritol acrylate compound) is preferably 90/10 to 10/90, and more preferably 80. / 20 ~ 50/50.
<聚環氧丙烯酸酯> 聚環氧丙烯酸酯例如可列舉以(甲基)丙烯酸對環氧樹脂的縮水甘油基進行酯化並將官能基設為(甲基)丙烯酸酯基而成者,有對雙酚A型環氧樹脂的(甲基)丙烯酸加成物、對酚醛清漆型環氧樹脂的(甲基)丙烯酸加成物等。<Polyepoxy Acrylate> Examples of the polyepoxy acrylate include (meth) acrylic acid esterifying a glycidyl group of an epoxy resin and having a functional group as a (meth) acrylate group. (Meth) acrylic acid adduct to bisphenol A epoxy resin, (meth) acrylic acid adduct to novolac epoxy resin, and the like.
<胺基甲酸酯丙烯酸酯> 胺基甲酸酯丙烯酸酯例如有:使聚異氰酸酯與具有羥基的(甲基)丙烯酸酯類反應而得者;使多元醇與聚異氰酸酯在異氰酸酯基過剩的條件下反應而成的含異氰酸酯基的胺基甲酸酯預聚物、與具有羥基的(甲基)丙烯酸酯類反應而得者等。或者,也可使多元醇與聚異氰酸酯在羥基過剩的條件下反應而成的含有羥基的胺基甲酸酯預聚物、與具有異氰酸酯基的(甲基)丙烯酸酯類反應而獲得。<Urethane acrylate> Examples of the urethane acrylate include those obtained by reacting a polyisocyanate with a (meth) acrylate having a hydroxyl group; and a condition in which a polyol and a polyisocyanate have an excess of isocyanate groups. An isocyanate group-containing urethane prepolymer obtained by the following reaction, a product obtained by reacting with a (meth) acrylate having a hydroxyl group, and the like. Alternatively, it may be obtained by reacting a polyol with a polyisocyanate under conditions in which a hydroxyl group is excessive, and a urethane-containing urethane prepolymer that reacts with a (meth) acrylate having an isocyanate group.
以下示出胺基甲酸酯丙烯酸酯的製造方法,但此為一例,並不限定於這些製造方法。 例如,胺基甲酸酯丙烯酸酯可在適當的胺基甲酸酯化催化劑的存在下,且在氧環境下、以60℃~100℃、4小時~8小時的條件對聚異氰酸酯與含羥基的(甲基)丙烯酸酯進行攪拌而獲得。 作為胺基甲酸酯化催化劑的具體例,可列舉:環烷酸銅、環烷酸鈷、環烷酸鋅、二丁基錫二月桂酸酯、三乙基胺、1,4-二氮雜雙環[2.2.2]辛烷、2,6,7-三甲基-1,4-二氮雜雙環[2.2.2]辛烷等。這些具體例中,特別較佳為二丁基錫二月桂酸酯等。A method for producing a urethane acrylate is shown below, but this is an example and is not limited to these methods. For example, urethane acrylates can be used to oxidize polyisocyanates and hydroxyl groups in the presence of a suitable urethanization catalyst and in an oxygen environment at 60 ° C to 100 ° C for 4 to 8 hours. (Meth) acrylate was obtained by stirring. Specific examples of the urethane catalyst include copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, and 1,4-diazabicyclo [2.2.2] octane, 2,6,7-trimethyl-1,4-diazabicyclo [2.2.2] octane, etc. Among these specific examples, dibutyltin dilaurate and the like are particularly preferable.
所述聚異氰酸酯可列舉芳香族二異氰酸酯、脂肪族二異氰酸酯、脂環族二異氰酸酯等,但並不限定於這些聚異氰酸酯。例如可列舉1,5-萘二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯(MDI)、4,4'-二苯基二甲基甲烷二異氰酸酯、4,4'-二苄基異氰酸酯、二烷基二苯基甲烷二異氰酸酯、四烷基二苯基甲烷二異氰酸酯、1,3-亞苯基二異氰酸酯、1,4-亞苯基二異氰酸酯、甲苯二異氰酸酯、丁烷-1,4-二異氰酸酯、六亞甲基二異氰酸酯、亞異丙基二異氰酸酯、亞甲基二異氰酸酯、2,2,4-三甲基六亞甲基二異氰酸酯、賴胺酸二異氰酸酯、環己烷-1,4-二異氰酸酯、二甲苯二異氰酸酯、異佛爾酮二異氰酸酯、二環己基甲烷-4,4'-二異氰酸酯、1,3-雙(異氰酸酯甲基)環己烷、甲基環己烷二異氰酸酯、降冰片烷二異氰酸酯、間四甲基二甲苯二異氰酸酯、4,4-二苯基甲烷二異氰酸酯、雙-氯甲基-二苯基甲烷-二異氰酸酯、2,6-二異氰酸酯-苄基氯或將二聚酸的羧基轉變成異氰酸酯基而成的二聚二異氰酸酯等,但並不限定於這些聚異氰酸酯。這些聚異氰酸酯也可形成三聚物而形成異氰脲酸酯環結構。這些聚異氰酸酯可單獨使用或混合使用兩種以上。 其中,較佳為甲苯二異氰酸酯、異佛爾酮二異氰酸酯、二甲苯二異氰酸酯、氫化二甲苯二異氰酸酯、六亞甲基二異氰酸酯、及六亞甲基二異氰酸酯的異氰脲酸酯體。Examples of the polyisocyanate include aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate, but are not limited to these polyisocyanates. Examples include 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate , Dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, toluene diisocyanate, butane-1, 4-diisocyanate, hexamethylene diisocyanate, isopropylidene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, cyclohexane -1,4-diisocyanate, xylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, methyl ring Hexane diisocyanate, norbornane diisocyanate, m-tetramethylxylene diisocyanate, 4,4-diphenylmethane diisocyanate, bis-chloromethyl-diphenylmethane-diisocyanate, 2,6-di Isocyanate-benzyl chloride or dimeric diisocyanate obtained by converting the carboxyl group of a dimer acid into an isocyanate group, etc., but not It is limited to these polyisocyanates. These polyisocyanates may also form a trimer to form an isocyanurate ring structure. These polyisocyanates can be used alone or in combination of two or more. Among these, isocyanurate of toluene diisocyanate, isophorone diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, hexamethylene diisocyanate, and hexamethylene diisocyanate is preferred.
作為含羥基的(甲基)丙烯酸酯,可列舉:三羥甲基丙烷二(甲基)丙烯酸酯、三羥甲基乙烷二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯等多官能(甲基)丙烯酸酯;(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-1-羥基丙酯、(甲基)丙烯酸-2-羥基丙酯、(甲基)丙烯酸-3-羥基丙酯、(甲基)丙烯酸-1-羥基丁酯、(甲基)丙烯酸-2-羥基丁酯、(甲基)丙烯酸-3-羥基丁酯、(甲基)丙烯酸-4-羥基丁酯、(甲基)丙烯酸-6-羥基己酯、(甲基)丙烯酸-8-羥基辛酯、環己烷二甲醇單(甲基)丙烯酸酯、(甲基)丙烯酸-10-羥基癸酯、(甲基)丙烯酸-12-羥基月桂酯、(甲基)丙烯酸乙基-α-(羥基甲基)酯、單官能(甲基)丙烯酸甘油酯等(甲基)丙烯酸酯類;或者在含所述羥基的(甲基)丙烯酸酯中、ε-己內酯經開環加成而得到在末端具有羥基的(甲基)丙烯酸酯、或對所述含羥基的(甲基)丙烯酸酯反覆加成環氧乙烷、環氧丙烷、環氧丁烷等環氧烷而成的環氧烷加成(甲基)丙烯酸酯等含羥基的(甲基)丙烯酸酯類,但並不限定於這些(甲基)丙烯酸酯。其中,較佳為選自三羥甲基丙烷二(甲基)丙烯酸酯、三羥甲基乙烷二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯中的至少一種。Examples of the hydroxyl-containing (meth) acrylate include trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, Polyfunctional (meth) acrylates such as dipentaerythritol penta (meth) acrylate; 2-hydroxyethyl (meth) acrylate, -1-hydroxypropyl (meth) acrylate, -2 -Hydroxypropyl ester, 3-hydroxypropyl (meth) acrylate, -1-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxy (meth) acrylate Butyl ester, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylic acid Esters, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, ethyl-α- (hydroxymethyl) (meth) acrylate, monofunctional (meth) acrylic acid (Meth) acrylates such as glycerides; or (meth) acrylates containing the hydroxyl group, ε-caprolactone is subjected to ring-opening addition to obtain (meth) acrylates having a hydroxyl group at the terminal, Or for the hydroxyl-containing (methyl) Hydroxyl-containing (meth) acrylates such as alkylene oxide (meth) acrylates obtained by repeating addition of acrylates to alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide, but not It is not limited to these (meth) acrylates. Among them, it is preferably selected from the group consisting of trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (methyl) At least one of acrylates.
<聚酯丙烯酸酯> 聚酯丙烯酸酯例如可使對多元酸及多元醇進行縮聚而獲得的聚酯多羧酸、與含羧基或羥基的(甲基)丙烯酸酯反應而獲得。 作為所述多元酸,可列舉脂肪族系、脂環族系、及芳香族系,分別可無特別限制地使用。例如,作為脂肪族系多元酸,可列舉乙二酸、丙二酸、丁二酸、己二酸、癸二酸、壬二酸、辛二酸、順丁烯二酸、氯順丁烯二酸、反丁烯二酸、十二烷二酸、庚二酸、檸康酸、戊二酸、衣康酸、丁二酸酐、順丁烯二酸酐等,可利用這些脂肪族二羧酸及其無水物。另外,也可利用丁二酸酐的衍生物(甲基丁二酸酐、2,2-二甲基丁二酸酐、丁基丁二酸酐、異丁基丁二酸酐、己基丁二酸酐、辛基丁二酸酐、十二烯基丁二酸酐、苯基丁二酸酐等)、戊二酸酐的衍生物(戊二酸酐、3-烯丙基戊二酸酐、2,4-二甲基戊二酸酐、2,4-二乙基戊二酸酐、丁基戊二酸酐、己基戊二酸酐等)、順丁烯二酸酐的衍生物(2-甲基順丁烯二酸酐、2,3-二甲基順丁烯二酸酐、丁基順丁烯二酸酐、戊基順丁烯二酸酐、己基順丁烯二酸酐、辛基順丁烯二酸酐、癸基順丁烯二酸酐、十二烷基順丁烯二酸酐、2,3-二氯順丁烯二酸酐、苯基順丁烯二酸酐、2,3-二苯基順丁烯二酸酐等)等無水物衍生物。<Polyester Acrylate> The polyester acrylate can be obtained, for example, by reacting a polyester polycarboxylic acid obtained by polycondensing a polybasic acid and a polyhydric alcohol with a (meth) acrylate containing a carboxyl group or a hydroxyl group. Examples of the polybasic acid include aliphatic systems, alicyclic systems, and aromatic systems, and each of them can be used without particular limitation. For example, examples of the aliphatic polybasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, and chloromaleic acid. Acids, fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, glutaric acid, itaconic acid, succinic anhydride, maleic anhydride, etc. These aliphatic dicarboxylic acids and Its anhydrous. In addition, derivatives of succinic anhydride (methylsuccinic anhydride, 2,2-dimethylsuccinic anhydride, butylsuccinic anhydride, isobutylsuccinic anhydride, hexylsuccinic anhydride, octylbutanedioic acid) Dianhydride, dodecenyl succinic anhydride, phenylsuccinic anhydride, etc.), derivatives of glutaric anhydride (glutaric anhydride, 3-allyl glutaric anhydride, 2,4-dimethylglutaric anhydride, 2,4-diethylglutaric anhydride, butylglutaric anhydride, hexylglutaric anhydride, etc.), maleic anhydride derivatives (2-methylmaleic anhydride, 2,3-dimethyl Maleic anhydride, butyl maleic anhydride, pentyl maleic anhydride, hexyl maleic anhydride, octyl maleic anhydride, decyl maleic anhydride, dodecyl maleic anhydride , 2,3-dichloromaleic anhydride, phenylmaleic anhydride, 2,3-diphenylmaleic anhydride, etc.) and other anhydrous derivatives.
另外,作為所述多元醇,例如可列舉:乙二醇、丙二醇、二丙二醇、二乙二醇、三乙二醇、丁二醇、3-甲基-1,5-戊二醇、2,4-二乙基-1,5-戊二醇、2-甲基-1,8-辛二醇、3,3'-二羥甲基庚烷、2-丁基-2-乙基-1,3-丙二醇、聚氧乙二醇(加成莫耳數為10以下)、聚氧丙二醇(加成莫耳數為10以下)、丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,9-壬二醇、新戊二醇、辛二醇、丁基乙基戊二醇、2-乙基-1,3-己二醇、環己二醇、環己烷二甲醇、三環癸烷二甲醇、環戊二烯二甲醇、二聚物二醇等脂肪族或脂環式二醇類;Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, and 2, 4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3'-dimethylolheptane, 2-butyl-2-ethyl-1 , 3-propanediol, polyoxyethylene glycol (additional mole number is less than 10), polyoxypropylene glycol (additional mole number is less than 10), propylene glycol, 1,3-butanediol, 1,4-butanediol Glycol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1 , Aliphatic or alicyclic diols such as 3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, cyclopentadienedimethanol, dimer diol;
1,3-雙(2-羥基乙氧基)苯、1,2-雙(2-羥基乙氧基)苯、1,4-雙(2-羥基乙氧基)苯、4,4'-亞甲基二苯酚、4,4'-(2-亞降冰片烯)二苯酚、4,4'-二羥基聯苯酚、鄰二羥基苯、間二羥基苯及對二羥基苯、4,4'-亞異丙基苯酚、在雙酚中加成有環氧烷的加成型雙酚等芳香族二醇類等,但並不限定於這些多元醇。1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4'- Methylene diphenol, 4,4 '-(2-norbornene) diphenol, 4,4'-dihydroxybiphenol, o-dihydroxybenzene, m-dihydroxybenzene and p-dihydroxybenzene, 4,4 Aromatic diols such as' -isopropylidenephenol and addition bisphenols in which alkylene oxide is added to bisphenols are not limited to these polyols.
作為加成型雙酚的原料雙酚,可列舉雙酚A、雙酚F等,作為原料環氧烷,可列舉環氧乙烷、環氧丙烷等,但並不限定於這些化合物。Examples of the bisphenol as a raw material of the addition-molded bisphenol include bisphenol A, bisphenol F, and the like, and examples of the raw material alkylene oxide include ethylene oxide and propylene oxide, but are not limited to these compounds.
另外,也可使用一部分甘油、三羥甲基丙烷、季戊四醇、二季戊四醇等含有三個以上的羥基的多元醇。In addition, polyhydric alcohols containing three or more hydroxyl groups, such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol, may also be used.
所述多元醇中,就寡聚物的黏接性、耐熱性等方面而言,較佳為新戊二醇、3-甲基-1,5-戊二醇、2,4-二乙基-1,5-戊二醇、2-甲基-1,8-辛二醇、3,3'-二羥甲基庚烷、2-丁基-2-乙基-1,3-丙二醇、丁基乙基戊二醇、2-乙基-1,3-己二醇、三羥甲基丙烷等在分支的烷烴中導入有兩個以上的羥基的多元醇。Among the polyols, neopentyl glycol, 3-methyl-1,5-pentanediol, and 2,4-diethyl are preferred in terms of adhesion and heat resistance of the oligomer. -1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3'-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, Polyols having two or more hydroxyl groups introduced into a branched alkane, such as butylethylpentanediol, 2-ethyl-1,3-hexanediol, and trimethylolpropane.
聚酯丙烯酸酯首先利用已知的方法對多元酸及多元醇進行縮聚而獲得聚酯。此時,利用羧基量與羥基量的平衡來調整分子量及末端官能基等。The polyester acrylate first obtains a polyester by polycondensing a polybasic acid and a polyhydric alcohol by a known method. At this time, the molecular weight, the terminal functional group, and the like are adjusted using the balance between the amount of carboxyl groups and the amount of hydroxyl groups.
在「多元酸中所含的羧基量>多元醇中所含的羥基量」的情況下,末端官能基為羧基,通過使所述含羥基的(甲基)丙烯酸酯的羥基與所述末端官能基進行縮合反應,可獲得目標聚酯丙烯酸酯。In the case of "the amount of carboxyl groups contained in the polybasic acid> the amount of hydroxyl groups contained in the polyhydric alcohol", the terminal functional group is a carboxyl group, and the hydroxyl groups of the hydroxyl-containing (meth) acrylate and the terminal functional groups The group undergoes a condensation reaction to obtain a target polyester acrylate.
作為含羥基的(甲基)丙烯酸酯,可列舉與上述相同的含羥基的(甲基)丙烯酸酯,其中較佳為包括選自三羥甲基丙烷二(甲基)丙烯酸酯、三羥甲基乙烷二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯中的至少一種。Examples of the hydroxy-containing (meth) acrylate include the same hydroxy-containing (meth) acrylate as described above. Among them, it is preferable to include a group selected from the group consisting of trimethylolpropane di (meth) acrylate and trimethylol. At least one of ethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate.
另外,聚酯丙烯酸酯也可通過使多元酸酐與含羥基的(甲基)丙烯酸酯反應,並使所生成的羧基進一步與環氧化合物反應而獲得。作為多元酸酐,可列舉3,3',4,4'-聯苯四羧酸二酐、9,9-雙(3,4-二羧基苯基)芴二酐、1,2,4,5-苯四羧酸二酐、1,2,3,4-丁烷四羧酸二酐等四羧酸二酐等,較佳為具有芴結構或聯苯結構的多元酸酐。作為環氧化合物,可列舉聯苯縮水甘油醚、甲基丙烯酸縮水甘油酯、及丙烯酸-4-羥基丁酯縮水甘油醚等,但並不限定於這些環氧化合物。The polyester acrylate can also be obtained by reacting a polybasic acid anhydride with a hydroxyl group-containing (meth) acrylate, and further reacting the generated carboxyl group with an epoxy compound. Examples of the polybasic acid anhydride include 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 1,2,4,5 -Tetracarboxylic dianhydride such as pyromellitic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride and the like, and a polybasic acid anhydride having a fluorene structure or a biphenyl structure is preferred. Examples of the epoxy compound include biphenyl glycidyl ether, glycidyl methacrylate, and glycidyl ether of 4-hydroxybutyl acrylate. However, the epoxy compound is not limited to these epoxy compounds.
<聚合抑制劑> 所述質量平均分子量為700~10000的丙烯酸酯樹脂可包含聚合抑制劑。作為聚合抑制劑,可列舉對苯二酚系的化合物,較佳為對苯二酚、甲基對苯二酚。再者,含量較佳為相對於丙烯酸酯樹脂而為100 ppm~500 ppm。<Polymerization inhibitor> The acrylate resin having a mass average molecular weight of 700 to 10,000 may contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone-based compounds, and hydroquinone and methylhydroquinone are preferred. The content is preferably 100 ppm to 500 ppm based on the acrylate resin.
作為所述具有6個以上的(甲基)丙烯醯基且質量平均分子量為700~10000的丙烯酸酯樹脂的市售品,可例示以下市售品。 東亞合成(股)製造的:阿羅尼斯(Aronix)M-7100、阿羅尼斯(Aronix)M-8030、阿羅尼斯(Aronix)M-8060,化藥沙多瑪(Sartomer)(股)製造的:CN986NS、CN9010NS,大賽璐・奧魯尼克斯(Daicel Allnex)(股)製造的:艾巴克力(Ebecryl)220、艾巴克力(Ebecryl)1290、艾巴克力(Ebecryl)1830,新中村化學工業(股)製造的:NK寡聚(NK OLIGO)U6LPA、NK寡聚(NK OLIGO)U10PA、NK寡聚(NK OLIGO)U10HA、NK寡聚(NK OLIGO)UA-33H、NK寡聚(NK OLIGO)UA-53H,荒川化學工業(股)製造的:畢姆賽特(Beamset)371、畢姆賽特(Beamset)575、畢姆賽特(Beamset)577,根上工業(股)製造的:亞特來津(Art resin)UN-3320HA、亞特來津(Art resin)UN-3320HB、亞特來津(Art resin)UN-3320HC、亞特來津(Art resin)UN-3320HS、亞特來津(Art resin)UN-9000H、亞特來津(Art resin)UN-901T、亞特來津(Art resin)UN-904、亞特來津(Art resin)UN-905、亞特來津(Art resin)UN-952、亞特來津(Art resin)HDP、亞特來津(Art resin)HDP-3、亞特來津(Art resin)H61,日本合成化學工業(股)製造的:紫光UV-7600B、紫光UV-7610B、紫光UV-7620EA、紫光UV-7630B、紫光UV-1700B、紫光UV-6300B、紫光UV-7640B,共榮社化學(股)製造的:UA-306H、UA-306T、UA-306I。As a commercial item of the said acrylate resin which has 6 or more (meth) acryl fluorenyl groups, and whose mass average molecular weight is 700-10000, the following commercial item can be illustrated. Made by East Asia Synthetic (Aronix): Aronix M-7100, Aronix M-8030, Aronix M-8060, chemical drug Sartomer (stock) : CN986NS, CN9010NS, made by Daicel Allnex (shares): Ebecryl 220, Ebecryl 1290, Ebecryl 1830, Shin Nakamura Chemical Industrial (stock) manufacturing: NK oligo (NK OLIGO) U6LPA, NK oligo (NK OLIGO) U10PA, NK oligo (NK OLIGO) U10HA, NK oligo (NK OLIGO) UA-33H, NK oligo (NK OLIGO) OLIGO) UA-53H, manufactured by Arakawa Chemical Industry Co., Ltd .: Beamset 371, Beamset 575, Beamset 577, manufactured by Genjo Industry: Art resin UN-3320HA, Art resin UN-3320HB, Art resin UN-3320HC, Art resin UN-3320HS, Art Art resin UN-9000H, Art resin UN-901T, Art resin UN-904, Art resin Art resin UN-905, Art resin UN-952, Art resin HDP, Art resin HDP-3, Art resin ) H61, manufactured by Japan Synthetic Chemical Industry Co., Ltd .: Violet UV-7600B, Violet UV-7610B, Violet UV-7620EA, Violet UV-7630B, Violet UV-1700B, Violet UV-6300B, Violet UV-7640B, Gongrong Made by social chemical (stock): UA-306H, UA-306T, UA-306I.
<其他單體> 本發明的活性能量線硬化性組成物可含有5官能以下的(甲基)丙烯酸酯單體。例如,作為3官能~4官能的(甲基)丙烯酸酯單體,可列舉二-三羥甲基丙烷四丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三(2-羥基乙基)異氰脲酸酯三丙烯酸酯、乙氧基化三羥甲基丙烷三丙烯酸酯、丙氧基化三羥甲基丙烷三丙烯酸酯,但並不限定於這些單體。<Other monomers> The active energy ray-curable composition of the present invention may contain a (meth) acrylic acid ester monomer having 5 or less functions. For example, examples of the trifunctional to tetrafunctional (meth) acrylate monomers include di-trimethylolpropane tetraacrylate, trimethylolpropane tri (meth) acrylate, and tri (2-hydroxyethyl). Group) isocyanurate triacrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane triacrylate, but are not limited to these monomers.
作2官能的(甲基)丙烯酸酯單體,例如可列舉三羥甲基丙烷二(甲基)丙烯酸酯、二環戊基二亞甲基二(甲基)丙烯酸酯、5-乙基-2-(2-羥基-1,1-二甲基乙基)-5-(羥基甲基)-1,3-二氧雜二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、甘油二甲基丙烯酸酯、己二醇二(甲基)丙烯酸酯、二羥甲基三環癸烷二(甲基)丙烯酸酯等,但並不限定於這些單體。作為較佳為的具體例,可列舉:三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷(ethylene oxide,EO)改質三羥甲基三丙烯酸酯、環氧丙烷(propylene oxide,PO)改質三羥甲基三(甲基)丙烯酸酯等。這些(甲基)丙烯酸酯可單獨使用,或者可混合使用兩種以上。Examples of the bifunctional (meth) acrylate monomer include trimethylolpropane di (meth) acrylate, dicyclopentyl dimethylene di (meth) acrylate, and 5-ethyl- 2- (2-hydroxy-1,1-dimethylethyl) -5- (hydroxymethyl) -1,3-dioxadi (meth) acrylate, neopentyl glycol di (methyl) Acrylate, 1,6-hexanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene Glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, glycerol dimethacrylate, Hexanediol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, and the like are not limited to these monomers. As preferred specific examples, trimethylolpropane tri (meth) acrylate, ethylene oxide (EO) modified trimethylol triacrylate, and propylene oxide can be listed. , PO) modified trimethylol tris (meth) acrylate and the like. These (meth) acrylic acid esters may be used alone or in combination of two or more.
作為1官能的(甲基)丙烯酸酯單體,例如可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸正硬脂酯、(甲基)丙烯酸正丁氧基乙酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丁酯等,但並不限定於這些單體。Examples of the monofunctional (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, N-stearyl (meth) acrylate, n-butoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and the like are not limited to these monomers.
關於所述金屬氧化物、季戊四醇丙烯酸酯系化合物、具有6個以上的(甲基)丙烯醯基且質量平均分子量為700~10000的(甲基)丙烯酸酯樹脂的調配量,較佳為以70/10/20~10/50/40的比例而含有,且較佳為在組成物的固體成分100質量%中含有70質量%~100質量%。如果調配量為所述範圍,則可獲得耐擦傷性優異的折射率匹配層。The blending amount of the metal oxide, pentaerythritol acrylate-based compound, and (meth) acrylic acid ester resin having 6 (meth) acrylfluorenyl groups and a mass average molecular weight of 700 to 10,000 is preferably 70. It is contained at a ratio of / 10/20 to 10/50/40, and is preferably contained at 70% by mass to 100% by mass of 100% by mass of the solid content of the composition. When the blending amount is within the above range, a refractive index matching layer excellent in abrasion resistance can be obtained.
<有機溶劑> 本發明的活性能量線硬化性組成物可包含有機溶劑作為液狀介質。作為所使用的有機溶劑,較佳為以混合溶劑的形式使用,可使用甲苯、二甲苯等芳香族系有機溶劑;甲基乙基酮、甲基異丁基酮等酮系有機溶劑;乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸異丁酯等酯系有機溶劑;甲醇、乙醇、正丙醇、異丙醇、正丁醇等醇系有機溶劑;丙二醇單甲醚等二醇醚系有機溶劑等已知的有機溶劑。特別較佳為包含二醇醚系有機溶劑。<Organic solvent> The active-energy-ray-curable composition of this invention may contain an organic solvent as a liquid medium. As the organic solvent to be used, it is preferable to use it as a mixed solvent. Aromatic organic solvents such as toluene and xylene can be used; ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone; ethyl acetate Esters, n-propyl acetate, isopropyl acetate, isobutyl acetate and other ester-based organic solvents; methanol, ethanol, n-propanol, isopropanol, n-butanol and other alcohol-based organic solvents; propylene glycol monomethyl ether and other glycols Known organic solvents such as ether-based organic solvents. It is particularly preferable to include a glycol ether-based organic solvent.
作為所述二醇醚系有機溶劑,例如可列舉:乙二醇單甲醚、乙二醇單乙醚、乙二醇二甲醚、乙二醇二乙醚、乙二醇單正丙醚、乙二醇單異丙醚、乙二醇二丙醚、乙二醇單丁醚、乙二醇單異丁醚、乙二醇二丁醚、乙二醇異戊醚、乙二醇單己醚、乙二醇單2-乙基己醚、甲氧基乙氧基乙醇、乙二醇單烯丙基醚等乙二醇醚類;丙二醇單甲醚、丙二醇單乙醚、丙二醇單丙醚、丙二醇單丁醚、丁氧基丙醇等丙二醇醚類;但並不限定於這些有機溶劑。作為本發明的活性能量線硬化性組成物中使用的有機溶劑,其中較佳為甲基丙二醇、3-甲氧基-1-丁醇。Examples of the glycol ether-based organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-propyl ether, and ethylene glycol. Alcohol monoisopropyl ether, ethylene glycol dipropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol dibutyl ether, ethylene glycol isoamyl ether, ethylene glycol monohexyl ether, ethyl alcohol Glycol mono 2-ethylhexyl ether, methoxyethoxy ethanol, ethylene glycol monoallyl ether, and other glycol ethers; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether Propylene glycol ethers such as ether and butoxypropanol; but not limited to these organic solvents. Among the organic solvents used in the active energy ray-curable composition of the present invention, methyl propylene glycol and 3-methoxy-1-butanol are preferred.
<光聚合起始劑> 活性能量線硬化性組成物還可包含光聚合起始劑。作為光聚合起始劑,只要具有如下功能,即,可通過光激發而引發用以形成活性能量線硬化膜的(甲基)丙烯醯基的乙烯基聚合的功能,則無特別限定,例如可使用單羰基化合物、二羰基化合物、苯乙酮化合物、安息香醚化合物、醯基氧化膦化合物、胺基羰基化合物等。<Photopolymerization initiator> The active energy ray-curable composition may further include a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it has a function of initiating photopolymerization of a (meth) acrylfluorene-based vinyl group to form an active energy ray-cured film by photoexcitation. A monocarbonyl compound, a dicarbonyl compound, an acetophenone compound, a benzoin ether compound, a fluorenylphosphine oxide compound, an aminocarbonyl compound, or the like is used.
具體而言,作為單羰基化合物,可列舉二苯甲酮、4-甲基-二苯甲酮、2,4,6-三甲基二苯甲酮、鄰苯甲醯基苯甲酸甲酯、4-苯基二苯甲酮、4-(4-甲基苯硫基)苯基-乙酮、3,3'-二甲基-4-甲氧基二苯甲酮、4-(1,3-丙烯醯基-1,3-二甲基-4-甲氧基)二苯甲酮、4-(1,3-丙烯醯基-1,4,7,10,13-五氧代十三烷基)二苯甲酮、3,3',4,4'-四(第三丁基過氧化羰基)二苯甲酮、4-苯甲醯基-N,N,N-三甲基-1-丙胺鹽酸鹽、4-苯甲醯基-N,N-二甲基-N-2-(1-氧代-2-丙烯基氧基乙基)偏草酸銨鹽、2-/4-異-丙基硫雜蒽酮、2,4-二乙基硫雜蒽酮、2,4-二氯硫雜蒽酮、1-氯-4-丙氧基硫雜蒽酮、2-羥基-3-(3,4-二甲基-9-氧代-9H-硫雜蒽酮-2-基氧基)-N,N,N-三甲基-1-丙胺鹽酸鹽、苯甲醯基亞甲基-3-甲基萘並(1,2-d)噻唑啉等,但並不限定於這些化合物。Specifically, examples of the monocarbonyl compound include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4- (4-methylphenylthio) phenyl-ethanone, 3,3'-dimethyl-4-methoxybenzophenone, 4- (1, 3-propenyl-1,3-dimethyl-4-methoxy) benzophenone, 4- (1,3-propenyl-1,4,7,10,13-pentaoxo (Trialkyl) benzophenone, 3,3 ', 4,4'-tetrakis (third butylperoxycarbonyl) benzophenone, 4-benzylidene-N, N, N-trimethyl 1-propylamine hydrochloride, 4-benzylamino-N, N-dimethyl-N-2- (1-oxo-2-propenyloxyethyl) ammonium metaoxalate, 2- / 4-iso-propylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- Hydroxy-3- (3,4-dimethyl-9-oxo-9H-thiaxanthone-2-yloxy) -N, N, N-trimethyl-1-propylamine hydrochloride, benzene Formamidine methylene-3-methylnaphtho (1,2-d) thiazoline and the like are not limited to these compounds.
作為二羰基化合物,可列舉1,2,2-三甲基-雙環[2.1.1]庚烷-2,3-二酮、苯甲醯、2-乙基蒽醌、9,10-菲醌、α-氧代苯乙酸甲酯、4-苯基苯甲醯等,但並不限定於這些化合物。 作為苯乙酮化合物,可列舉2-羥基-2-甲基-1-苯基丙烷-1-酮、1-(4-異丙基苯基)-2-羥基-2-甲基-1-苯基丙烷-1-酮、1-(4-異丙基苯基)-2-羥基-二-2-甲基-1-苯基丙烷-1-酮、1-羥基-環己基苯基酮、2-羥基-2-甲基-1-苯乙烯基丙烷-1-酮聚合物、二乙氧基苯乙酮、二丁氧基苯乙酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、2,2-二乙氧基-1,2-二苯基乙烷-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)丁烷-1-酮、1-苯基-1,2-丙二酮-2-(鄰乙氧基羰基)肟、3,6-雙(2-甲基-2-嗎啉基-丙醯基)-9-丁基哢唑等,但並不限定於這些化合物。Examples of the dicarbonyl compound include 1,2,2-trimethyl-bicyclo [2.1.1] heptane-2,3-dione, benzamidine, 2-ethylanthraquinone, and 9,10-phenanthrenequinone. , Methyl α-oxophenylacetate, 4-phenylbenzidine, and the like, but are not limited to these compounds. Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropane-1-one and 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1- Phenylpropane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-di-2-methyl-1-phenylpropane-1-one, 1-hydroxy-cyclohexylphenyl ketone , 2-hydroxy-2-methyl-1-styrylpropane-1-one polymer, diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1, 2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butane-1-one, 1-phenyl -1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 3,6-bis (2-methyl-2-morpholinyl-propionyl) -9-butyloxazole, etc., It is not limited to these compounds.
作為安息香醚化合物,可列舉安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚、安息香正丁醚等,但並不限定於這些化合物。 作為醯基氧化膦化合物,可列舉2,4,6-三甲基苯甲醯基二苯基氧化膦、4-正丙基苯基-二(2,6-二氯苯甲醯基)氧化膦等,但並不限定於這些化合物。Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin n-butyl ether, but are not limited to these compounds. Examples of the fluorenylphosphine oxide compounds include 2,4,6-trimethylbenzylidenediphenylphosphine oxide and 4-n-propylphenyl-bis (2,6-dichlorobenzyl) oxide Phosphine and the like are not limited to these compounds.
作為胺基羰基化合物,可列舉4-(二甲氧基胺基)苯甲酸甲酯、4-(二甲基胺基)苯甲酸乙酯、4-(二甲基胺基)苯甲酸-2-正丁氧基乙酯、4-(二甲基胺基)苯甲酸異戊酯、苯甲酸-2-(二甲基胺基)乙酯、4,4'-雙-4-二甲基胺基二苯甲酮、4,4'-雙-4-二乙基胺基二苯甲酮、2,5'-雙(4-二乙基胺基亞苄基)環戊酮等,但並不限定於這些化合物。 作為光聚合起始劑的市售品,可列舉IGM樹脂(IGM Resins)製造的歐曼拉德(Omnirad)73、歐曼拉德(Omnirad)481、歐曼拉德(Omnirad)659、歐曼拉德(Omnirad)248、歐曼拉德(Omnirad)264、歐曼拉德(Omnirad)4817、歐曼拉德(Omnirad)BDK、歐曼拉德(Omnirad)TPO、歐曼拉德(Omnirad)TPO-L、歐曼拉德(Omnirad)380、歐曼珀(Omnipol)910、歐曼珀(Omnipol)BP、歐曼珀(Omnipol)2702、艾薩庫爾1(Esacure One)、艾薩庫爾(Esacure)1001M、艾薩庫爾(Esacure)A198、艾薩庫爾(Esacure)KIP150等。Examples of the aminocarbonyl compound include methyl 4- (dimethoxyamino) benzoate, ethyl 4- (dimethylamino) benzoate, and 4- (dimethylamino) benzoate-2 -N-butoxyethyl ester, 4- (dimethylamino) isoamyl benzoate, 2- (dimethylamino) ethyl benzoate, 4,4'-bis-4-dimethyl Aminobenzophenone, 4,4'-bis-4-diethylaminobenzophenone, 2,5'-bis (4-diethylaminobenzylidene) cyclopentanone, etc., but It is not limited to these compounds. Examples of commercially available photopolymerization initiators include Omnirad 73 manufactured by IGM Resins, Omnirad 481, Omnirad 659, and Auman Omnirad 248, Omnirad 264, Omnirad 4817, Omnirad BDK, Omnirad TPO, Omnirad TPO-L, Omnirad 380, Omnipol 910, Omnipol BP, Omnipol 2702, Esacure One, Esacure Esacure 1001M, Esacure A198, Esacure KIP150 and so on.
光聚合起始劑並不限定於所述化合物,只要具有通過光激發而引發聚合的能力,則可為任意化合物。這些光聚合起始劑可使用一種,也可混合使用兩種以上。 關於光聚合起始劑的使用量,並無特別限制,較佳為相對於本發明中的形成折射率匹配層的活性能量線硬化性組成物中的除金屬氧化物以外的固體成分100質量%,而在1質量%~20質量%的範圍內使用。再者,作為增感劑,也可添加已知的有機胺等。進而,除了所述自由基聚合用引發劑以外,還可併用陽離子聚合用的引發劑。The photopolymerization initiator is not limited to the compound, and may be any compound as long as it has the ability to initiate polymerization by photoexcitation. These photopolymerization initiators may be used singly or in combination of two or more kinds. The use amount of the photopolymerization initiator is not particularly limited, but is preferably 100% by mass relative to the solid content other than the metal oxide in the active energy ray-curable composition forming the refractive index matching layer in the present invention. , And used within the range of 1% to 20% by mass. In addition, as the sensitizer, a known organic amine or the like may be added. Furthermore, in addition to the initiator for radical polymerization, an initiator for cationic polymerization may be used in combination.
<其他的併用樹脂> 本發明中的活性能量線硬化性組成物也可含有其他高分子材料,可列舉但並不限定於:氯化聚丙烯樹脂、聚烯烴樹脂、乙烯-乙酸乙烯酯共聚物樹脂、乙酸乙烯酯樹脂、醇酸樹脂、聚氯乙烯樹脂、松香系樹脂、松香改質順丁烯二酸樹脂、萜烯樹脂、苯酚改質萜烯樹脂、酮樹脂、環化橡膠、氯化橡膠、縮丁醛、石油樹脂、及這些樹脂的改質樹脂等。這些樹脂可單獨使用,或者混合使用兩種以上,其含量較佳為在活性能量線硬化性組成物中的樹脂固體成分100質量%中為1質量%~20質量%。<Other combined resins> The active energy ray-curable composition in the present invention may also contain other polymer materials, and examples include but are not limited to chlorinated polypropylene resins, polyolefin resins, and ethylene-vinyl acetate copolymers. Resin, vinyl acetate resin, alkyd resin, polyvinyl chloride resin, rosin-based resin, rosin modified maleic acid resin, terpene resin, phenol modified terpene resin, ketone resin, cyclized rubber, chlorinated Rubber, butyral, petroleum resin, and modified resins of these resins. These resins can be used singly or in combination of two or more, and the content thereof is preferably 1 to 20% by mass based on 100% by mass of the resin solid content in the active energy ray-curable composition.
<添加劑> 本發明的活性能量線硬化性組成物可在不損及本發明的目的或效果的範圍內進一步包含多種添加劑。具體而言,可列舉:季戊四醇(甲基)丙烯酸酯系化合物及具有6個以上的(甲基)丙烯醯基且質量平均分子量為700~10000的丙烯酸酯樹脂以外的光硬化性化合物、聚合抑制劑、光增感劑、勻平劑、界面活性劑、抗菌劑、抗結塊劑、塑化劑、紫外線吸收劑、紅外線吸收劑、抗氧化劑、矽烷偶聯劑、導電性聚合物、導電性界面活性劑、無機填充劑、顏料、染料等,但並不限定於這些添加劑。<Additives> The active energy ray-curable composition of the present invention may further include various additives within a range that does not impair the object or effect of the present invention. Specific examples include photocurable compounds other than pentaerythritol (meth) acrylate-based compounds and acrylic resins having 6 or more (meth) acrylfluorene groups and a mass average molecular weight of 700 to 10,000, and polymerization inhibition. Agents, photosensitizers, levelling agents, surfactants, antibacterial agents, anticaking agents, plasticizers, ultraviolet absorbers, infrared absorbers, antioxidants, silane coupling agents, conductive polymers, conductivity Surfactants, inorganic fillers, pigments, dyes, etc. are not limited to these additives.
<活性能量線硬化性組成物的製造> 本發明的活性能量線硬化性組成物只要可均勻地攪拌混合則並無問題,例如可通過使用既定的攪拌機、分散機或均質機等,對構成活性能量線硬化性組成物的金屬氧化物、季戊四醇系化合物、丙烯酸酯樹脂、有機溶劑等均勻地進行攪拌來製造。關於氧化鋯、氧化鈦、氧化鋅等金屬氧化物,可調配與季戊四醇丙烯酸酯系化合物、胺基甲酸酯丙烯酸酯、聚酯丙烯酸酯等丙烯酸酯樹脂、及有機溶劑一起使用三根輥、砂磨機、錘磨機等進行了分散的金屬氧化物,也可調配市售的有機溶劑的分散體等來使用。<Production of active energy ray-curable composition> The active energy ray-curable composition of the present invention is not a problem as long as it can be uniformly stirred and mixed. For example, a predetermined blender, disperser, or homogenizer can be used to activate the composition. A metal oxide, a pentaerythritol-based compound, an acrylate resin, an organic solvent, and the like of the energy ray-curable composition are produced by uniformly stirring. For metal oxides such as zirconia, titanium oxide, and zinc oxide, three rollers and sanding can be used together with pentaerythritol acrylates, urethane acrylates, polyester acrylates and other acrylate resins, and organic solvents. A metal oxide that has been dispersed, such as a mill, a hammer mill, or the like, may be used by dispersing a commercially available organic solvent.
<折射率匹配層的製造> 繼而,對將活性能量線硬化性組成物進行硬化而成的折射率匹配層的製造方法進行說明。 折射率匹配層的製造方法例如包括:將活性能量線硬化性組成物塗布於基材上;以及照射活性能量線,使基材上的活性能量線硬化性組成物硬化。更具體而言,可通過以下方式形成:在將所述活性能量線硬化性組成物以乾燥後的膜厚成為較佳為0.02 μm~30 μm、更較佳為0.02 μm~20 μm的方式塗敷於基材上後,進行硬化處理。<Manufacture of a refractive index matching layer> Next, the manufacturing method of the refractive index matching layer which hardened the active-energy-ray-curable composition is demonstrated. A method for manufacturing the refractive index matching layer includes, for example, applying an active energy ray-curable composition to a substrate; and irradiating the active energy ray to harden the active energy ray-curable composition on the substrate. More specifically, it can be formed by coating the active energy ray-curable composition so that the film thickness after drying becomes preferably 0.02 μm to 30 μm, and more preferably 0.02 μm to 20 μm. After being applied to a substrate, a hardening treatment is performed.
作為塗敷方法,可使用已知的方法,例如可使用:利用棒(rod)或線棒(wire bar)等的方法,或微凹版、凹版、模、簾幕、模唇(lip)、狹縫(slot)或旋轉等各種塗布方法。As the coating method, a known method can be used, for example, a method using a rod or a wire bar, or a micro-gravure, a gravure, a mold, a curtain, a lip, a slit, or the like can be used. Various coating methods such as slot or rotation.
作為硬化方法,可通過使用已知的技術,例如照射紫外線、電子束、波長為400 nm~500 nm的可見光線等活性能量線來進行。紫外線及波長400 nm~500 nm的可見光線的線源(光源)例如可使用高壓水銀燈、超高壓水銀燈、金屬鹵化物燈、鎵燈、氙燈、碳弧燈等。電子束源可使用熱電子放射槍、電解放射槍等。就在步驟上容易管理的方面而言,所照射的活性能量線量的累計光量較佳為50 mJ/cm2 ~1000 mJ/cm2 的範圍內。照射這些活性能量線時可併用利用紅外線、遠紅外線、熱風、高頻加熱等的熱處理。The hardening method can be performed by using a known technique such as irradiation of active energy rays such as ultraviolet rays, electron beams, and visible rays having a wavelength of 400 to 500 nm. As the line source (light source) of ultraviolet rays and visible rays with a wavelength of 400 nm to 500 nm, for example, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, or a carbon arc lamp can be used. As the electron beam source, a thermionic radiation gun, an electrolytic radiation gun, or the like can be used. In terms of easy management in terms of steps, the cumulative light amount of the amount of active energy rays irradiated is preferably within a range of 50 mJ / cm 2 to 1000 mJ / cm 2 . When these active energy rays are irradiated, heat treatment using infrared rays, far infrared rays, hot air, and high-frequency heating can be used in combination.
折射率匹配層可在基材上塗敷活性能量線硬化性組成物,使其自然乾燥或強制乾燥後進行硬化處理而形成,也可在塗敷並進行硬化處理後使其自然乾燥或強制乾燥,但更較佳為在自然乾燥或強制乾燥後進行硬化處理。特別是在以電子束進行硬化的情況下,為了防止水導致的硬化阻礙或有機溶劑的殘留導致的塗膜的強度降低,更較佳為在自然乾燥或強制乾燥後進行硬化處理。硬化處理的時序可為與塗敷同時,也可為塗敷後。The refractive index matching layer can be formed by coating an active energy ray-curable composition on a substrate, and then subjecting it to natural drying or forced drying, followed by hardening treatment. Alternatively, it can be naturally dried or forced dried after being coated and hardened. However, it is more preferable to perform the hardening treatment after natural drying or forced drying. In particular, in the case of hardening by an electron beam, in order to prevent a reduction in the strength of the coating film due to the hindrance of hardening caused by water or the residue of an organic solvent, it is more preferable to perform the hardening treatment after natural drying or forced drying. The timing of the hardening treatment may be simultaneous with or after the application.
所獲得的硬化膜的透明性、黏接性優異,因此可較佳為作為光學材料來利用。硬化膜的厚度較佳為0.02 μm~30 μm。進而,硬化膜的折射率較佳為1.4~2.0的範圍,更較佳為1.5~1.9的範圍。Since the obtained cured film is excellent in transparency and adhesiveness, it can be preferably used as an optical material. The thickness of the cured film is preferably 0.02 μm to 30 μm. The refractive index of the cured film is preferably in the range of 1.4 to 2.0, and more preferably in the range of 1.5 to 1.9.
<透明導電層> 作為透明導電層的材料,可使用觸控螢幕的電極中使用的已知材料。例如可列舉:氧化錫、氧化銦、氧化銻、氧化鋅、銦錫氧化物(ITO)、氧化銻錫(Antimony Tin Oxide,ATO)等金屬氧化物,但並不限定於這些金屬氧化物。這些金屬氧化物中較佳為使用ITO。<Transparent conductive layer> As a material of the transparent conductive layer, a known material used for electrodes of a touch screen can be used. Examples include, but are not limited to, metal oxides such as tin oxide, indium oxide, antimony oxide, zinc oxide, indium tin oxide (ITO), and antimony tin oxide (Antimony Tin Oxide (ATO)). Among these metal oxides, ITO is preferably used.
例如就確保表面電阻值為103 Ω/□以下的良好導電性的觀點而言,透明導電層的厚度較佳為10 nm以上,更較佳為15 nm以上,特別較佳為20 nm以上。另一方面,如果透明導電層的厚度變得過大,則有時會產生透明性下降的不良情況,因此透明導電層的厚度的上限較佳為60 nm以下,更較佳為50 nm以下,特別較佳為40 nm以下。另外,透明導電層的折射率較佳為1.81以上,更較佳為1.85以上,進而較佳為1.90以上。透明導電層的折射率的上限較佳為2.20以下,更較佳為2.10以下。For example, from the viewpoint of ensuring good conductivity with a surface resistance value of 10 3 Ω / □ or less, the thickness of the transparent conductive layer is preferably 10 nm or more, more preferably 15 nm or more, and particularly preferably 20 nm or more. On the other hand, if the thickness of the transparent conductive layer becomes too large, there may be a problem that the transparency decreases. Therefore, the upper limit of the thickness of the transparent conductive layer is preferably 60 nm or less, more preferably 50 nm or less. It is preferably 40 nm or less. The refractive index of the transparent conductive layer is preferably 1.81 or more, more preferably 1.85 or more, and even more preferably 1.90 or more. The upper limit of the refractive index of the transparent conductive layer is preferably 2.20 or less, and more preferably 2.10 or less.
透明導電層的形成方法並無特別限定,可使用現有已知的方法。具體而言,例如可使用:真空蒸鍍法、濺鍍法、離子鍍法等乾式制程(dry process)。 對於以上述方式成膜的透明導電層,可根據透明導電膜所應用的用途而形成各種圖案。再者,通過透明導電層的圖案化而形成圖案部與非圖案部。作為圖案部的形狀,例如可列舉條紋(stripe)狀、格子狀等,但並不限定於這些形狀。透明導電層的圖案化通常是通過蝕刻來進行。例如,通過利用光顯影法、雷射曝光法、或印刷法,在透明導電層上形成圖案狀的抗蝕刻膜後進行蝕刻處理,從而使透明導電層圖案化。作為蝕刻液,可使用現有已知的蝕刻液,例如可使用氯化氫、溴化氫、硫酸、硝酸、磷酸等無機酸,乙酸等有機酸,及這些酸的混合物、以及它們的水溶液。The method for forming the transparent conductive layer is not particularly limited, and a conventionally known method can be used. Specifically, for example, a dry process such as a vacuum evaporation method, a sputtering method, or an ion plating method can be used. For the transparent conductive layer formed in the above manner, various patterns can be formed according to the application to which the transparent conductive film is applied. Furthermore, the patterned portion and the non-patterned portion are formed by patterning the transparent conductive layer. Examples of the shape of the pattern portion include a stripe shape and a lattice shape, but are not limited to these shapes. The patterning of the transparent conductive layer is usually performed by etching. For example, a photoresist method, a laser exposure method, or a printing method is used to form a patterned anti-etching film on the transparent conductive layer and then perform an etching process to pattern the transparent conductive layer. As the etching solution, conventionally known etching solutions can be used. For example, inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid, nitric acid, and phosphoric acid; organic acids such as acetic acid; a mixture of these acids;
本發明的層疊體只要具有基材、作為活性能量線硬化膜的折射率匹配層、以及透明導電層,且基材與折射率匹配層鄰接即可。除此以外的層構成為任意,可視需要在基材或折射率匹配層的單面設置折射率不同的膜或黏合層等。The laminate of the present invention is only required to have a substrate, a refractive index matching layer as an active energy ray cured film, and a transparent conductive layer, and the substrate and the refractive index matching layer may be adjacent to each other. The structure of the other layers is arbitrary, and if necessary, a film or an adhesive layer having a different refractive index is provided on one side of the base material or the refractive index matching layer.
以下列舉本發明的層疊體的若干較佳為構成例,但本發明並不限定於這些構成例。再者,下述構成例中,透明導電層為經圖案化的透明導電層。透明導電層以外的其他層未經圖案化。 (I)基材/折射率匹配層/透明導電層 (II)基材/折射率匹配層/(M)/透明導電層 (III)(M)/基材/折射率匹配層/透明導電層 (IV)(M)/基材/折射率匹配層/(M)/透明導電層 (V)(M)/折射率匹配層/基材/折射率匹配層/透明導電層 (VI)折射率匹配層/基材/折射率匹配層/透明導電層 其中,(M)表示折射率不同的膜或黏合層的任一層。Some preferred examples of the laminate of the present invention are listed below, but the present invention is not limited to these examples. In the following configuration examples, the transparent conductive layer is a patterned transparent conductive layer. The layers other than the transparent conductive layer are not patterned. (I) substrate / index matching layer / transparent conductive layer (II) substrate / index matching layer / (M) / transparent conductive layer (III) (M) / substrate / index matching layer / transparent conductive layer (IV) (M) / Substrate / Refractive index matching layer / (M) / Transparent conductive layer (V) (M) / Refractive index matching layer / Substrate / Refractive index matching layer / Transparent conductive layer (VI) Refractive index In the matching layer / base material / refractive index matching layer / transparent conductive layer, (M) represents any of films or adhesive layers having different refractive indexes.
折射率不同的膜為具有本發明的折射率匹配層所具有的功能以外的功能的膜。其形成方法並無特別限定,可利用已知的方法來形成。例如可使用:蒸鍍、濺鍍等乾式塗布法,利用棒(rod)、線棒的方法,或微凹版、凹版、模、簾幕、模唇、狹縫或旋轉等濕式塗布方法。所使用的材料也無限定,視需要可使用能夠對層疊體賦予信息記錄功能、防眩功能、牛頓環(Newton's rings)防止功能、黏合功能、特定波長的遮斷、色調修正等一種以上功能的任意的材料。The films having different refractive indexes are films having functions other than those of the refractive index matching layer of the present invention. The formation method is not particularly limited, and it can be formed by a known method. For example, a dry coating method such as vapor deposition or sputtering, a method using a rod or a wire rod, or a wet coating method such as a micro gravure, a gravure, a mold, a curtain, a die lip, a slit, or a spin can be used. The materials to be used are not limited, and if necessary, one or more functions capable of imparting an information recording function, an anti-glare function, a Newton's rings prevention function, a sticking function, blocking at a specific wavelength, and hue correction to the laminated body can be used. Any material.
本發明的層疊體在其製造時,在折射率匹配層或任意層的硬化時、或透明導電層的圖案化時照射活性能量線。本發明的層疊體在其製造過程中,即便對折射率匹配層照射的活性能量線的合計以累計光量計為6500 mJ/cm2 以上,基材與作為活性能量線硬化膜的折射率匹配層的黏接性也優異。再者,所謂所述累計光量,是指活性能量線的光量的合計值,可為一次照射的光量,也可為分數次照射的光量的合計。再者,在本發明中也包括用以形成折射率匹配層的硬化時的累計光量。再者,作為折射率匹配層的相對於累計光量的耐久性,較佳為6500 mJ/cm2 以上,更較佳為8000 mJ/cm2 以上。進而較佳為10000 mJ/cm2 以上。The laminated body of the present invention is irradiated with active energy rays during the manufacture of the refractive index matching layer or any layer during hardening or the patterning of the transparent conductive layer. In the manufacturing process of the laminate of the present invention, even if the total amount of active energy rays irradiated to the refractive index matching layer is 6500 mJ / cm 2 or more in cumulative light amount, the substrate and the refractive index matching layer as an active energy ray hardened film It is also excellent in adhesion. It should be noted that the cumulative light amount refers to a total value of the light amount of the active energy ray, and may be a total amount of light irradiated at one time or a total amount of light irradiated in fractions. It should be noted that the present invention also includes an integrated light amount during hardening for forming a refractive index matching layer. The durability of the refractive index matching layer with respect to the accumulated light amount is preferably 6500 mJ / cm 2 or more, and more preferably 8000 mJ / cm 2 or more. It is more preferably 10,000 mJ / cm 2 or more.
關於本發明的具有基材、折射率匹配層、以及透明導電層的層疊體的黏接性,就利用依據JIS K5600-5-6的附著性交叉切割法來評價的黏接性而言,為每單位面積中的剝離面積未滿15%,進而透明性及耐擦傷性也非常優異。剝離面積較佳為未滿10%,更較佳為未滿5%。 實施例The adhesiveness of the laminate having the substrate, the refractive index matching layer, and the transparent conductive layer of the present invention is, as far as the adhesiveness is evaluated by the adhesive cross-cut method according to JIS K5600-5-6, The peeling area per unit area is less than 15%, and the transparency and scratch resistance are also excellent. The peeling area is preferably less than 10%, and more preferably less than 5%. Examples
以下,列舉實施例對本發明進行詳細說明,但本發明不限定於這些實施例。再者,本發明中的份及%在無特別注釋的情況下,表示質量份及質量%。Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited to these examples. In addition, the part and% in this invention show a mass part and a mass% without a special note.
(平均粒徑) 使用日機裝公司製造的「納奇克(Nanotrac)UPA」,利用動態光散射法來測定,並使用D50的值。(Average particle diameter) The "Nanoc UPA" manufactured by Nikkiso Co., Ltd. was used to measure the dynamic light scattering method, and the value of D50 was used.
(比表面積) 依照JIS Z 8830:2001中記載的方法來求出。(Specific surface area) It calculated | required according to the method described in JIS Z 8830: 2001.
(酸價的測定方法) 依據JIS K 0070的電位差滴定法,對所測定的酸價(mgKOH/g)進行固體成分換算。(Measurement Method of Acid Value) The measured acid value (mgKOH / g) was converted into a solid content in accordance with the potentiometric titration method of JIS K 0070.
(質量平均分子量) 質量平均分子量是使用膠體滲透層析法(gel permeation chromatography,GPC)裝置(東曹(Tosoh)股份有限公司製造的HLC-8220)來測定分子量分佈,並作為將聚苯乙烯用作標準物質的換算分子量來求出。以下表示測定條件。 管柱:串聯連結使用以下管柱。 東曹(Tosoh)股份有限公司製造 TSKgel SuperAW2500 東曹(Tosoh)股份有限公司製造 TSKgel SuperAW3000 東曹(Tosoh)股份有限公司製造 TSKgel SuperAW4000 東曹(Tosoh)股份有限公司製造 TSKgel guardcolumn SuperAWH 檢測器:RI(示差折射率計) 測定條件:管柱溫度40℃ 溶離液:四氫呋喃 流速:1.0 mL/min(Mass average molecular weight) The mass average molecular weight is measured using a gel permeation chromatography (GPC) device (HLC-8220 manufactured by Tosoh Co., Ltd.), and is used for polystyrene. Calculate the molecular weight as a reference material. The measurement conditions are shown below. Tubing: Use the following tubing in series. TSKgel SuperAW2500 manufactured by Tosoh Co., Ltd. TSKgel SuperAW3000 manufactured by Tosoh Co., Ltd. TSKgel SuperAW4000 manufactured by Tosoh Co., Ltd. TSKgel guardcolumn SuperAWH detector manufactured by Tosoh Co., Ltd .: RI ( Differential refractive index meter) Measurement conditions: column temperature 40 ° C eluent: tetrahydrofuran flow rate: 1.0 mL / min
(合成例1)<胺基甲酸酯丙烯酸酯PU1> 在具備攪拌翼、溫度計、回流冷卻器、氣體導入管的燒瓶中投入150份的乙酸丙酯、17份的六亞甲基二異氰酸酯,一邊在溫度90℃下吹入空氣,一邊將60質量%的二季戊四醇五丙烯酸酯與40質量%的二季戊四醇六丙烯酸酯的混合物(製品名:「阿羅尼斯(Aronix)M403」東亞合成(股)製造)182份、及49份的乙酸丙酯充分混合後滴加,在滴加結束後維持10小時攪拌。再者,源自六亞甲基二異氰酸酯的異氰酸酯基與源自二季戊四醇五丙烯酸酯的羥基的莫耳比為異氰酸酯基:羥基=1:1。利用IR光譜確認到源自異氰酸酯基的峰值消失後,冷卻至室溫,獲得胺基甲酸酯丙烯酸酯與二季戊四醇六丙烯酸酯的混合物PU1。再者,PU1為以下性狀。 <PU1的性狀> ・PU1中的胺基甲酸酯丙烯酸酯與二季戊四醇六丙烯酸酯的固體成分質量比為61:39。 ・PU1中的胺基甲酸酯丙烯酸酯具有10个丙烯酰基。 ・PU1的质量平均分子量为1900。(Synthesis example 1) <urethane acrylate PU1> 150 parts of propyl acetate and 17 parts of hexamethylene diisocyanate were put into a flask equipped with a stirring blade, a thermometer, a reflux cooler, and a gas introduction tube, While blowing in air at a temperature of 90 ° C, a mixture of 60% by mass of dipentaerythritol pentaacrylate and 40% by mass of dipentaerythritol hexaacrylate (product name: "Aronix M403") (Production) 182 parts and 49 parts of propyl acetate were thoroughly mixed and added dropwise, and the stirring was maintained for 10 hours after the completion of the dropwise addition. The molar ratio of the isocyanate group derived from hexamethylene diisocyanate to the hydroxyl group derived from dipentaerythritol pentaacrylate is isocyanate group: hydroxyl group = 1: 1. After confirming that the peak derived from the isocyanate group disappeared by IR spectrum, it was cooled to room temperature to obtain PU1, a mixture of urethane acrylate and dipentaerythritol hexaacrylate. Furthermore, PU1 has the following properties. <Properties of PU1>-The solid content mass ratio of the urethane acrylate and dipentaerythritol hexaacrylate in PU1 was 61:39. -The urethane acrylate in PU1 has 10 acryl groups.・ The mass average molecular weight of PU1 is 1900.
(合成例2)<胺基甲酸酯丙烯酸酯PU2> 使用22份的異佛爾酮二異氰酸酯來代替合成例1中使用的17份的六亞甲基二異氰酸酯,除此以外,進行與合成例1相同的操作,獲得胺基甲酸酯丙烯酸酯與二季戊四醇六丙烯酸酯的混合物PU2。再者,PU2為以下性狀。 <PU2的性狀> ・PU2中的胺基甲酸酯丙烯酸酯與二季戊四醇六丙烯酸酯的固體成分質量比為63:37。 ・PU2中的胺基甲酸酯丙烯酸酯具有10个丙烯酰基。 ・PU2的质量平均分子量为2100。(Synthesis Example 2) <Carbamate Acrylate PU2> In addition to 22 parts of isophorone diisocyanate, 17 parts of hexamethylene diisocyanate used in Synthesis Example 1 were replaced and synthesized. In the same manner as in Example 1, a mixture PU2 of a urethane acrylate and dipentaerythritol hexaacrylate was obtained. Furthermore, PU2 has the following properties. <Properties of PU2>-The solid content mass ratio of the urethane acrylate and dipentaerythritol hexaacrylate in PU2 was 63:37. -The urethane acrylate in PU2 has 10 acryl groups.・ The mass average molecular weight of PU2 is 2100.
(合成例3)<胺基甲酸酯丙烯酸酯PU3> 使用22份的異佛爾酮二異氰酸酯來代替合成例1中使用的17份的六亞甲基二異氰酸酯,進而使用季戊四醇三丙烯酸酯與季戊四醇四丙烯酸酯的質量比為70:30的混合物(製品名:「阿羅尼斯(Aronix)M306」東亞合成(股)製造)90重量份來代替合成例1中使用的「阿羅尼斯(Aronix)M403」(二季戊四醇五丙烯酸酯與二季戊四醇六丙烯酸酯的質量比為60:40的混合物)182份,除此以外,進行與合成例1相同的操作,獲得胺基甲酸酯丙烯酸酯與季戊四醇三丙烯酸酯的混合物PU3。再者,PU3為以下性狀。 <PU3的性狀> ・PU3中的胺基甲酸酯丙烯酸酯與季戊四醇三丙烯酸酯的固體成分質量比為73:27。 ・PU3中的胺基甲酸酯丙烯酸酯具有6个丙烯酰基。 ・PU3的质量平均分子量为1500。(Synthesis Example 3) <Urethane acrylate PU3> 22 parts of isophorone diisocyanate were used instead of 17 parts of hexamethylene diisocyanate used in Synthesis Example 1, and pentaerythritol triacrylate and 90 parts by weight of a mixture of pentaerythritol tetraacrylate with a mass ratio of 70:30 (product name: "Aronix M306" manufactured by Toa Kosei Co., Ltd.) was used in place of "Aronix (Aronix ) M403 "(mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate in a mass ratio of 60:40) 182 parts, except that the same operation as in Synthesis Example 1 was performed to obtain a urethane acrylate and A mixture of pentaerythritol triacrylate PU3. Furthermore, PU3 has the following properties. <Properties of PU3>-The solid content mass ratio of urethane acrylate and pentaerythritol triacrylate in PU3 was 73:27. -The urethane acrylate in PU3 has 6 acryl groups.・ The mass average molecular weight of PU3 is 1500.
(合成例4)<聚酯丙烯酸酯PE1> 在具備攪拌機、回流冷卻器、乾燥空氣導入管、溫度計的四口燒瓶中投入80.0份的3,3',4,4'-聯苯四羧酸二酐、250.0份的羥基價為122 mgKOH/g的季戊四醇三丙烯酸酯(日本化藥公司製造 季戊四醇三丙烯酸酯 製品名:卡亞拉得(KAYARAD)PET-30,作為副產物而包含季戊四醇四丙烯酸酯)、0.24份的甲基對苯二酚、217.8份的環己酮,升溫至60℃。繼而,添加1.65份的1,8-二氮雜雙環[5.4.0]-7-十一烯作為催化劑,在90℃下攪拌8小時。利用反應物的IR測定而確認到酸酐基的峰值、即1780 cm-1 及1850 cm-1 附近的峰值消失後,加以冷卻並停止反應。在該時間點測定反應物的酸價,結果為94 mgKOH/g。 其後,添加78.3份的甲基丙烯酸縮水甘油醚、54.0份的環己酮,繼而添加2.65份的二甲基苄基胺作為催化劑,在100℃下攪拌6小時,一邊繼續反應一邊定期測定反應物的酸價,在酸價成為5.0 mgKOH/g以下時,冷卻至室溫並停止反應。所獲得的樹脂清漆為淡黃色且透明,固體成分為60%,最終的酸價為3.0 mgKOH/g。自酸價進行換算,獲得聚酯丙烯酸酯與季戊四醇四丙烯酸酯的混合物PE1。 <PE1的性狀> ・PE1中的聚酯丙烯酸酯與季戊四醇四丙烯酸酯的固體成分質量比為76:24。 ・PE1中的聚酯丙烯酸酯具有8个丙烯酰基。 ・PE1的质量平均分子量为3500。(Synthesis Example 4) <Polyester Acrylate PE1> 80.0 parts of 3,3 ', 4,4'-biphenyltetracarboxylic acid was put into a four-necked flask equipped with a stirrer, a reflux cooler, a dry air introduction tube, and a thermometer. Dianhydride, 250.0 parts of pentaerythritol triacrylate with a hydroxyl value of 122 mgKOH / g (Pentaerythritol triacrylate manufactured by Nippon Kayaku Co., Ltd. Product name: KAYARAD PET-30, containing pentaerythritol tetraacrylic acid as a by-product Ester), 0.24 parts of methyl hydroquinone, and 217.8 parts of cyclohexanone, and the temperature was raised to 60 ° C. Then, 1.65 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and it stirred at 90 degreeC for 8 hours. It was confirmed by IR measurement of the reactant that the peak of the acid anhydride group, that is, peaks around 1780 cm -1 and 1850 cm -1 disappeared, and then the reaction was cooled to stop the reaction. The acid value of the reactant was measured at this time point, and it was 94 mgKOH / g. Thereafter, 78.3 parts of glycidyl methacrylate and 54.0 parts of cyclohexanone were added, and then 2.65 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C for 6 hours. The reaction was periodically measured while continuing the reaction. When the acid value of the product becomes 5.0 mgKOH / g or less, it is cooled to room temperature and the reaction is stopped. The obtained resin varnish was light yellow and transparent, had a solid content of 60%, and the final acid value was 3.0 mgKOH / g. Conversion from the acid value yielded a mixture PE1 of polyester acrylate and pentaerythritol tetraacrylate. <Properties of PE1>-The solid content mass ratio of polyester acrylate and pentaerythritol tetraacrylate in PE1 was 76:24.・ The polyester acrylate in PE1 has 8 acryl groups.・ The mass average molecular weight of PE1 is 3500.
(合成例5)<聚酯丙烯酸酯PE2> 在具備攪拌機、回流冷卻器、乾燥空氣導入管、溫度計的四口燒瓶中投入80.0份的3,3',4,4'-聯苯四羧酸二酐、359.0份的羥基價為85 mgKOH/g的二季戊四醇五丙烯酸酯(新中村化學工業(股)製造,二季戊四醇五丙烯酸酯 製品名:A-9570W,作為副產物也包含二季戊四醇六丙烯酸酯)、0.29份的甲基對苯二酚、290.1份的環己酮,升溫至60℃。繼而,添加2.19份的1,8-二氮雜雙環[5.4.0]-7-十一烯作為催化劑,在90℃下攪拌8小時。利用反應物的IR測定而確認到酸酐基的峰值、即1780 cm-1 及1850 cm-1 附近的峰值消失後,加以冷卻並停止反應。 在該時間點測定反應物的酸價,結果為74 mgKOH/g。 其後,添加78.3份的甲基丙烯酸縮水甘油醚、48.7份的環己酮,繼而添加3.53份的二甲基苄基胺作為催化劑,在100℃下攪拌6小時,一邊繼續反應一邊定期測定反應物的酸價,在酸價成為5.0 mgKOH/g以下時,冷卻至室溫並停止反應。所獲得的樹脂清漆為淡黃色且透明,固體成分為60%,最終的酸價為3.0 mgKOH/g。自酸價進行換算,獲得聚酯丙烯酸酯與二季戊四醇六丙烯酸酯的混合物PE2。 <PE2的性狀> ・PE2中的聚酯丙烯酸酯與二季戊四醇六丙烯酸酯的固體成分質量比為69:31。 ・PE2中的聚酯丙烯酸酯具有12个丙烯酰基。 ・PE2的质量平均分子量为4000。(Synthesis Example 5) <Polyester Acrylate PE2> 80.0 parts of 3,3 ', 4,4'-biphenyltetracarboxylic acid was put into a four-necked flask equipped with a stirrer, a reflux cooler, a dry air introduction tube, and a thermometer. Dianhydride, 359.0 parts of dipentaerythritol pentaacrylate with a hydroxyl value of 85 mgKOH / g (manufactured by Shin Nakamura Chemical Industry Co., Ltd., dipentaerythritol pentaacrylate product name: A-9570W, as a by-product also includes dipentaerythritol hexaacrylic acid Ester), 0.29 parts of methyl hydroquinone, and 290.1 parts of cyclohexanone, and the temperature was raised to 60 ° C. Then, 2.19 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and it stirred at 90 degreeC for 8 hours. It was confirmed by IR measurement of the reactant that the peak of the acid anhydride group, that is, peaks around 1780 cm -1 and 1850 cm -1 disappeared, and then the reaction was cooled to stop the reaction. The acid value of the reactant was measured at this time point, and it was 74 mgKOH / g. Thereafter, 78.3 parts of glycidyl methacrylate and 48.7 parts of cyclohexanone were added, followed by 3.53 parts of dimethylbenzylamine as a catalyst, and the mixture was stirred at 100 ° C for 6 hours. The reaction was periodically measured while continuing the reaction. When the acid value of the product becomes 5.0 mgKOH / g or less, it is cooled to room temperature and the reaction is stopped. The obtained resin varnish was light yellow and transparent, had a solid content of 60%, and the final acid value was 3.0 mgKOH / g. Converted from the acid value, a mixture PE2 of polyester acrylate and dipentaerythritol hexaacrylate was obtained. <Properties of PE2>-The solid content mass ratio of polyester acrylate and dipentaerythritol hexaacrylate in PE2 was 69:31.・ The polyester acrylate in PE2 has 12 acryl groups.・ The mass average molecular weight of PE2 is 4000.
(比較合成例1)<胺基甲酸酯丙烯酸酯PU4> 使用67份的異佛爾酮二異氰酸酯(NOC基:2個)來代替合成例1中使用的17份的六亞甲基二異氰酸酯,進而使用139重量份的丙烯酸-2-羥基乙酯來代替合成例1中使用的「阿羅尼斯(Aronix)M403」(二季戊四醇五丙烯酸酯與二季戊四醇六丙烯酸酯的混合物)182份,除此以外,進行與合成例3相同的操作,獲得胺基甲酸酯丙烯酸酯PU4。再者,源自異佛爾酮二異氰酸酯的異氰酸酯基與源自丙烯酸-2-羥基乙酯的羥基的莫耳比為異氰酸酯基:羥基(源自丙烯酸-2-羥基乙酯)=1:1。將PU4的性狀示於以下。 <PU4的性狀> ・PU4中不包含季戊四醇丙烯酸酯系化合物。 ・PU4具有2个丙烯酰基。 ・PU4的质量平均分子量为1000。(Comparative Synthesis Example 1) <Urethane acrylate PU4> 67 parts of isophorone diisocyanate (NOC group: 2) were used instead of 17 parts of hexamethylene diisocyanate used in Synthesis Example 1 139 parts by weight of 2-hydroxyethyl acrylate was used instead of 182 parts of "Aronix M403" (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate) used in Synthesis Example 1, except that Other than that, the same operation as in Synthesis Example 3 was performed to obtain a urethane acrylate PU4. Moreover, the molar ratio of the isocyanate group derived from isophorone diisocyanate to the hydroxyl group derived from 2-hydroxyethyl acrylate is isocyanate group: hydroxyl group (derived from 2-hydroxyethyl acrylate) = 1: 1 . The properties of PU4 are shown below. <Properties of PU4>-PU4 does not contain pentaerythritol acrylate compounds.・ PU4 has 2 acryl groups.・ The mass average molecular weight of PU4 is 1,000.
本說明書中,實施例5~9與實施例15~16以外為參考例 (實施例1)<活性能量線硬化性組成物S1的製作> 作為金屬氧化物,使用以ZrO2 固體成分計為47份的ZrO2 分散體(1):粒子濃度為30質量%、平均粒徑為4 nm(堺化學公司製造 製品名:「SZR-K」)、以及以TiO2 固體成分計為5份的TiO2 分散體(1):粒子濃度為15質量%、平均粒徑為36 nm、比表面積為45 m2 /g 金紅石型氧化鈦 球狀粒子(CIK納泰克(CIK NanoTeck)公司製造 製品名:「納泰克(NanoTeck)TiO2 」),並混合作為季戊四醇丙烯酸酯系化合物的44份的季戊四醇四丙烯酸酯(東亞合成公司製造 製品名:「阿羅尼斯(Aronix)M450」),進而添加作為光聚合起始劑的4份的艾薩庫爾1(ESACURE ONE)(IGM樹脂(IGM Resins)製造 寡聚[2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮]),並以將固體成分調整為40%的方式添加作為有機溶劑的丙二醇單甲醚,獲得活性能量線硬化性組成物S1。In this specification, Examples 5 to 9 and Examples 15 to 16 are reference examples (Example 1) <Production of active energy ray-curable composition S1> As the metal oxide, 47 based on the solid content of ZrO 2 was used. Parts of ZrO 2 dispersion (1): a particle concentration of 30% by mass, an average particle size of 4 nm (product name manufactured by Sakai Chemical Co., Ltd .: "SZR-K"), and 5 parts of TiO as a solid content of TiO 2 2 Dispersion (1): The particle concentration is 15% by mass, the average particle size is 36 nm, and the specific surface area is 45 m 2 / g. Rutile titanium oxide spherical particles (CIK NanoTeck) Product name: "NanoTeck TiO 2 "), and 44 parts of pentaerythritol tetraacrylate as a pentaerythritol acrylate-based compound (product name of Toa Sangyo Co., Ltd .: "Aronix M450") were mixed, and further added as light Oligomeric [2-hydroxy-2-methyl-1- [4- (1-methylvinyl)] made of 4 parts of ESACURE ONE (IGM Resins) as a polymerization initiator Phenyl] acetone]), and added as organic by adjusting the solid content to 40% Agent is propylene glycol monomethyl ether, to obtain an active energy ray curable composition S1.
(實施例2~實施例20)<活性能量線硬化性組成物S2~活性能量線硬化性組成物S20的製作> 除使用表1中記載的原料及組成比例以外,以與實施例1相同的順序製作活性能量線硬化性組成物S2~活性能量線硬化性組成物S20。再者,表1中的略稱示於以下。 ZrO2 分散體(2):粒子濃度為30質量%、平均粒徑為19 nm 一次粒徑為10 nm以下(艾泰克(ITEC)公司製造 製品名:「吉考奈(Zirconeo)-Ck」) TiO2 分散體(2):粒子濃度為20質量%、平均粒徑為13 nm 比表面積為120 m2 /g 金紅石型氧化鈦(日揮催化劑公司製造 製品名:「奧普托雷克(Optolake)6320Z」) ZnO分散體:粒子濃度為15質量%、平均粒徑為34 nm 體積密度0.36 g/cm3 比表面積為30 m2 /g(CIK納泰克(CIK NanoTeck)公司製造 製品名:「納泰克(NanoTeck)ZnO」) PET4A:季戊四醇四丙烯酸酯(東亞合成(股)製造,製品名:「阿羅尼斯(Aronix)M450」) DPHA:二季戊四醇六丙烯酸酯(沙多瑪(Sartomer)公司製造,製品名:「DPHA」) PET3A/PET4A=70/30:季戊四醇三丙烯酸酯/季戊四醇四丙烯酸酯=70/30的混合物(東亞合成(股)製造,製品名:「阿羅尼斯(Aronix)M306」) DPPA/DPHA=60/40:二季戊四醇五丙烯酸酯/二季戊四醇六丙烯酸酯=60/40的混合物(東亞合成(股)製造,製品名:「阿羅尼斯(Aronix)M403」)(Examples 2 to 20) <Production of active energy ray-curable composition S2 to active energy ray-curable composition S20> The same materials as in Example 1 were used except that the raw materials and composition ratios described in Table 1 were used. The active-energy-ray-curable composition S2 to the active-energy-ray-curable composition S20 are sequentially prepared. The abbreviations in Table 1 are shown below. ZrO 2 dispersion (2): particle concentration is 30% by mass, average particle size is 19 nm, and primary particle size is 10 nm or less (Product name of "ITEC" company: "Zirconeo-Ck") TiO 2 dispersion (2): particle concentration of 20% by mass, average particle size of 13 nm, specific surface area of 120 m 2 / g, rutile titanium oxide (product name manufactured by Niwa Catalyst Co., Ltd .: "Optolake ) 6320Z ") ZnO dispersion: particle concentration is 15% by mass, average particle size is 34 nm, bulk density is 0.36 g / cm 3, specific surface area is 30 m 2 / g (CIK NanoTeck) product name:" NanoTeck ZnO ") PET4A: Pentaerythritol tetraacrylate (manufactured by Toa Kosei Co., Ltd., product name:" Aronix M450 ") DPHA: dipentaerythritol hexaacrylate (Sartomer) Manufactured, product name: "DPHA") PET3A / PET4A = 70/30: Pentaerythritol triacrylate / Pentaerythritol tetraacrylate = 70/30 mixture (manufactured by East Asia Synthesis Co., Ltd., product name: "Aronix" M306 ") DPPA / DPHA = 60/4 0: A mixture of dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate = 60/40 (manufactured by Toa Kosei Co., Ltd., product name: "Aronix M403")
(實施例21)<層疊體R1的製作> 利用棒塗布機,以乾燥後的膜厚成為1.5 μm的方式,將活性能量線硬化性組成物S1塗敷於125 μm厚的易黏接處理聚酯(PET)膜(東麗(Toray)(股)製造的「露米勒(Lumirror)UH13」)上後,利用高壓水銀燈照射500 mJ/cm2 的紫外線,形成折射率匹配層。進而,在所獲得的折射率匹配層上,以作為透明導電層的ITO膜的厚度成為30 nm的方式利用濺鍍法來層疊後,僅對透明導電層進行圖案加工(蝕刻處理)而形成為條紋狀,獲得本發明的層疊體R1。(Example 21) <Preparation of laminated body R1> An active energy ray-curable composition S1 was applied to a 125 μm-thick, easily-adhesive polymer using a bar coater so that the film thickness after drying became 1.5 μm. After the polyester (PET) film ("Lumirror UH13" manufactured by Toray Co., Ltd.) was applied, 500 mJ / cm 2 of ultraviolet light was irradiated with a high-pressure mercury lamp to form a refractive index matching layer. Furthermore, on the obtained refractive index matching layer, after laminating by a sputtering method so that the thickness of the ITO film as a transparent conductive layer became 30 nm, only the transparent conductive layer was patterned (etched) to form Stripe shape, to obtain the laminate R1 of the present invention.
(實施例22~實施例40)<層疊體R2~層疊體R20的製作> 除使用表1中記載的活性能量線硬化性組成物S2~活性能量線硬化性組成物S20以外,以與實施例21相同的順序製作層疊體R2~層疊體R20。(Examples 22 to 40) <Preparation of Laminated Body R2 to Laminated Body R20> Except that the active energy ray curable composition S2 to the active energy ray curable composition S20 described in Table 1 were used, the same procedures as in the examples were used. In the same order as 21, a laminated body R2 to a laminated body R20 were produced.
(比較例1~比較例10)<活性能量線硬化性組成物SS1~活性能量線硬化性組成物SS10的製作> 除使用表2中記載的原料及組成比例以外,以與實施例1相同的順序製作活性能量線硬化性組成物SS1~活性能量線硬化性組成物SS10。再者,表2中的略稱示於以下。 Al2 O3 分散體:粒子濃度為15質量%、平均粒徑為31 nm 比表面積為55 m2 /g(製品名:「納泰克(NanoTeck)Al2 O3 」,CIK納泰克(CIK NanoTeck)(股)公司製造) SiO2 分散體:粒子濃度為15質量%、平均粒徑為25 nm 比表面積為110 m2 /g(製品名:「納泰克(NanoTeck)SiO2 」,CIK納泰克(CIK NanoTeck)(股)公司製造) TMPTA:三羥甲基丙烷三丙烯酸酯 新中村化學公司製造 DTMPTA:二-三羥甲基丙烷四丙烯酸酯 新中村化學公司製造(Comparative example 1 to comparative example 10) <Production of active energy ray curable composition SS1 to active energy ray curable composition SS10> The same materials as in Example 1 were used except that the raw materials and composition ratios shown in Table 2 were used. The active energy ray-curable composition SS1 to the active energy ray-curable composition SS10 were sequentially prepared. The abbreviations in Table 2 are shown below. Al 2 O 3 dispersion: particle concentration is 15% by mass, average particle size is 31 nm, specific surface area is 55 m 2 / g (product name: "NanoTeck" Al 2 O 3 ", CIK NanoTeck (Manufactured by the company) SiO 2 dispersion: particle concentration is 15% by mass, average particle size is 25 nm, specific surface area is 110 m 2 / g (product name: "NanoTeck SiO 2 ", CIK Nateck (Manufactured by CIK NanoTeck) TMPTA: trimethylolpropane triacrylate manufactured by Shin Nakamura Chemical Co., Ltd. DTMPTA: di-trimethylolpropane tetraacrylate manufactured by Shin Nakamura Chemical Co., Ltd.
(比較例11~比較例20)<層疊體RR1~層疊體RR10的製作> 除使用表2中記載的活性能量線硬化性組成物SS1~活性能量線硬化性組成物SS10以外,以與實施例21相同的順序製作層疊體RR1~層疊體RR10。(Comparative Example 11 to Comparative Example 20) <Preparation of Laminate RR1 to Laminate RR10> Except that the active energy ray-curable composition SS1 to the active energy ray-curable composition SS10 described in Table 2 were used, the examples were the same as the examples. In the same order as 21, a laminated body RR1 to a laminated body RR10 were produced.
[評價] 使用上述中所獲得的活性能量線硬化性組成物S1~活性能量線硬化性組成物S20(實施例)及活性能量線硬化性組成物SS1~活性能量線硬化性組成物SS10(比較例)、層疊體R1~層疊體R20(實施例)、層疊體RR1~層疊體RR10(比較例),進行以下評價。再者,將評價結果示於表3及表4。[Evaluation] The active energy ray curable composition S1 to the active energy ray curable composition S20 (Example) and the active energy ray curable composition SS1 to the active energy ray curable composition SS10 (Comparative) Example), laminated body R1 to laminated body R20 (example), laminated body RR1 to laminated body RR10 (comparative example), and the following evaluations were performed. The evaluation results are shown in Tables 3 and 4.
<黏接性>(基材/折射率匹配層間) 在層疊體R1~層疊體R20(實施例)、層疊體RR1~層疊體RR10(比較例)中,利用高壓水銀燈照射以累計光量計為6500 mJ/cm2 、10500 mJ/cm2 、14500 mJ/cm2 的紫外線後,針對層疊體的未層疊ITO層的部分,依據JIS K5600-5-6,利用附著性交叉切割法對基材/折射率匹配層間的黏接性進行評價。再者,將所述JIS標準中的0~5的評價分別替換為A~F來表述。 <評價基準> A:切口的邊緣完全光滑,任一格子孔中均無剝落。 B:切口的交叉點處的層疊體有小的剝落。每單位面積中的剝落未滿5%。 C:層疊體沿著切口的邊緣、及/或在交叉點處剝落。每單位面積中的剝落為5%以上且未滿15%。 D:層疊體沿著切口的邊緣,局部地或全面性地產生大的剝落,及/或孔的許多部分局部地或全面性地剝落。每單位面積中的剝落為15%以上且未滿35%。 E:層疊體沿著切口的邊緣,局部地或全面性地產生大的剝落,及/或數個部位的孔局部地或全面性地剝落。每單位面積中的剝落未滿35%。 F:每單位面積中的剝落為35%以上。 再者,A及B為實用上無問題的水平。<Adhesiveness> (Substrate / Refractive Index Matching Layer) In the laminated body R1 to laminated body R20 (Example), laminated body RR1 to laminated body RR10 (comparative example), a high-pressure mercury lamp was irradiated with a cumulative light amount of 6,500. After ultraviolet rays of mJ / cm 2 , 10500 mJ / cm 2 , 14500 mJ / cm 2 , the substrate / refraction is determined by the adhesive cross-cut method according to JIS K5600-5-6 for the non-laminated ITO layer of the laminate. The adhesion between layers was evaluated by rate matching. In addition, the evaluation of 0 to 5 in the JIS standard is replaced by A to F, respectively. <Evaluation Criteria> A: The edge of the cut was completely smooth, and no peeling occurred in any of the grid holes. B: The laminate at the intersection of the cuts has small peeling. Exfoliation is less than 5% per unit area. C: The laminate is peeled off along the edge of the cut and / or at the intersection. Exfoliation per unit area is 5% or more and less than 15%. D: The laminated body locally or comprehensively exfoliates along the edges of the cuts, and / or many parts of the holes exfoliate locally or comprehensively. The peeling per unit area is 15% or more and less than 35%. E: The laminated body is locally or comprehensively exfoliated along the edge of the incision, and / or the holes in several locations are locally or fully exfoliated. Exfoliation is less than 35% per unit area. F: Peeling per unit area is 35% or more. Furthermore, A and B are practically problem-free levels.
<黏接性>(折射率匹配層/透明電極間) 在層疊體R1~層疊體R20(實施例)、層疊體RR1~層疊體RR10(比較例)中,利用高壓水銀燈照射以累計光量計為6500 mJ/cm2 、10500 mJ/cm2 、14500 mJ/cm2 的紫外線後,針對層疊體的未層疊ITO層的部分,依據JIS K5600-5-6,利用附著性交叉切割法對折射率匹配層/透明電極間的黏接性進行評價。評價基準如上所述。<Adhesiveness> (between refractive index matching layer / transparent electrode) In the laminated body R1 to laminated body R20 (Example), laminated body RR1 to laminated body RR10 (comparative example), a high-pressure mercury lamp was irradiated with the cumulative light amount as: After 6500 mJ / cm 2 , 10500 mJ / cm 2 , and 14500 mJ / cm 2 ultraviolet rays, the refractive index of the part of the laminated body without the ITO layer was matched according to JIS K5600-5-6 by the adhesive cross cutting method. The adhesion between the layers / transparent electrodes was evaluated. The evaluation criteria are as described above.
<透明性(霧度值)> 在層疊體R1~層疊體R20(實施例)、層疊體RR1~層疊體RR10(比較例)中,針對層疊體的未層疊ITO層的部分,關於透明性(霧度值),使用霧度計(haze meter)(須賀試驗機公司製造)對濁度進行測定。 A:霧度值未滿1.0%。 B:霧度值為1.0%以上且未滿1.5%。 C:霧度值為1.5%以上且未滿2.0%。 D:霧度值為2.0%以上且未滿3.0%。 E:霧度值為3.0%以上。 再者,A、B為實用上無問題的水平。<Transparency (haze value)> In the laminated body R1 to laminated body R20 (Example), the laminated body RR1 to laminated body RR10 (comparative example), regarding the part of the laminated body where the ITO layer is not laminated, the transparency ( Haze value), and the haze was measured using a haze meter (manufactured by Suga Test Machine Co., Ltd.). A: The haze value is less than 1.0%. B: The haze value is 1.0% or more and less than 1.5%. C: The haze value is 1.5% or more and less than 2.0%. D: The haze value is 2.0% or more and less than 3.0%. E: The haze value is 3.0% or more. Furthermore, A and B are practically problem-free levels.
<耐擦傷性> 將層疊體R1~層疊體R20(實施例)、層疊體RR1~層疊體RR10(比較例)分別設置於學振試驗機上,使用No.0000的鋼絲絨以負載250 g刮擦10次。針對所取出的層疊體,依照以下5個階段的目視評價來判斷受損情況。 A:完全未劃傷。 B:輕微劃傷。 C:雖有劃傷,但未看到基材。 D:有劃傷,且一部分硬化膜剝落。 E:硬化膜剝落,而為基材露出的狀態。 再者,A及B為實用上無問題的水平。<Scratch resistance> Laminates R1 to R20 (Examples) and Laminates RR1 to RR10 (Comparative Examples) were respectively set on a school vibration test machine, and steel wool No. 0000 was used to load 250 g of scrape Rub 10 times. About the removed laminated body, the damage was judged according to the following 5 stages of visual evaluation. A: No scratch at all. B: Slight scratches. C: Although scratched, the substrate was not seen. D: There are scratches, and part of the cured film is peeled off. E: The cured film is peeled and the base material is exposed. Furthermore, A and B are practically problem-free levels.
根據表3及表4的結果而判明,層疊體R1~層疊體R20(實施例)在透明性、耐擦傷性與黏接性上均平衡性良好而優異。另外,即便作為活性能量線硬化膜的折射率匹配層中包含金屬氧化物,透明性與黏接性也平衡性良好而優異。From the results of Tables 3 and 4, it was found that the laminates R1 to R20 (Examples) are excellent in balance in transparency, abrasion resistance, and adhesion, and are excellent. Moreover, even if a metal oxide is contained in the refractive index matching layer as an active energy ray hardened film, transparency and adhesiveness are well balanced and excellent.
與此相對,層疊體RR1~層疊體RR10(比較例)的聚酯基材與作為活性能量線硬化膜的折射率匹配層的黏接性以及作為活性能量線硬化膜的折射率匹配層與透明導電層的黏接性大體上不充足。另外判明,在黏接性良好的情況下,透明性或耐擦傷性劣化。In contrast, the adhesion between the polyester substrate of the laminate RR1 to the laminate RR10 (comparative example) and the refractive index matching layer as the active energy ray cured film, and the refractive index matching layer as the active energy ray cured film is transparent. The adhesiveness of the conductive layer is generally insufficient. In addition, it was found that when the adhesiveness was good, the transparency or scratch resistance deteriorated.
根據本發明,可提供一種用以形成折射率匹配層的活性能量線硬化性組成物,所述折射率匹配層即便過量地照射活性能量線,透明性與耐擦傷性也良好,且可保持相對於基材及透明導電層的黏接性。According to the present invention, it is possible to provide an active energy ray-curable composition for forming a refractive index matching layer. Even if the refractive index matching layer is excessively irradiated with active energy rays, the transparency and scratch resistance are good, and the relative resistance Adhesion to substrate and transparent conductive layer.
[表1]
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JP6750666B2 (en) * | 2018-12-27 | 2020-09-02 | 東洋インキScホールディングス株式会社 | Laminated body and method for manufacturing laminated body |
JP2020176215A (en) * | 2019-04-19 | 2020-10-29 | 株式会社Adeka | Composition, cured material, and production method of cured material |
KR20220044113A (en) * | 2020-09-30 | 2022-04-06 | 아라까와 가가꾸 고교 가부시끼가이샤 | Active energy ray-curable resin composition and laminate |
JP7137726B1 (en) | 2022-03-31 | 2022-09-14 | サカタインクス株式会社 | Active energy ray-curable adhesive composition |
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