TWI656971B - Polarizing plate and liquid crystal display panel - Google Patents
Polarizing plate and liquid crystal display panel Download PDFInfo
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- TWI656971B TWI656971B TW104108051A TW104108051A TWI656971B TW I656971 B TWI656971 B TW I656971B TW 104108051 A TW104108051 A TW 104108051A TW 104108051 A TW104108051 A TW 104108051A TW I656971 B TWI656971 B TW I656971B
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3075—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state for use in the UV
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
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- Crystallography & Structural Chemistry (AREA)
- Polarising Elements (AREA)
- Laminated Bodies (AREA)
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Abstract
本發明係提供一種偏光板,係包括偏光片、積層於偏光片的一側的面之第1(甲基)丙烯酸系樹脂膜、以及積層於偏光片的另一側的面之第2(甲基)丙烯酸系樹脂膜;其中,前述第1(甲基)丙烯酸系樹脂膜係含有紫外線吸收劑且在190至380nm的波長全部區域的穿透率為20%以下,前述第2(甲基)丙烯酸系樹脂膜之紫外線吸收劑的含量為1重量%以下;以及使用該偏光板之液晶面板。 The present invention provides a polarizing plate comprising a polarizer, a first (meth) acrylic resin film laminated on one side of the polarizer, and a second (a) layer laminated on the other side of the polarizer. Base) an acrylic resin film; wherein the first (meth) acrylic resin film contains an ultraviolet absorber and has a transmittance of 20% or less in the entire region at a wavelength of 190 to 380 nm, and the second (meth) The content of the ultraviolet absorber of the acrylic resin film is 1% by weight or less; and a liquid crystal panel using the polarizing plate.
Description
本發明係關於(甲基)丙烯酸系樹脂膜貼合於偏光片之兩面的偏光板及使用該偏光板之液晶面板。 The present invention relates to a polarizing plate in which a (meth) acrylic resin film is bonded to both sides of a polarizer, and a liquid crystal panel using the same.
偏光板已被廣泛使用作為液晶顯示裝置等的圖像顯示裝置中之偏光的供應元件,或者偏光的檢測元件。作為偏光板,一般係於偏光片的單面或兩面,使用接著劑貼合保護膜的構成者。 A polarizing plate has been widely used as a polarized light supply element or a polarized light detection element in an image display device such as a liquid crystal display device. As a polarizing plate, it is a structure which attach | attaches a protective film to the single surface or both surfaces of a polarizer normally using an adhesive agent.
於日本特開2009-122663號公報(專利文獻1),記載其中作為可滿足在加濕條件下的耐久性、顯示均勻性(mura)之偏光板,於貼合在偏光片兩面的保護膜使用(甲基)丙烯酸系樹脂膜之偏光板。 In Japanese Patent Application Laid-Open No. 2009-122663 (Patent Document 1), it is described that a polarizing plate capable of satisfying durability under humidified conditions and showing uniformity (mura) is used for a protective film bonded to both sides of a polarizer. A polarizing plate of a (meth) acrylic resin film.
通常,於保護膜中為了提高偏光板的耐久性(耐光性),而調配紫外線吸收劑。將保護膜貼合於偏光片的兩面時,一般係調配紫外線吸收劑於該兩面的保護膜。 Generally, an ultraviolet absorber is blended in the protective film in order to improve the durability (light resistance) of the polarizing plate. When a protective film is bonded to both sides of a polarizer, a protective film of an ultraviolet absorber is usually prepared on both sides.
但是,藉由本發明人的檢討而明確知道,若藉由熔融擠出法製作含有紫外線吸收劑的保護膜,即使非常少,也 有加熱熔融樹脂時蒸發而再次固化之紫外線吸收劑的粒子附著於所得的保護膜的表面,或由於擠出熔融裝置的長時間作業,於T型模頭等產生包含紫外線吸收劑的液狀附著物,因滴落而附著於保護膜表面或混入保護膜內成為與樹脂不同的相。如此的問題,於保護膜使用(甲基)丙烯酸系樹脂時特別顯著。(甲基)丙烯酸系樹脂膜因從可見光區域至紫外光區域的穿透率高,必須較增多紫外線吸收劑的含量。 However, it is clear from the review by the present inventors that if a protective film containing an ultraviolet absorbent is produced by a melt extrusion method, even if it is very small, Particles with ultraviolet absorbers that evaporate and solidify again when the molten resin is heated are attached to the surface of the resulting protective film, or due to the long-term operation of the extrusion melting device, liquid adhesion of ultraviolet absorbers to T-die and the like occurs. Objects adhere to the surface of the protective film due to dripping or are mixed into the protective film to become a phase different from the resin. Such a problem is particularly noticeable when a (meth) acrylic resin is used for the protective film. Since the (meth) acrylic resin film has a high transmittance from the visible light region to the ultraviolet light region, it is necessary to increase the content of the ultraviolet absorber.
上述來自紫外線吸收劑的異物,當然可成為本身的問題,但將具有異物的保護膜使用來作為配置於液晶胞側的保護膜時,因成為形成於液晶面板的交叉尼柯爾(Cross Nicol)中含有異物,黑色顯示時產生漏光等,辨識性恐會降低。特別是使用於超過40英吋的大型液晶監視器、液晶電視,畫素數目(橫×縱)超過2000×1000的高解像度液晶面板時,即使些許異物,也容易被識別,該問題變得顯著。而且,於低於10英吋的小型平板終端、攜帶型終端,畫面尺寸小,因使用者集中一點觀看畫面,與大型顯示裝置比較,異物有容易被識別的傾向,再者由於該等小型液晶面板的高解析度化,因異物造成的辨識性的降低變得更顯著。 Of course, the above-mentioned foreign matter derived from the ultraviolet absorber may be a problem in itself. However, when a protective film having a foreign matter is used as a protective film disposed on the liquid crystal cell side, it becomes a cross nicol formed on the liquid crystal panel. Foreign matter is contained, light leakage may occur during black display, and the visibility may be reduced. Especially when used in large LCD monitors and LCD TVs larger than 40 inches, and high-resolution LCD panels with a number of pixels (horizontal × vertical) exceeding 2000 × 1000, even foreign objects can be easily identified, and this problem becomes significant. . Moreover, in small tablet terminals and portable terminals less than 10 inches, the screen size is small. Because users concentrate on viewing the screen, compared with large display devices, foreign objects tend to be easily identified, and because of these small liquid crystals, The higher the resolution of the panel, the lower the visibility due to foreign objects.
本發明的目的在於提供將一種(甲基)丙烯酸系樹脂膜貼合於偏光片的兩面之偏光板,且具有充分的耐久性(耐光性),同時不會有來自紫外線吸收劑的異物混入之虞的偏光板,以及使用其之液晶面板。 An object of the present invention is to provide a polarizing plate in which a (meth) acrylic resin film is bonded to both sides of a polarizer, and has sufficient durability (light resistance), and at the same time, no foreign matter from an ultraviolet absorber is mixed in Yu's polarizers, and LCD panels using them.
本發明提供以下的偏光板及液晶面板。 The present invention provides the following polarizing plates and liquid crystal panels.
[1]偏光板係包括:偏光片、積層於偏光片的一側的面之第1(甲基)丙烯酸系樹脂膜、以及積層於偏光片的另一側的面之第2(甲基)丙烯酸系樹脂膜;其中,前述第1(甲基)丙烯酸系樹脂膜,含有紫外線吸收劑且在190至380nm的波長全部區域的穿透率為20%以下;前述第2(甲基)丙烯酸系樹脂膜之紫外線吸收劑的含量為1重量%以下。 [1] A polarizing plate includes a polarizer, a first (meth) acrylic resin film laminated on one side of the polarizer, and a second (methyl) layer laminated on the other side of the polarizer. An acrylic resin film; wherein the first (meth) acrylic resin film contains an ultraviolet absorber and has a transmittance of 20% or less in the entire region of a wavelength of 190 to 380 nm; the second (meth) acrylic resin The content of the ultraviolet absorber in the resin film is 1% by weight or less.
[2]如[1]記載的偏光板,其中,前述第2(甲基)丙烯酸系樹脂膜之260至320nm的波長區域的穿透率為20%以上。 [2] The polarizing plate according to [1], wherein the transmittance of the second (meth) acrylic resin film in a wavelength range of 260 to 320 nm is 20% or more.
[3]如[1]或[2]記載的偏光板,其中,前述第1及第2(甲基)丙烯酸系樹脂膜,係隔著由紫外線硬化性接著劑所形成的接著劑層,積層於前述偏光片。 [3] The polarizing plate according to [1] or [2], wherein the first and second (meth) acrylic resin films are laminated with an adhesive layer formed of an ultraviolet-curable adhesive through the adhesive layer. On the aforementioned polarizer.
[4]如[1]至[3]中任一項記載的偏光板,其中,在260至380nm的波長區域的穿透率的最大值為3%以下。 [4] The polarizing plate according to any one of [1] to [3], wherein a maximum value of a transmittance in a wavelength region of 260 to 380 nm is 3% or less.
[5]如[1]至[4]中任一項記載的偏光板,更包括積層於前述第2(甲基)丙烯酸系樹脂膜的外面之黏著劑層。 [5] The polarizing plate according to any one of [1] to [4], further comprising an adhesive layer laminated on an outer surface of the second (meth) acrylic resin film.
[6]如[1]至[5]中任一項記載的偏光板,更包括積層於前述第1(甲基)丙烯酸系樹脂膜的外面之塗佈層。 [6] The polarizing plate according to any one of [1] to [5], further including a coating layer laminated on an outer surface of the first (meth) acrylic resin film.
[7]液晶面板,係包括液晶胞、及配置於其至少一側的面之[1]至[6]中任一項所述的偏光板。 [7] A liquid crystal panel includes a liquid crystal cell and the polarizing plate according to any one of [1] to [6] arranged on a surface on at least one side thereof.
[8]如[7]記載的液晶面板,其中,前述偏光板係配置成該第2(甲基)丙烯酸系樹脂膜為前述液晶胞側。 [8] The liquid crystal panel according to [7], wherein the polarizing plate is arranged such that the second (meth) acrylic resin film is the liquid crystal cell side.
[9]如[8]記載的液晶面板,其中,前述液晶胞為IPS(橫 向電場效應)模式的液晶胞。 [9] The liquid crystal panel according to [8], wherein the liquid crystal cell is an IPS (horizontal To the electric field effect) mode.
根據本發明,可提供一種將(甲基)丙烯酸系樹脂膜貼合於偏光片的兩面之偏光板,具有充分的耐久性(耐光性)且減少來自紫外線吸收劑的異物之偏光板。該偏光板可適合應用於液晶面板。 According to the present invention, it is possible to provide a polarizing plate in which a (meth) acrylic resin film is bonded to both sides of a polarizer, and has sufficient durability (light resistance) and reduces foreign matter from ultraviolet absorbers. This polarizing plate can be suitably used for a liquid crystal panel.
1‧‧‧偏光板 1‧‧‧ polarizing plate
2‧‧‧液晶面板 2‧‧‧ LCD panel
10‧‧‧偏光片 10‧‧‧ Polaroid
15‧‧‧第1接著劑層 15‧‧‧The first adhesive layer
21‧‧‧第1(甲基)丙烯酸系樹脂膜 21‧‧‧The first (meth) acrylic resin film
22‧‧‧第2(甲基)丙烯酸系樹脂膜 22‧‧‧ 2nd (meth) acrylic resin film
25‧‧‧第2接著劑層 25‧‧‧The second adhesive layer
30‧‧‧黏著劑層 30‧‧‧ Adhesive layer
40‧‧‧液晶胞 40‧‧‧ LCD cell
第1圖係表示關於本發明的偏光板的層構成的一例之剖面示意圖。 FIG. 1 is a schematic cross-sectional view showing an example of a layer configuration of a polarizing plate of the present invention.
第2圖係表示關於本發明的液晶面板的層構成的一例之剖面示意圖。 FIG. 2 is a schematic cross-sectional view showing an example of a layer configuration of a liquid crystal panel of the present invention.
第3圖係表示實施例1製作的第1(甲基)丙烯酸系樹脂膜的190至380nm的波長區域的穿透率的圖。 FIG. 3 is a graph showing a transmittance in a wavelength region of 190 to 380 nm of the first (meth) acrylic resin film produced in Example 1. FIG.
第4圖係表示實施例1製作的第2(甲基)丙烯酸系樹脂膜的190至380nm的波長區域的穿透率的圖。 FIG. 4 is a graph showing a transmittance in a wavelength region of 190 to 380 nm of the second (meth) acrylic resin film produced in Example 1. FIG.
第5圖係表示比較例2製作的(甲基)丙烯酸系樹脂膜的190至380nm的波長區域的穿透率的圖。 FIG. 5 is a graph showing a transmittance in a wavelength region of 190 to 380 nm of the (meth) acrylic resin film produced in Comparative Example 2. FIG.
第6圖係表示實施例4製作的第1(甲基)丙烯酸系樹脂膜的190至380nm的波長區域的穿透率的圖。 FIG. 6 is a graph showing a transmittance in a wavelength region of 190 to 380 nm of the first (meth) acrylic resin film produced in Example 4. FIG.
第7圖係表示實施例4製作的第2(甲基)丙烯酸系樹脂膜的190至380nm的波長區域的穿透率的圖。 FIG. 7 is a graph showing a transmittance in a wavelength region of 190 to 380 nm of the second (meth) acrylic resin film produced in Example 4. FIG.
以下,顯示實施態樣,詳細地說明本發明的偏光板。 Hereinafter, an embodiment is shown and the polarizing plate of this invention is demonstrated in detail.
〈偏光板〉 <Polarizer>
第1圖係表示關於本發明的偏光板的層構成的一例之剖面示意圖。如第1圖所示的偏光板1之本發明的偏光板,係包括:偏光片10;積層於偏光片10的一側的面之第1(甲基)丙烯酸系樹脂膜21;以及積層於偏光片10的另一側的面之第2(甲基)丙烯酸系樹脂膜22。通常第1及第2(甲基)丙烯酸系樹脂膜21、22,分別隔著第1接著劑層15、第2接著劑層25而貼合、積層於偏光片10。如第1圖所示,本發明的偏光板係可更包含積層於第2(甲基)丙烯酸系樹脂膜22的外面之黏著劑層30。於本說明書中,所謂「(甲基)丙烯酸」係指選自丙烯酸及甲基丙烯酸所成之群的至少一者。關於「(甲基)丙烯酸酯」、或「(甲基)丙烯醯基」也相同。 FIG. 1 is a schematic cross-sectional view showing an example of a layer configuration of a polarizing plate of the present invention. The polarizing plate 1 according to the present invention of the polarizing plate 1 shown in FIG. 1 includes: a polarizing plate 10; a first (meth) acrylic resin film 21 laminated on one side of the polarizing plate 10; The second (meth) acrylic resin film 22 on the other side of the polarizer 10. The first and second (meth) acrylic resin films 21 and 22 are usually bonded and laminated on the polarizer 10 with the first adhesive layer 15 and the second adhesive layer 25 interposed therebetween, respectively. As shown in FIG. 1, the polarizing plate system of the present invention may further include an adhesive layer 30 laminated on the outer surface of the second (meth) acrylic resin film 22. In the present specification, the "(meth) acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The same applies to "(meth) acrylate" or "(meth) acrylfluorenyl".
(1)偏光片 (1) Polarizer
偏光片(亦稱為偏光膜)10係具有吸收具有平行於光學軸的振動面之直線偏光且穿透具有垂直光學軸的振動面之直線偏光的性質之光學膜,例如可為一軸延伸的二色性色素吸附配向的聚乙烯醇系樹脂膜。作為二色性色素係使用碘、二色性有機染料。構成偏光片10的聚乙烯醇系樹脂膜,除可為聚乙酸乙烯酯的皂化物的聚乙烯醇外,亦可為乙酸乙烯酯及可與其共聚合的其他單體(例如乙烯、不飽和羧酸等)的共聚物的皂化物的聚乙烯醇系共聚物。偏光片10的厚度通常為5至40μm左右。 A polarizer (also referred to as a polarizing film) 10 is an optical film having the property of absorbing linearly polarized light having a vibration plane parallel to the optical axis and penetrating linearly polarized light having a vibration plane having a vertical optical axis. Polyvinyl alcohol-based resin film in which a chromatic dye is adsorbed and aligned. As the dichroic dye system, iodine and a dichroic organic dye are used. The polyvinyl alcohol-based resin film constituting the polarizing plate 10 may be, in addition to polyvinyl alcohol which is a saponified product of polyvinyl acetate, vinyl acetate and other monomers (e.g., ethylene, unsaturated carboxylic acid) copolymerizable therewith. Acid, etc.) saponified copolymer of polyvinyl alcohol. The thickness of the polarizer 10 is usually about 5 to 40 μm.
偏光片10可經由聚乙烯醇系樹脂膜進行一 軸延伸的步驟、聚乙烯醇系樹脂膜以二色性色素染色而使該二色性色素吸附的步驟、二色性色素吸附的聚乙烯醇系樹脂膜以硼酸水溶液處理的步驟、以及藉由硼酸水溶液的處理後進行水洗的步驟製造。二色性色素的染色,可藉由將膜浸漬於含有二色性色素的水溶液進行,藉由硼酸水溶液的處理,可藉由將膜浸漬於硼酸水溶液進行。 The polarizer 10 can be made through a polyvinyl alcohol-based resin film. A step of shaft extension, a step of dyeing a polyvinyl alcohol-based resin film with a dichroic dye to adsorb the dichroic dye, a step of treating a polyvinyl alcohol-based resin film with the dichroic dye adsorbing an aqueous boric acid solution, and It is produced by a step of washing with a boric acid aqueous solution followed by washing with water. Dyeing of a dichroic dye can be performed by immersing a film in an aqueous solution containing a dichroic dye, and treatment of an aqueous boric acid solution can be performed by immersing the film in an aqueous solution of boric acid.
聚乙烯醇系樹脂膜的一軸延伸,可在二色性色素的染色前、與染色同時或染色後進行。使一軸延伸在染色後進行時,該一軸延伸可在硼酸處理前或硼酸處理中進行。而且,可以該等的複數階段進行一軸延伸。 The uniaxial extension of the polyvinyl alcohol-based resin film can be performed before, simultaneously with, or after dyeing the dichroic pigment. When the one-axis extension is performed after dyeing, the one-axis extension may be performed before or during the boric acid treatment. Furthermore, one-axis extension may be performed in the plural stages.
(2)第1(甲基)丙烯酸系樹脂膜 (2) 1st (meth) acrylic resin film
第1(甲基)丙烯酸系樹脂膜21係為了賦予偏光板耐久性(耐光性),係含有紫外線吸收劑的保護膜,使偏光板應用於液晶面板時,辨識側的偏光板時為配置於其辨識側的保護膜(與液晶胞的相反側),背光側的偏光板時為配置於其背光側(與液晶胞的相反側)的保護膜。 The first (meth) acrylic resin film 21 is a protective film containing an ultraviolet absorber in order to impart durability (light resistance) to the polarizing plate. When the polarizing plate is applied to a liquid crystal panel, the polarizing plate on the identification side is disposed on The protective film on the identification side (opposite to the liquid crystal cell), and the polarizing plate on the backlight side is a protective film disposed on the backlight side (opposite to the liquid crystal cell).
[(甲基)丙烯酸系樹脂] [(Meth) acrylic resin]
構成第1(甲基)丙烯酸系樹脂膜21的(甲基)丙烯酸系樹脂,係包含來自(甲基)丙烯酸系單體的構成單元的聚合物。該聚合物典型地係包含甲基丙烯酸酯的聚合物,較理想為甲基丙烯酸酯為主體,亦即以全部單體量為基準,包含50重量%以上的來自甲基丙烯酸酯的構成單元之聚合物。(甲基)丙烯酸系樹脂可為甲基丙烯酸酯的均聚物,亦可為以全部單體量為基準,包含50重量%以上的來自甲基 丙烯酸酯的構成單元、以及50重量%以下的來自其他聚合性單體的構成單元的共聚物。 The (meth) acrylic resin constituting the first (meth) acrylic resin film 21 is a polymer containing a structural unit derived from a (meth) acrylic monomer. The polymer is typically a polymer containing a methacrylate, and it is more preferable that the methacrylate is the main body, that is, based on the total amount of monomers, it contains 50% by weight or more of the constituent units derived from the methacrylate. polymer. The (meth) acrylic resin may be a homopolymer of methacrylate, or may be based on the total monomer amount, and may contain at least 50% by weight of methyl-derived A copolymer of a structural unit of an acrylic ester and a structural unit derived from another polymerizable monomer in an amount of 50% by weight or less.
作為可構成(甲基)丙烯酸系樹脂的甲基丙烯酸酯,可使用甲基丙烯酸烷酯,其具體例,包括甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸異丙酯、甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸第三丁酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸環己酯、甲基丙烯酸2-羥基乙酯之烷基的碳數為1至8的甲基丙烯酸烷酯。烷基的碳數,較理想為1至4。於(甲基)丙烯酸系樹脂中,甲基丙烯酸酯可使用單獨1種,亦可併用2種以上。 As the methacrylate that can constitute the (meth) acrylic resin, an alkyl methacrylate can be used, and specific examples thereof include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, and methyl Isopropyl acrylate, n-butyl methacrylate, isobutyl methacrylate, third butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, 2-hydroxy methacrylate The alkyl group of the ethyl ester has 1 to 8 carbon methacrylates. The carbon number of the alkyl group is preferably from 1 to 4. In the (meth) acrylic resin, a methacrylate may be used individually by 1 type, and may use 2 or more types together.
其中,從耐久性的觀點,(甲基)丙烯酸系樹脂較理想為包含來自甲基丙烯酸甲酯的構成單元,該構成單元以全部單體量為基準,包含50重量%以上更理想。 Among them, from the viewpoint of durability, the (meth) acrylic resin preferably contains a constituent unit derived from methyl methacrylate, and the constituent unit is more preferably contained in an amount of 50% by weight or more based on the total monomer amount.
作為可構成(甲基)丙烯酸系樹脂的上述其他聚合性單體,例如丙烯酸酯、甲基丙烯酸酯及丙烯酸酯以外的聚合性單體。作為丙烯酸酯,可使用丙烯酸烷酯,其具體例,包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸異丙酯、丙烯酸正丁酯、丙烯酸異丁酯、丙烯酸第三丁酯、丙烯酸2-乙基己酯、丙烯酸環己酯、丙烯酸2-羥基乙酯之烷基的碳數為1至8的甲基丙烯酸烷酯。烷基的碳數,較理想為1至4。於(甲基)丙烯酸系樹脂中,丙烯酸酯,可使用單獨1種,亦可併用2種以上。 Examples of the other polymerizable monomer that can constitute the (meth) acrylic resin include polymerizable monomers other than acrylate, methacrylate, and acrylate. As the acrylate, an alkyl acrylate can be used, and specific examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, third butyl acrylate, and acrylic acid. The alkyl groups of 2-ethylhexyl acrylate, cyclohexyl acrylate, and 2-hydroxyethyl acrylate have 1 to 8 alkyl methacrylates. The carbon number of the alkyl group is preferably from 1 to 4. In the (meth) acrylic resin, acrylate may be used alone or in combination of two or more.
作為甲基丙烯酸酯及丙烯酸酯以外的聚合 性單體,例如於分子內具有1個聚合性碳-碳雙鍵的單官能基單體、於分子內具有至少2個聚合性碳-碳雙鍵的多官能基單體,使用單官能基單體較理想。單官能基單體的具體例,包括:如苯乙烯、α-甲基苯乙烯、乙烯基甲苯、鹵化苯乙烯、羥基苯乙烯的苯乙烯系單體;如丙烯腈、甲基丙烯腈的氰乙烯;如丙烯酸、甲基丙烯酸、順丁烯二酸酐、亞甲基丁二酸酐的不飽和酸;如N-甲基馬來醯亞胺、N-環己基馬來醯亞胺、N-苯基馬來醯亞胺的馬來醯亞胺;如甲基烯丙醇、烯丙醇等的烯丙醇;如乙酸乙烯酯、氯化乙烯、乙烯、丙烯、4-甲基-1-戊烯、2-羥基甲基-1-丁烯、甲基乙烯基酮、N-乙烯基吡咯烷酮、N-乙烯基咔唑的其他單體。 Polymerization other than methacrylate and acrylate Monofunctional monomers, such as a monofunctional monomer having one polymerizable carbon-carbon double bond in the molecule, and a polyfunctional monomer having at least two polymerizable carbon-carbon double bonds in the molecule, using a monofunctional group Monomers are ideal. Specific examples of the monofunctional monomer include: styrene-based monomers such as styrene, α-methylstyrene, vinyl toluene, halogenated styrene, and hydroxystyrene; cyanide such as acrylonitrile and methacrylonitrile Ethylene; unsaturated acids such as acrylic acid, methacrylic acid, maleic anhydride, and methylene succinic anhydride; such as N-methylmaleimide, N-cyclohexylmaleimide, N-benzene Maleimide of maleimide; allyl alcohol such as methallyl alcohol, allyl alcohol, etc .; such as vinyl acetate, vinyl chloride, ethylene, propylene, 4-methyl-1-pentyl Ene, 2-hydroxymethyl-1-butene, methyl vinyl ketone, N-vinyl pyrrolidone, other monomers of N-vinylcarbazole.
而且,多官能基單體的具體例,包括:如乙二醇二甲基丙烯酸酯、丁二醇二甲基丙烯酸酯、三羥甲基丙烷三丙烯酸酯的多價醇的聚不飽和羧酸酯;如丙烯酸烯丙酯、甲基丙烯酸烯丙酯、肉桂酸烯丙酯的不飽和羧酸的烯酯;鄰苯二甲酸二烯丙酯、順丁烯二酸二烯丙酯、氰脲酸三烯丙酯、異氰脲酸三烯丙酯的多元酸的聚烯酯、如二乙烯基苯的芳香族聚烯化合物。甲基丙烯酸酯及丙烯酸酯以外的聚合性單體,可使用單獨1種,亦可併用2種以上。 Further, specific examples of the polyfunctional monomer include polyunsaturated carboxylic acids of polyvalent alcohols such as ethylene glycol dimethacrylate, butanediol dimethacrylate, and trimethylolpropane triacrylate. Esters; such as allyl acrylate, allyl methacrylate, allyl cinnamate, unsaturated carboxylic acid allyl esters; diallyl phthalate, diallyl maleate, cyanuramide Triallyl acid, polyallyl esters of polyacids of triallyl isocyanurate, and aromatic polyene compounds such as divinylbenzene. The polymerizable monomers other than methacrylate and acrylate may be used individually by 1 type, and may use 2 or more types together.
(甲基)丙烯酸系樹脂的較理想組成,以全部單體量為基準,甲基丙烯酸烷酯為50至100重量%,丙烯酸烷酯為0至50重量%,該等以外的聚合性單體為0至50重量%,更理想係甲基丙烯酸烷酯為50至99.9重量%,丙 烯酸烷酯為0.1至50重量%,該等以外的聚合性單體為0至49.9重量%。 The preferable composition of the (meth) acrylic resin is based on the total amount of monomers, 50 to 100% by weight of alkyl methacrylate, 0 to 50% by weight of alkyl acrylate, and other polymerizable monomers other than these. 0 to 50% by weight, more preferably 50 to 99.9% by weight of alkyl methacrylate, The alkyl acrylate is 0.1 to 50% by weight, and the polymerizable monomers other than these are 0 to 49.9% by weight.
而且,(甲基)丙烯酸系樹脂由於可提高膜的耐久性,於高分子主鏈可具有環構造。環構造較理想為環狀酸酐構造、環狀醯亞胺構造、內酯環構造等的雜環構造。具體地,戊二酸酐構造、丁二酸酐構造等的環狀酸酐構造、戊二醯亞胺構造、丁二醯亞胺構造等的環狀醯亞胺構造、丁內酯、戊內酯等的內酯環構造。主鏈中的環構造的含量越大,(甲基)丙烯酸系樹脂的玻璃轉化溫度越高。環狀酸酐構造、環狀醯亞胺構造可藉由使具有順丁烯二酸酐、馬來醯亞胺等的環狀構造的單體共聚合而導入的方法、聚合後藉由脫水/脫甲醇縮合反應導入環狀酸酐構造的方法、藉由使胺基化合物反應而導入環狀醯亞胺構造的方法等來導入。具有內酯環構造的樹脂(聚合物),可藉由調製於高分子鏈具有羥基及酯基的聚合物後,所得的聚合物之羥基及酯基藉由加熱,依需要在如有機磷化合物的觸媒存在下環化縮合而形成內酯環構造的方法得到。 In addition, the (meth) acrylic resin can improve the durability of the film, and can have a ring structure in the polymer main chain. The ring structure is preferably a heterocyclic structure such as a cyclic acid anhydride structure, a cyclic amidine structure, and a lactone ring structure. Specifically, cyclic anhydride structures such as glutaric anhydride structure and succinic anhydride structure, cyclic diimide structures such as glutarimide structure, succinimide structure, butyrolactone, valerolactone, etc. Lactone ring structure. The larger the content of the ring structure in the main chain, the higher the glass transition temperature of the (meth) acrylic resin. The cyclic acid anhydride structure and the cyclic fluorene imine structure can be introduced by copolymerizing a monomer having a cyclic structure such as maleic anhydride, maleimide, and the like, and dehydration / demethanol can be used after polymerization. A method of introducing a cyclic acid anhydride structure into a condensation reaction, a method of introducing a cyclic amidine structure by reacting an amine compound, and the like are introduced. A resin (polymer) having a lactone ring structure can be prepared from a polymer having a hydroxyl group and an ester group in a polymer chain, and the hydroxyl group and the ester group of the obtained polymer can be heated, for example, to an organic phosphorus compound as required. It is obtained by a method of cyclization and condensation under the presence of a catalyst to form a lactone ring structure.
於高分子鏈具有羥基及酯基的聚合物,例如藉由使用如2-(羥基甲基)丙烯酸甲酯、2-(羥基甲基)丙烯酸乙酯、2-(羥基甲基)丙烯酸異丙酯、2-(羥基甲基)丙烯酸正丁酯、2-(羥基甲基)丙烯酸第三丁酯之具有羥基及酯基的(甲基)丙烯酸酯作為單體的一部分而得。具有內酯環構造的聚合物的更具體的調製方法,例如特開2007-254726號公報的記載。 For polymers having a hydroxyl group and an ester group in the polymer chain, for example, by using, for example, methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, and isopropyl 2- (hydroxymethyl) acrylate An ester, (butyl) 2- (hydroxymethyl) acrylate, and (meth) acrylic acid ester having a hydroxy group and an ester group as the third butyl 2- (hydroxymethyl) acrylate are obtained as part of the monomer. A more specific method for preparing a polymer having a lactone ring structure is described in, for example, Japanese Patent Application Laid-Open No. 2007-254726.
藉由使包含如上述的單體之單體組成物進行自由基聚合,可調製(甲基)丙烯酸系樹脂。單體組成物依據需要可包含溶劑、聚合引發劑。 By radically polymerizing a monomer composition containing the monomers as described above, a (meth) acrylic resin can be prepared. The monomer composition may contain a solvent and a polymerization initiator as needed.
[其他樹脂] [Other resins]
第1(甲基)丙烯酸系樹脂膜21,可含有上述(甲基)丙烯酸系樹脂以外的其他樹脂。該其他樹脂的含有比例,較理想為0至50重量%,更理想為0至25重量%,更加理想為0至10重量%。該樹脂例如為如聚乙烯、聚丙烯、乙烯-丙烯共聚物、聚(4-甲基-1-戊烯)的烯烴系聚合物;如氯乙烯、氯乙烯樹脂的含有鹵素系聚合物;如聚苯乙烯、苯乙烯-甲基丙烯酸甲酯共聚物、苯乙烯-丙烯腈共聚物的苯乙烯系聚合物;如聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯之聚酯;芳香族二醇與芳香族二羧酸所成的聚芳酯;聚乳酸、聚丁二酸丁二酯的生物分解性聚酯;聚碳酸酯;如尼龍6、尼龍66、尼龍610的聚醯胺;聚縮醛;聚苯醚;聚苯硫醚;聚醚醚酮;聚醚腈;聚碸;聚醚碸;聚氧苯甲酯;聚醯胺醯亞胺等。 The 1st (meth) acrylic-type resin film 21 may contain resins other than the said (meth) acrylic-type resin. The content ratio of the other resin is more preferably 0 to 50% by weight, more preferably 0 to 25% by weight, and even more preferably 0 to 10% by weight. The resin is, for example, an olefin-based polymer such as polyethylene, polypropylene, an ethylene-propylene copolymer, or poly (4-methyl-1-pentene); a halogen-containing polymer such as vinyl chloride or vinyl chloride resin; such as Polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer styrenic polymer; such as polyethylene terephthalate, polybutylene terephthalate, polynaphthalene Polyester of ethylene diformate; Polyarylate of aromatic diol and aromatic dicarboxylic acid; Biodegradable polyester of polylactic acid and polybutylene succinate; Polycarbonate; such as nylon 6 , Polyamide 66, nylon 610; polyacetal; polyphenylene ether; polyphenylene sulfide; polyether ether ketone; polyether nitrile; polyfluorene; polyether fluorene; polyoxyphenyl methyl ester; polyfluorene fluorene Imine and so on.
[紫外線吸收劑] [Ultraviolet absorbent]
包含於第1(甲基)丙烯酸系樹脂膜21之紫外線吸收劑,可為於波長約200至400nm具有最大吸收的紫外線吸收劑,其種類無特別限制,例如三嗪(triazine)系紫外線吸收劑、二苯甲酮(benzophenone)系紫外線吸收劑、苯並***(benzotriazole)系紫外線吸收劑、苯甲酸酯系紫外線吸收劑、氰基丙烯酸酯系紫外線吸收劑等。 The ultraviolet absorbent contained in the first (meth) acrylic resin film 21 may be an ultraviolet absorbent having a maximum absorption at a wavelength of about 200 to 400 nm, and the type thereof is not particularly limited. For example, a triazine ultraviolet absorber , Benzophenone-based ultraviolet absorber, benzotriazole-based ultraviolet absorber, benzoate-based ultraviolet absorber, cyanoacrylate-based ultraviolet absorber, and the like.
(三嗪系紫外線吸收劑) (Triazine UV absorber)
三嗪系紫外線吸收劑係以下述通式(i):Q1-Q2-OH (i)表示。式中,Q1表示1,3,5-三嗪環,Q2表示芳香族環。 The triazine-based ultraviolet absorber is represented by the following general formula (i): Q 1 -Q 2 -OH (i). In the formula, Q 1 represents a 1,3,5-triazine ring, and Q 2 represents an aromatic ring.
作為上述通式(i)所示的三嗪系紫外線吸收劑,例如下述通式(i-A):
式中,R2、R2’、R2”、R11、R11’及R11”表示與後述通式(i-B)中的R2、R2’、R2”、R11、R11’及R11”相同的官能基,R18’及R18”表示互相獨立之氫原子、羥基或烷氧基(OR1)。 In the formula, R 2 , R 2 ′ , R 2 ″ , R 11 , R 11 ′, and R 11 ″ represent the same as R 2 , R 2 ′ , R 2 ″ , R 11 , and R 11 in the general formula (iB) described later. ' And R 11 "are the same functional group, and R 18' and R 18" represent a hydrogen atom, a hydroxyl group, or an alkoxy group (OR 1 ) independently of each other.
通式(i-A)所示的三嗪系紫外線吸收劑中,較理想使用的三嗪系紫外線吸收劑為下述通式(i-B):
式中,R1表示碳原子數1至18的烷基;碳原子數5至12的環烷基;碳原子數3至18的烯基;苯基;被苯基、羥基、碳原子數1至18的烷氧基、碳原子數5至12的環烷基、碳原子數3至18的烯氧基、鹵原子、-COOH、-COOR4、-O-CO-R5、-O-CO-O-R6、-CO-NH2、-CO-NHR7、-CO-N(R7)(R8)、CN、NH2、NHR7、-N(R7)(R8)、-NH-CO-R5、苯氧基、碳原子數1至18的烷基取代的苯氧基、被苯基-碳原子數1至4的烷氧基、碳原子數6至15的雙環烷氧基、碳原子數6至15的雙環烷基烷氧基或碳原子數6至15的三環烷氧基取代的碳原子數1至18的烷基;被羥基、碳原子數1至4的烷基、碳原子數2至6的烯基或-O-CO-R5取代的碳原子數5至12的環烷基;環氧丙基;-CO-R9或-SO2-R10表示;或R1表示被1個以上的氧原子中斷的及/或被羥基、苯氧基或碳原子數7至18的烷基苯氧基取代的碳原子數3至50的烷基;或R1表示-A;-CH2-CH(XA)-CH2-O-R12;-CR13R13’-(CH2)m-X-A;-CH2-CH(OA)-R14;-CH2-CH(OH)-CH2-
XA;
R2、R2’及R2”,互相獨立表示碳原子數6至18的烷基;碳原子數2至6的烯基;苯基;碳原子數7至11的苯基烷基;COOR4;CN;-NH-CO-R5;鹵原子;三氟甲基;-O-R3。 R 2 , R 2 ′ and R 2 ″ , independently of each other, represent an alkyl group having 6 to 18 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; a phenyl group; a phenyl alkyl group having 7 to 11 carbon atoms; COOR 4; CN; -NH-CO- R 5; a halogen atom; trifluoromethyl; -OR 3.
R3表示對R1賦予的定義;R4表示碳原子數1至18的烷基;碳原子數3至18的烯基;苯基;碳原子數7至11的苯基烷基;碳原子數5至12的環烷基;或者R4表示被1個以上的-O-、-NH-、NR7-、-S-中斷及可被OH、苯氧基或碳原子數7至18的烷基苯氧基取代之碳原子數3至50的烷基;R5表示H;碳原子數1至18的烷基;碳原子數2至18的烯基;碳原子數5至12的環烷基;苯基;碳原子數7至11的苯基烷基;碳原子數6至15的雙環烷基;碳原子數6至15的雙環烯基;碳原子數6至15的三環烷基;R6表示H;碳原子數1至18的烷基;碳原子數3至18的烯基;苯基;碳原子數7至11的苯基烷基;碳原子數5至12的環烷基;R7及R8互相獨立表示碳原子數1至12的烷基;碳原子數3至12的烷氧基烷基;碳原子數4至16的二烷基胺基烷基;或者表示碳原子數5至12的環烷基;或 者R7及R8表示一起成為碳原子數3至9的伸烷基、碳原子數3至9的氧伸烷基或碳原子數3至9的氮雜伸烷基;R9表示碳原子數1至18的烷基;碳原子數2至18的烯基;苯基;碳原子數5至12的環烷基;碳原子數7至11的苯基烷基;碳原子數6至15的雙環烷基;碳原子數6至15的雙環烷基烷基;碳原子數6至15的雙環烯基;或碳原子數6至15的三環烷基;R10表示碳原子數1至12的烷基;苯基;萘基;或碳原子數7至14的烷基苯基;R11、R11’及R11”互相獨立表示H;碳原子數1至18的烷基;碳原子數3至6的烯基;苯基;碳原子數7至11的苯基烷基;鹵原子;碳原子數1至18的烷氧基;R12表示碳原子數1至18的烷基;碳原子數3至18的烯基;苯基;被碳原子數1至8的烷基、碳原子數1至8的烷氧基、碳原子數3至8的烯氧基、鹵原子或三氟甲基取代1至3次的苯基;或碳原子數7至11的苯基烷基;碳原子數5至12的環烷基;碳原子數6至15的三環烷基;碳原子數6至15的雙環烷基;碳原子數6至15的雙環烷基烷基;碳原子數6至15的雙環烯基烷基;-CO-R5;或R12表示被1個以上的-O-、-NH-、NR7-、-S-中斷及可被OH、苯氧基或碳原子數7至18的烷基苯氧基取代之碳原子數3至50的烷基;R13及R13’互相獨立表示H;碳原子數1至18的烷基;苯基;R14表示碳原子數1至18的烷基;碳原子數3至12的烷氧基烷基;苯基;苯基-碳原子數1至4的烷基;R15、R15’及R15”互相獨立表示H或CH3;R16表示H;-CH2-COO-R4;碳原 子數1至4的烷基;或CN;R17表示H;-COOR4;碳原子數1至17的烷基;或苯基;X表示-NH-;-NR7-;-O-;-NH-(CH2)p-NH-;或-O-(CH2)q-NH-;以及m表示數0至19;n表示數0至8;p表示數0至4;q表示2至4;但是通式(i-B)中,R1、R2、R2’、R2”、R11、R11’及R11”的至少1個包含2個以上的碳原子。 R 3 represents the definition given to R 1 ; R 4 represents an alkyl group having 1 to 18 carbon atoms; alkenyl group having 3 to 18 carbon atoms; phenyl group; phenyl alkyl group having 7 to 11 carbon atoms; carbon atom A cycloalkyl group of 5 to 12; or R 4 represents a group interrupted by one or more -O-, -NH-, NR 7- , -S- and may be interrupted by OH, phenoxy, or 7 to 18 carbon atoms Alkylphenoxy substituted alkyl having 3 to 50 carbon atoms; R 5 represents H; alkyl having 1 to 18 carbon atoms; alkenyl having 2 to 18 carbon atoms; ring having 5 to 12 carbon atoms Alkyl; phenyl; phenylalkyl with 7 to 11 carbon atoms; bicycloalkyl with 6 to 15 carbon atoms; bicycloalkenyl with 6 to 15 carbon atoms; tricycloalkane with 6 to 15 carbon atoms R 6 represents H; alkyl group having 1 to 18 carbon atoms; alkenyl group having 3 to 18 carbon atoms; phenyl group; phenyl alkyl group having 7 to 11 carbon atoms; ring having 5 to 12 carbon atoms Alkyl; R 7 and R 8 each independently represent an alkyl group having 1 to 12 carbon atoms; an alkoxyalkyl group having 3 to 12 carbon atoms; a dialkylamino alkyl group having 4 to 16 carbon atoms; or represents a cycloalkyl group having 5 to 12 carbon atoms; or R 7 and R 8 together represent carbon atoms, an alkoxy become stretched 3 to 9 Carbon atoms, 3-9 oxygen or alkylene group having a carbon number aza 3-9 alkylene group; R 9 represents an alkyl group having 1 to 18 carbon atoms; an alkenyl group having a carbon number of 2 to 18; Benzene Cycloalkyl having 5 to 12 carbon atoms; Phenylalkyl having 7 to 11 carbon atoms; Bicycloalkyl having 6 to 15 carbon atoms; Bicycloalkylalkyl having 6 to 15 carbon atoms; Carbon Bicycloalkenyl with 6 to 15 atoms; or tricycloalkyl with 6 to 15 carbon atoms; R 10 represents an alkyl group with 1 to 12 carbon atoms; phenyl; naphthyl; or 7 to 14 carbon atoms Alkylphenyl; R 11 , R 11 ′ and R 11 ″ each independently represent H; an alkyl group having 1 to 18 carbon atoms; an alkenyl group having 3 to 6 carbon atoms; a phenyl group; Phenylalkyl; halogen atom; alkoxy group having 1 to 18 carbon atoms; R 12 represents alkyl group having 1 to 18 carbon atoms; alkenyl group having 3 to 18 carbon atoms; phenyl group; An alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms, a halogen atom, or a phenyl group substituted 1 to 3 times with a trifluoromethyl group; or 7 to 6 carbon atoms 11 phenylalkyl; cycloalkyl having 5 to 12 carbon atoms; tricyclic alkyl having 6 to 15 carbon atoms Bicyclic alkyl group having a carbon number of 6 to 15; bicyclic carbon atoms, cycloalkylalkyl of 6 to 15; bicyclic carbon atoms, an alkenyl group having 6 to 15; -CO-R 5; or R 12 represents a The above -O-, -NH-, NR 7- , -S- is interrupted and the alkyl group having 3 to 50 carbon atoms may be substituted by OH, phenoxy or alkylphenoxy group having 7 to 18 carbon atoms R 13 and R 13 ′ each independently represent H; an alkyl group having 1 to 18 carbon atoms; a phenyl group; R 14 represents an alkyl group having 1 to 18 carbon atoms; an alkoxyalkyl group having 3 to 12 carbon atoms Phenyl; phenyl-alkyl having 1 to 4 carbon atoms; R 15 , R 15 ′ and R 15 ″ each independently represent H or CH 3 ; R 16 represents H; -CH 2 -COO-R 4 ; carbon Alkyl group having 1 to 4 atoms; or CN; R 17 represents H; -COOR 4 ; alkyl group having 1 to 17 carbon atoms; or phenyl group; X represents -NH-; -NR 7- ; -O-; -NH- (CH 2 ) p -NH-; or -O- (CH 2 ) q -NH-; and m represents the number 0 to 19; n represents the number 0 to 8; p represents the number 0 to 4; q represents 2 To 4; however, in the general formula (iB), at least one of R 1 , R 2 , R 2 ′ , R 2 ″ , R 11 , R 11 ′, and R 11 ″ contains 2 or more carbon atoms.
作為三嗪系紫外線吸收劑的具體例,可舉例如2,4-二苯基-6-(2-羥基-4-甲氧基苯基)-1,3,5-三嗪、2,4-二苯基-6-(2-羥基-4-乙氧基苯基)-1,3,5-三嗪、2,4-二苯基-(2-羥基-4-丙氧基苯基)-1,3,5-三嗪、2,4-二苯基-(2-羥基-4-丁氧基苯基)-1,3,5-三嗪、2,4-二苯基-6-(2-羥基-4-丁氧基苯基)-1,3,5-三嗪、2,4-二苯基-6-(2-羥基-4-己氧基苯基)-1,3,5-三嗪、2,4-二苯基-6-(2-羥基-4-辛氧基苯基)-1,3,5-三嗪、2,4-二苯基-6-(2-羥基-4-十二烷氧基苯基)-1,3,5-三嗪、2,4-二苯基-6-(2-羥基-4-苯甲氧基苯基)-1,3,5-三嗪等。 Specific examples of the triazine-based ultraviolet absorber include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4 -Diphenyl-6- (2-hydroxy-4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) ) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- 6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1 , 3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6 -(2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1,3,5-triazine and so on.
(二苯甲酮系紫外線吸收劑) (Benzophenone-based UV absorber)
二苯甲酮系紫外線吸收劑係以下述通式(ii):
作為二苯甲酮系紫外線吸收劑,可舉例如2,4-二羥基-二苯甲酮、2-羥基-4-甲氧基-二苯甲酮、2-羥基 -4-正辛氧基-二苯甲酮、2-羥基-4-十二烷氧基-二苯甲酮、2-羥基-4-十八烷氧基-二苯甲酮、2,2’-二羥基-4-甲氧基-二苯甲酮、2,2’-二羥基-4,4’-二甲氧基-二苯甲酮、2,2’,4,4’-四羥基-二苯甲酮等。 Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, and 2-hydroxy 4-n-octyloxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2 '-Dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2', 4,4'-tetrakis Hydroxy-benzophenone and the like.
(苯並***系紫外線吸收劑) (Benzotriazole UV absorber)
苯並***系紫外線吸收劑係以下述通式(iii):
作為苯並***系紫外線吸收劑,可舉例如2-(2’-羥基-5-甲基苯基)苯並***、2-(2’-羥基-3’,5’-二第三丁基苯基)苯並***、2-(2’-羥基-3’-第三丁基-5’-甲基苯基)苯並***、2-(2’-羥基-5’-甲基苯基)苯並***、2-(2’-羥基-3’,5’-二第三丁基苯基)-5-氯苯並***、2-(2’-羥基-3’-(3”,4”,5”,6”-四氫鄰苯二甲醯亞胺基甲基)-5’-甲基苯基)苯並***、2,2-亞甲基雙(4-(1,1,3,3-四甲基丁基)-6-(2H-苯並***-2-基)酚)、2-(2’-羥基-3’-第三丁基-5’-甲基苯基)-5-氯苯並***、2-(2’-羥基-3’,5’-二第三戊基苯基)-5-氯苯並***等。 Examples of the benzotriazole-based ultraviolet absorber include 2- (2'-hydroxy-5-methylphenyl) benzotriazole and 2- (2'-hydroxy-3 ', 5'-secondary Butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-third butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'- Methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 '-(3 ”, 4”, 5 ”, 6” -tetrahydrophthalimidoiminomethyl) -5'-methylphenyl) benzotriazole, 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2'-hydroxy-3'-tertiary butyl -5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-third-pentylphenyl) -5-chlorobenzotriazole, etc. .
(苯甲酸酯系紫外線吸收劑) (Benzoate UV absorber)
苯甲酸酯系紫外線吸收劑係以下述通式(iv):
作為苯甲酸酯系紫外線吸收劑,可舉例如2,4-二第三丁基苯基-3’,5’-二第三丁基-4’-羥基苯甲酸酯、2,6-二第三丁基苯基-3’,5’-二第三丁基-4’-羥基苯甲酸酯、正十六烷基-3,5-二第三丁基-4-羥基苯甲酸酯及正十八烷基-3,5-二第三丁基-4-羥基苯甲酸酯等。 Examples of the benzoate-based ultraviolet absorber include 2,4-di-tert-butylphenyl-3 ', 5'-di-tert-butyl-4'-hydroxybenzoate, and 2,6- Di-tert-butylphenyl-3 ', 5'-di-tert-butyl-4'-hydroxybenzoate, n-hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate Esters and n-octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate.
(氰基丙烯酸酯系紫外線吸收劑) (Cyanoacrylate UV absorber)
氰基丙烯酸酯系紫外線吸收劑係以下述通式(v):
作為紫外線吸收劑,可單獨使用上述的紫外線吸收劑,亦可併用2種以上。而且,於併用2種以上時,互相可為相同系的紫外線吸收劑,亦可為不同系的紫外線吸收劑。 As the ultraviolet absorbent, the above-mentioned ultraviolet absorbent may be used alone, or two or more kinds may be used in combination. Moreover, when two or more types are used in combination, they may be the same type of ultraviolet absorbent, or they may be different types of ultraviolet absorbent.
作為紫外線吸收劑,可使用市售品,可舉例如作為三嗪系紫外線吸收劑之CHEMIPRO化成公司製的「Kemisorb102」、ADEKA公司製的「ADEKA STAB LA46」、「ADEKA STAB LAF70」、BASF公司製的「TINUVIN 460」、「TINUVIN 405」、「TINUVIN 400」、「TINUVIN 477」、SUNCHEMI公司製的「CYASORB UV-1164」;作為苯並***系紫外線吸收劑之ADEKA公司製的「ADEKA STAB LA31」、ADEKA公司製的「ADEKA STAB LA36」、住化CHEMTEX公司製的「SUMISORB 200」、「SUMISORB 250」、「SUMISORB 300」、「SUMISORB 340」、「SUMISORB 350」、CHEMIPRO化成公司製的「Kemisorb74」、「Kemisorb79」、「Kemisorb279」、BASF公司製的「TINUVIN 99-2」、「TINUVIN 900」、「TINUVIN 928」等。 As the ultraviolet absorber, commercially available products can be used, and examples thereof include "Kemisorb 102" manufactured by CHEMIPRO Kasei Corporation, which is a triazine-based ultraviolet absorbent, "ADEKA STAB LA46", "ADEKA STAB LAF70", manufactured by ADEKA, and BASF Corporation. "TINUVIN 460", "TINUVIN 405", "TINUVIN 400", "TINUVIN 477", "CYASORB UV-1164" manufactured by SUNCHEMI Corporation; "ADEKA STAB LA31" manufactured by ADEKA Corporation as a benzotriazole UV absorber "," ADEKA STAB LA36 "by ADEKA," SUMISORB 200 "," SUMISORB 250 "," SUMISORB 300 "," SUMISORB 340 "," SUMISORB 350 "," SUMISORB 350 ", and" Kemisorb74 "manufactured by Chemipro "," Kemisorb79 "," Kemisorb279 "," TINUVIN 99-2 "made by BASF," TINUVIN 900 "," TINUVIN 928 ", etc.
紫外線吸收劑各別的重量平均分子量,從抑制第1(甲基)丙烯酸系樹脂膜21成形中蒸發的觀點,較理想為500至1000,更理想為550至800。重量平均分子量太小時,成形中容易蒸發,重量平均分子量太大時,與構成第1(甲基)丙烯酸系樹脂膜21的樹脂之相溶性容易變低。 The respective weight average molecular weights of the ultraviolet absorbers are preferably 500 to 1,000, and more preferably 550 to 800, from the viewpoint of suppressing evaporation during the molding of the first (meth) acrylic resin film 21. When the weight average molecular weight is too small, it is easy to evaporate during molding, and when the weight average molecular weight is too large, the compatibility with the resin constituting the first (meth) acrylic resin film 21 tends to be low.
紫外線吸收劑係其最大吸收的波長之莫耳吸光係數為10L/mol.cm較理想,以15L/mol.cm更理想。紫外線吸收劑的莫耳吸光係數為上述範圍時,可提高第1(甲基)丙烯酸系樹脂膜21的紫外線吸收能力,或者可維持良好的紫外線吸收能力,同時可減少紫外線吸收劑的含 量。 The ultraviolet absorption agent has a molar absorption coefficient of 10 L / mol at its maximum absorption wavelength. cm is ideal, at 15L / mol. cm is more ideal. When the molar absorption coefficient of the ultraviolet absorber is in the above range, the ultraviolet absorption ability of the first (meth) acrylic resin film 21 can be improved, or a good ultraviolet absorption ability can be maintained, and the content of the ultraviolet absorber can be reduced. the amount.
紫外線吸收劑在260至380nm的莫耳吸光係數,例如苯並***系紫外線吸收劑之ADEKA公司製的「ADEKA STAB LA31」,約於350nm具有最大吸收波長,該最大吸收波長的莫耳吸光係數為34821L/mol.cm。莫耳吸光係數係隨化學構造而異,藉由單獨使用或併用紫外線吸收劑,可吸收或穿透所期望的波長的紫外線。 The molar absorption coefficient of the ultraviolet absorber at 260 to 380 nm, for example, "ADEKA STAB LA31" manufactured by ADEKA Corporation, a benzotriazole-based ultraviolet absorbent, has a maximum absorption wavelength of about 350 nm, and the molar absorption coefficient of the maximum absorption wavelength It is 34621L / mol. cm. The Mohr absorption coefficient varies depending on the chemical structure. By using it alone or in combination with an ultraviolet absorbent, it can absorb or penetrate ultraviolet rays of a desired wavelength.
紫外線吸收劑的含量,為了賦予充分的耐光性,在190至380nm的波長全部區域(近紫外線區域的全部區域)的穿透率調整為20%以下,較理想為調整為18%以下。穿透率係因也取決於第1(甲基)丙烯酸系樹脂膜21的厚度,故也考慮所採用的厚度而決定紫外線吸收劑的含量。穿透率係以下述式:穿透率(%)=100×(穿透光的強度I/入射光的強度I0)定義,各波長的穿透率,可藉由紫外線可見光吸光光度計等測定。 In order to provide sufficient light resistance, the content of the ultraviolet absorber is adjusted to 20% or less, and more preferably 18% or less, in the entire range of the wavelength of 190 to 380 nm (all the near ultraviolet range). Since the transmittance depends on the thickness of the first (meth) acrylic resin film 21, the content of the ultraviolet absorber is also determined in consideration of the thickness to be used. The transmittance is defined by the following formula: transmittance (%) = 100 × (intensity of transmitted light I / intensity of incident light I 0 ). The transmittance of each wavelength can be determined by ultraviolet visible light absorption photometer, etc. Determination.
雖隨第1(甲基)丙烯酸系樹脂膜21的厚度而異,但該膜中的紫外線吸收劑的含量,通常為0.1重量%以上,較理想為0.5重量%以上。而且,通常紫外線吸收劑的含量為5重量%以下。再者,此處所謂之含量,係指膜的全部量設為100重量%時的紫外線吸收劑的含量。 Although it varies with the thickness of the 1st (meth) acrylic-type resin film 21, content of the ultraviolet absorber in this film is 0.1 weight% or more normally, Preferably it is 0.5 weight% or more. The content of the ultraviolet absorber is usually 5% by weight or less. The content herein refers to the content of the ultraviolet absorber when the total amount of the film is 100% by weight.
而且,關於作為偏光板全體的紫外線的穿透率,為了賦予充分的耐光性,以使該穿透率充分地降低較理想。具體地,在260至380nm的波長區域之穿透率的最大值為3% 以下較理想,以2%以下更理想。 Further, it is desirable that the transmittance of ultraviolet rays as the entire polarizing plate is sufficiently reduced in order to provide sufficient light resistance. Specifically, the maximum value of the transmittance in the wavelength region of 260 to 380 nm is 3% The following is ideal, and more preferably 2% or less.
第1(甲基)丙烯酸系樹脂膜21的厚度,例如為5至200μm左右,從偏光板薄膜化以及膜的強度及處理性的觀點,較理想為10至150μm,更理想為15至100μm。 The thickness of the first (meth) acrylic resin film 21 is, for example, about 5 to 200 μm. From the viewpoint of thinning the polarizing plate, and the strength and handling properties of the film, the thickness is preferably 10 to 150 μm, and more preferably 15 to 100 μm.
第1(甲基)丙烯酸系樹脂膜21,可含有1種或2種以上的紫外線吸收劑以外的其他添加劑。可舉出其他添加劑的例子如橡膠粒子、潤滑劑、分散劑、熱安定劑、紅外線吸收劑、抗靜電劑、抗氧化劑等。 The first (meth) acrylic resin film 21 may contain one or more additives other than the ultraviolet absorber. Examples of other additives include rubber particles, lubricants, dispersants, heat stabilizers, infrared absorbers, antistatic agents, antioxidants, and the like.
調配橡膠粒子係在可改善(甲基)丙烯酸系樹脂的製膜性、膜的耐衝擊性、膜表面的光滑性的點上為有利。所謂橡膠粒子,係指包含顯示橡膠彈性的層之橡膠彈性體粒子。 The blending of the rubber particles is advantageous in that the film forming property of the (meth) acrylic resin, the impact resistance of the film, and the smoothness of the film surface can be improved. The rubber particles are rubber elastomer particles including a layer exhibiting rubber elasticity.
橡膠粒子可為只由顯示橡膠彈性的層所構成的粒子,亦可為具有顯示橡膠彈性的層及其他層的多層構造的粒子。作為橡膠彈性體,例如烯烴系彈性聚合物、二烯系彈性聚合物、苯乙烯-二烯系彈性共聚物、丙烯酸系彈性聚合物等。其中,從耐光性及透明性的觀點,以使用丙烯酸系彈性聚合物較理想。 The rubber particles may be particles composed of only a layer exhibiting rubber elasticity, or particles having a multilayer structure including a layer exhibiting rubber elasticity and other layers. Examples of the rubber elastomer include olefin-based elastic polymers, diene-based elastic polymers, styrene-diene-based elastic copolymers, and acrylic-based elastic polymers. Among them, it is preferable to use an acrylic elastic polymer from the viewpoint of light resistance and transparency.
丙烯酸系彈性聚合物,可為以丙烯酸烷酯為主體,亦即全部單體量為基準,包含50重量%以上的來自丙烯酸烷酯的構成單元的聚合物。丙烯酸系彈性聚合物,可為丙烯酸烷酯的均聚物,亦可為包含50重量%以上的來自甲基丙烯酸酯的構成單元、以及50重量%以下的來 自其他聚合性單體的構成單元的共聚物。 The acrylic elastic polymer may be a polymer mainly composed of an alkyl acrylate, that is, based on the total amount of monomers, and containing 50% by weight or more of a constituent unit derived from an alkyl acrylate. The acrylic elastic polymer may be a homopolymer of an alkyl acrylate, or may be a structural unit containing 50% by weight or more of a methacrylate-derived structural unit and 50% by weight or less. Copolymer of constituent units from other polymerizable monomers.
作為構成丙烯酸系彈性聚合物的丙烯酸烷酯,通常可使用該烷基的碳數為4至8者。可舉出上述其他聚合性單體的例子如甲基丙烯酸甲酯、甲基丙烯酸乙酯的甲基丙烯酸烷酯;如苯乙烯、烷基苯乙烯的苯乙烯系單體;如丙烯腈、甲基丙烯腈的不飽和腈等的單官能基單體,再者,如(甲基)丙烯酸烯丙酯、(甲基)丙烯酸甲基烯丙酯等的不飽和羧酸的烯酯;如順丁烯二酸二烯丙酯的二元酸的二烯酯;如烷二醇二(甲基)丙烯酸酯的二醇的不飽和羧酸二酯等的多官能基單體。 As the alkyl acrylate constituting the acrylic elastic polymer, those having 4 to 8 carbon atoms in the alkyl group can be generally used. Examples of the other polymerizable monomers mentioned above include methyl methacrylate and alkyl methacrylate; styrene-based monomers such as styrene and alkylstyrene; acrylonitrile and methyl Monofunctional monomers such as unsaturated acrylonitrile based on acrylonitrile, and allyl esters of unsaturated carboxylic acids such as allyl (meth) acrylate, methallyl (meth) acrylate, etc. A polyfunctional monomer such as a diene ester of a dibasic acid of a diallyl butadiene acid; an unsaturated carboxylic acid diester of a diol such as an alkanediol di (meth) acrylate.
包含丙烯酸系彈性聚合物的橡膠粒子,較理想為具有丙烯酸系彈性聚合物的層之多層構造的粒子。具體地,例如於丙烯酸系彈性聚合物的層的外側,具有以甲基丙烯酸烷酯為主體的硬質的聚合物層的2層構造者,或再於丙烯酸系彈性聚合物的層的內側具有以甲基丙烯酸烷酯為主體的硬質的聚合物層的3層構造者。 The rubber particles containing the acrylic elastic polymer are preferably particles having a multilayer structure having a layer of the acrylic elastic polymer. Specifically, for example, a two-layer structure having a hard polymer layer mainly composed of an alkyl methacrylate on the outside of the acrylic elastic polymer layer, or having A three-layer structure of a rigid polymer layer mainly composed of alkyl methacrylate.
構成形成於丙烯酸系彈性聚合物的層之外側或內側之硬質聚合物層的甲基丙烯酸烷酯為主體的聚合物之單體組成的例,係與舉例作為(甲基)丙烯酸系樹脂的例之甲基丙烯酸烷酯為主體的聚合物的單體組成的例相同,特別是使用以甲基丙烯酸甲酯為主體的單體組成較理想。如此的多層構造之丙烯酸系橡膠彈性體粒子,例如可藉由特公昭55-27576號公報記載的方法製造。 Examples of the monomer composition of a polymer mainly composed of an alkyl methacrylate which is a hard polymer layer formed on the outer or inner side of the acrylic elastic polymer layer are examples of the (meth) acrylic resin Examples of the monomer composition of the polymer mainly composed of alkyl methacrylate are the same. In particular, it is preferable to use a monomer composition mainly composed of methyl methacrylate. The acrylic rubber elastomer particles having such a multilayer structure can be produced, for example, by the method described in Japanese Patent Publication No. 55-27576.
橡膠粒子從(甲基)丙烯酸系樹脂的製膜 性、膜的耐衝擊性、膜表面的光滑性的觀點,包含於其中的橡膠彈性體層(丙烯酸系彈性聚合物的層)之平均粒徑為10至350nm的範圍較理想。該平均粒徑更理想為30nm以上,進一步50nm以上,而且更理想為300nm以下,進一步280nm以下。 Film formation of rubber particles from (meth) acrylic resin From the viewpoints of properties, impact resistance of the film, and smoothness of the film surface, the average particle diameter of the rubber elastomer layer (layer of acrylic elastic polymer) included therein is preferably in a range of 10 to 350 nm. The average particle diameter is more preferably 30 nm or more, further 50 nm or more, and more preferably 300 nm or less, and further 280 nm or less.
橡膠粒子中至橡膠彈性體層(丙烯酸系彈性聚合物的層)的平均粒徑,係藉由以下方式測定。亦即,將如此的橡膠粒子混合於(甲基)丙烯酸系樹脂,使其薄膜化,其剖面以氧化釕的水溶液染色時,只有橡膠彈性體層著色,觀察到約圓形狀,母層的甲基丙烯酸系樹脂沒有被染色。所以,從如此作法而被染色的膜剖面,使用切片機等,調製薄片,以電子顯微鏡觀察。於是,隨機地取100個染色的橡膠粒子,算出各粒徑(橡膠彈性體層為止的直徑)後,以其數目平均值作為上述平均粒徑。因以如此的方法測定,故所得的上述平均粒徑為數目平均粒徑。 The average particle diameter of the rubber particles to the rubber elastomer layer (layer of the acrylic elastic polymer) was measured in the following manner. That is, when such rubber particles are mixed with a (meth) acrylic resin to make it into a thin film. When the cross section is dyed with an aqueous solution of ruthenium oxide, only the rubber elastomer layer is colored. The acrylic resin was not dyed. Therefore, from the cross section of the film dyed in this manner, a slice is prepared using a microtome or the like, and observed with an electron microscope. Then, 100 dyed rubber particles were randomly taken, each particle diameter (diameter of the rubber elastomer layer) was calculated, and the number average was used as the average particle diameter. Since it is measured by such a method, the said average particle diameter obtained is a number average particle diameter.
最外層為以甲基丙烯酸甲酯為主體的硬質聚合物,於其中橡膠彈性體層(丙烯酸系彈性聚合物的層)環繞的橡膠粒子時,若將其混合於母體的甲基丙烯酸系樹脂,橡膠粒子的最外層會與母體的甲基丙烯酸系樹脂混合。因此,其剖面以氧化釕染色,以電子顯微鏡觀察時,觀察到橡膠粒子為除去最外層的狀態的粒子。具體地,內層為丙烯酸系彈性聚合物,且外層為以甲基丙烯酸甲酯為主體的硬質聚合物之2層構造的橡膠粒子時,內層的丙烯酸系彈性聚合物部分被染色,觀察到單層構造的粒子。而 且,最內層為以甲基丙烯酸甲酯為主體的硬質聚合物、且中間層為丙烯酸系彈性聚合物、最外層為以甲基丙烯酸甲酯為主體的硬質聚合物之3層構造的橡膠粒子時,最內層的粒子中心部分未被染色,而只有中間層的丙烯酸系彈性聚合物部分被染色,觀察到2層構造的粒子。 The outermost layer is a hard polymer mainly composed of methyl methacrylate. When rubber particles surrounded by a rubber elastomer layer (acrylic elastic polymer layer) are mixed, if they are mixed with a base methacrylic resin, the rubber The outermost layer of the particles is mixed with the parent methacrylic resin. Therefore, when the cross section was stained with ruthenium oxide and observed with an electron microscope, rubber particles were observed as particles in a state where the outermost layer was removed. Specifically, when the inner layer is an acrylic elastic polymer and the outer layer is a rubber particle having a two-layer structure of a hard polymer mainly composed of methyl methacrylate, the acrylic elastic polymer portion of the inner layer is dyed, and it is observed that Single-layered particles. and In addition, a rubber having a three-layer structure in which the innermost layer is a hard polymer mainly composed of methyl methacrylate, the intermediate layer is an acrylic elastic polymer, and the outermost layer is a rigid polymer mainly composed of methyl methacrylate. In the case of particles, the inner part of the innermost particle was not dyed, and only the acrylic elastic polymer part of the middle layer was dyed, and particles with a two-layer structure were observed.
從甲基丙烯酸系樹脂的製膜性、膜的耐衝擊性、膜表面的光滑性的觀點,以構成第1(甲基)丙烯酸系樹脂膜21的甲基丙烯酸系樹脂的合計量為基準,調配橡膠粒子較理想為以3重量%以上、60重量%以下的比例,更理想為45重量%以下,更加理想為35重量%以下。橡膠彈性體粒子比60重量%還多時,膜的尺寸變化變大,其耐熱性降低。另一方面,橡膠彈性體粒子比3重量%還少時,雖然膜的耐熱性良好,但製膜時捲取性差、生產性低。再者,於本發明中,作為橡膠彈性體粒子,使用具有顯示橡膠彈性的層及其他層的多層構造的粒子時,顯示橡膠彈性的層及其內側的層所構成的部分的重量設為橡膠彈性體粒子的重量。例如使用上述3層構造的丙烯酸系橡膠彈性體粒子時,中間層的丙烯酸系彈性聚合物部分與以最內層的甲基丙烯酸甲酯為主體的硬質聚合物部分的合計重量設為橡膠彈性體粒子的重量。上述3層構造的丙烯酸系橡膠彈性體粒子溶解於丙酮時,中間層的丙烯酸系彈性聚合物部分與以最內層的甲基丙烯酸甲酯為主體的硬質聚合物部分因係不溶成分而殘留,故可容易地求得佔據3層構造的丙烯酸系橡膠粒子之中間層與最內層的合計重量比例。 From the viewpoint of the film-forming properties of the methacrylic resin, the impact resistance of the film, and the smoothness of the film surface, based on the total amount of the methacrylic resin constituting the first (meth) acrylic resin film 21, The blended rubber particles are preferably in a ratio of 3% by weight to 60% by weight, more preferably 45% by weight or less, and even more preferably 35% by weight or less. When the rubber elastomer particles are more than 60% by weight, the dimensional change of the film becomes large, and the heat resistance thereof decreases. On the other hand, when the rubber elastomer particles are less than 3% by weight, the film has good heat resistance, but has poor winding properties and low productivity during film formation. In addition, in the present invention, when the particles having a multilayer structure having a layer exhibiting rubber elasticity and other layers are used as the rubber elastomer particles, the weight of the portion composed of the layer exhibiting rubber elasticity and the layer on the inside thereof is rubber. The weight of the elastomer particles. For example, when using the acrylic rubber elastomer particles having the three-layer structure described above, the total weight of the acrylic elastic polymer portion of the intermediate layer and the hard polymer portion mainly composed of the innermost methyl methacrylate is set to the rubber elastomer. The weight of the particles. When the acrylic rubber elastomer particles of the above three-layer structure are dissolved in acetone, the acrylic elastic polymer part of the intermediate layer and the hard polymer part mainly composed of the innermost methyl methacrylate remain because of the insoluble component, Therefore, the total weight ratio of the intermediate layer and the innermost layer of the acrylic rubber particles occupying a three-layer structure can be easily obtained.
第1(甲基)丙烯酸系樹脂膜21包含橡膠粒子時,該薄膜的製作所使用的含有橡膠粒子的(甲基)丙烯酸系樹脂組成物,除可藉由將甲基丙烯酸系樹脂與橡膠粒子以熔融混練等混合而得到外,亦可首先製作橡膠粒子,於其存在下,藉由使成為甲基丙烯酸系樹脂的原料之單體組成物聚合的方法而得。 When the first (meth) acrylic resin film 21 contains rubber particles, the (meth) acrylic resin composition containing rubber particles used in the production of the film can be obtained by combining methacrylic resin and rubber particles with In addition to being obtained by mixing such as melt-kneading, rubber particles may be first prepared and obtained by a method of polymerizing a monomer composition that is a raw material of a methacrylic resin in the presence of the rubber particles.
(3)第2(甲基)丙烯酸系樹脂膜 (3) 2nd (meth) acrylic resin film
第2(甲基)丙烯酸系樹脂膜22係積層於偏光片10的另一側的面之保護膜,偏光板應用於液晶面板時,於辨識側的偏光板、背光側的偏光板之任一者,皆為配置於液晶胞側的保護膜。 The second (meth) acrylic resin film 22 is a protective film laminated on the other side of the polarizer 10. When a polarizing plate is applied to a liquid crystal panel, any of the polarizing plate on the identification side and the polarizing plate on the backlight side Both are protective films disposed on the liquid crystal cell side.
如此地本發明的偏光板,係於兩面保護膜使用相同種的樹脂所構成的膜者,藉此,因尺寸變化的行為變成上下對稱,可防止偏光板產生翹曲,進而防止液晶面板產生翹曲。因此,可防止面板的翹曲為起因的顯示上的缺陷,例如面板接觸於邊緣部(bezel)等所引起的漏光等上很有用。其特別對IPS模式很有效。此處,所謂由相同種的樹脂所構成的膜,只要是相同種的樹脂所構成,亦可為不相同的膜,例如樹脂的組成可為不同,且調配於膜的添加劑的量、種類亦可為不同。 In this way, the polarizing plate of the present invention is a film composed of the same kind of resin on both sides of the protective film, and thereby, the behavior of the change in size becomes vertical symmetry, which can prevent the polarizing plate from warping, and thus prevent the liquid crystal panel from warping. song. Therefore, it is useful to prevent display defects caused by warping of the panel, such as light leakage caused by the panel contacting a bezel or the like. It is especially effective for IPS mode. Here, the so-called films made of the same kind of resin may be different films as long as they are made of the same kind of resin. For example, the composition of the resin may be different, and the amount and type of additives formulated in the film may also be different. Can be different.
第2(甲基)丙烯酸系樹脂膜22係與第1(甲基)丙烯酸系樹脂膜21不同,且為提高紫外線的穿透率的保護膜,具體地該膜中的紫外線吸收劑的含量為1重量%以下,較理想為0.5重量%以下,更理想為0.2重量%以下,特別 理想為不含有紫外線吸收劑。 The second (meth) acrylic resin film 22 is different from the first (meth) acrylic resin film 21 and is a protective film that improves the transmittance of ultraviolet rays. Specifically, the content of the ultraviolet absorber in the film is 1% by weight or less, more preferably 0.5% by weight or less, more preferably 0.2% by weight or less, particularly It is desirable not to contain an ultraviolet absorber.
將第2(甲基)丙烯酸系樹脂膜22的紫外線吸收劑的含量與第1(甲基)丙烯酸系樹脂膜21比較而相對降低、或使第2(甲基)丙烯酸系樹脂膜22設為不含有紫外線吸收劑之本發明的偏光板,係例如在以下的點變得有利。 The content of the ultraviolet absorber of the second (meth) acrylic resin film 22 is relatively reduced compared with the first (meth) acrylic resin film 21, or the second (meth) acrylic resin film 22 is set to The polarizing plate of the present invention which does not contain an ultraviolet absorber is advantageous in the following points, for example.
[a]可防止或抑制如上述的來自紫外線吸收劑的異物的附著/混入。亦即,推測該異物的附著/混入,係在(甲基)丙烯酸系樹脂膜藉由熔融擠出法製作時之(甲基)丙烯酸系樹脂的加熱熔融時,在T型模頭蒸發,其再次固化為粒子狀所產生的粒子附著於膜表面,包含紫外線吸收劑的液狀物滴下而附著於膜表面或混入膜內所引起者,藉由極力抑制紫外線吸收劑的含量,可防止、抑制如此的異物的附著/混入。 [a] It is possible to prevent or suppress the adhesion / contamination of the foreign matter derived from the ultraviolet absorber as described above. That is, it is estimated that the adhesion / contamination of the foreign matter is caused by evaporation of the (meth) acrylic resin when the (meth) acrylic resin film is heated and melted when the (meth) acrylic resin film is produced by the melt extrusion method. Particles produced by re-solidification into particles are attached to the surface of the film, caused by the liquid substance containing the ultraviolet absorber dripping and adhering to the film surface or being mixed in the film. The content of the ultraviolet absorber can be prevented and suppressed by extremely suppressing the content of the ultraviolet absorber. Adhesion / contamination of such foreign matter.
而且,(甲基)丙烯酸系樹脂的未延伸膜以熔融擠出法製作,將其實施延伸處理時,亦可防止、抑制如上述的異物的附著/混入。(甲基)丙烯酸系樹脂膜如上述藉由熔融擠出法製作後,為了賦予所期望的光學特性、或機械特性,可實施延伸處理。延伸處理係可以傳統習知的方法進行,例如一軸延伸、二軸延伸等。作為延伸方向係例如未延伸膜的機械移動方向(MD)、與其垂直的方向(TD)、與機械移動方向斜交的方向等。二軸延伸係可為2個延伸方向同時延伸的同時二軸延伸,亦可在一方向延伸後,朝其他方向延伸之逐次二軸延伸。 In addition, an unstretched film of a (meth) acrylic resin is produced by a melt extrusion method, and when it is subjected to a stretching treatment, it is also possible to prevent or suppress the adhesion / contamination of foreign matter as described above. After the (meth) acrylic resin film is produced by the melt extrusion method as described above, in order to impart desired optical characteristics or mechanical characteristics, stretching treatment may be performed. The extension processing can be performed by conventional methods, such as one-axis extension, two-axis extension, and the like. Examples of the stretching direction include a mechanical moving direction (MD) of the unstretched film, a direction (TD) perpendicular thereto, and a direction oblique to the mechanical moving direction. The biaxial extension system can be a simultaneous biaxial extension in two extension directions, or a sequential biaxial extension in one direction and then in other directions.
特別是偏光板所具有的2個(甲基)丙烯酸系 樹脂膜中,藉由抑制成為液晶面板時配置於液晶胞側的第2(甲基)丙烯酸系樹脂膜22的紫外線吸收劑的含量,可抑制形成於液晶面板的正交尼科爾(Cross Nicol)中含有異物。如此可有效防止液晶顯示裝置的黑色顯示時產生漏光等的辨識性的降低。 Especially the two (meth) acrylics that the polarizer has In the resin film, by suppressing the content of the ultraviolet absorber of the second (meth) acrylic resin film 22 disposed on the liquid crystal cell side when it becomes a liquid crystal panel, it is possible to suppress Cross Nicol (Cross Nicol) formed in the liquid crystal panel. ) Contains foreign matter. In this way, it is possible to effectively prevent a decrease in visibility such as light leakage during black display of the liquid crystal display device.
[b]因第2(甲基)丙烯酸系樹脂膜22的紫外線吸收劑的含量低(較理想為不含有紫外線吸收劑),於使用紫外線硬化性接著劑貼合第1及第2(甲基)丙烯酸系樹脂膜21、22於偏光片10時,不選擇接著劑的光聚合引發劑的種類,可容易地使接著劑硬化,同時可提高硬化度。藉此,可提高所得之偏光板的偏光片10與(甲基)丙烯酸系樹脂膜的密合性及偏光板的機械強度。另一方面,於第1(甲基)丙烯酸系樹脂膜21係因調配充分量的紫外線吸收劑,可賦予偏光板充分的耐光性。 [b] Since the content of the ultraviolet absorber of the second (meth) acrylic resin film 22 is low (preferably without an ultraviolet absorbent), the first and second (methyl) ) When the acrylic resin films 21 and 22 are on the polarizer 10, the type of the photopolymerization initiator of the adhesive is not selected, the adhesive can be easily hardened, and at the same time, the degree of hardening can be improved. Thereby, the adhesiveness of the obtained polarizer 10 of a polarizing plate with a (meth) acrylic-type resin film, and the mechanical strength of a polarizing plate can be improved. On the other hand, a sufficient amount of an ultraviolet absorber is added to the first (meth) acrylic resin film 21 to provide sufficient light resistance to the polarizing plate.
第2(甲基)丙烯酸系樹脂膜22在紫外線中,特別是以260至320nm的波長區域的穿透率高較理想,具體地以260至320nm的波長區域的穿透率為20%以上較理想,30%以上更理想,40%以上更加理想。260至320nm的波長區域係貼合偏光片與保護膜用的紫外線硬化性接著劑一般感應的波長區域,藉由該波長區域的穿透率高,可提高紫外線硬化性接著劑的硬化速度及硬化度,可抑制接著劑中的光聚合引發劑的添加量。再者,於本發明中,所謂260至320nm的波長區域的穿透率為20%以上,係指260至320nm的波長區域的至少1處,穿透率為20% 以上。 The second (meth) acrylic resin film 22 preferably has a high transmittance in ultraviolet rays, particularly in a wavelength region of 260 to 320 nm, and specifically has a transmittance of 20% or more in a wavelength region of 260 to 320 nm. Ideal, more than 30% is more ideal, more than 40% is more ideal. The wavelength region of 260 to 320 nm is a wavelength region generally sensitive to ultraviolet curable adhesives used for bonding polarizers and protective films. The high transmittance of this wavelength region can increase the curing speed and curing of ultraviolet curable adhesives. The amount of the photopolymerization initiator in the adhesive can be suppressed. Furthermore, in the present invention, the transmittance in the wavelength region of 260 to 320 nm is 20% or more, which means that at least one of the wavelength regions in the range of 260 to 320 nm has a transmittance of 20%. the above.
將偏光板應用於使用IPS模式的液晶胞之液晶顯示裝置時,第2(甲基)丙烯酸系樹脂膜22為實質上不具有光學異向性較理想。具體地,第2(甲基)丙烯酸系樹脂膜22係波長590nm的面內相位差值R0為10nm以下較理想,5nm以下更理想。而且,波長590nm的厚度方向相位差值Rth的絕對值為10nm以下較理想,5nm以下更理想。 When a polarizing plate is applied to a liquid crystal display device using a liquid crystal cell of the IPS mode, it is preferable that the second (meth) acrylic resin film 22 has substantially no optical anisotropy. Specifically, it is preferable that the in-plane retardation value R 0 of the second (meth) acrylic resin film 22 based on a wavelength of 590 nm is 10 nm or less, and more preferably 5 nm or less. The absolute value of the thickness direction retardation value R th at a wavelength of 590 nm is preferably 10 nm or less, and more preferably 5 nm or less.
面內相位差值R0、厚度方向相位差值Rth,分別以下述式定義。 The in-plane phase difference value R 0 and the thickness direction phase difference value R th are defined by the following formulas, respectively.
R0=(nx-ny)×d R 0 = (n x -n y ) × d
Rth=[(nx+ny)/2-nz]×d nx為膜的面內延遲相位軸方向的折射率,ny為面內前進相位軸方向(在面內垂直於面內延遲相位軸方向的方向)的折射率,nz為厚度方向的折射率,d為膜的厚度。 R th = [(n x + n y ) / 2-n z ] × dn x is the refractive index in the in-plane retardation phase axis direction of the film, and n y is the in-plane advancing phase axis direction (in-plane perpendicular to in-plane) The refractive index in the direction of the retardation phase axis), n z is the refractive index in the thickness direction, and d is the thickness of the film.
關於構成第2(甲基)丙烯酸系樹脂膜22的(甲基)丙烯酸系樹脂、含有紫外線吸收劑時之種類、膜的厚度以及調配於膜的其他添加劑(例如橡膠粒子),引用關於第1(甲基)丙烯酸系樹脂膜21的上述記載。特別是(甲基)丙烯酸系樹脂容易帶電,由於環境異物等容易附著,第2(甲基)丙烯酸系樹脂膜22中或第2(甲基)丙烯酸系樹脂膜22上,添加0.01至10重量份的帶電防止劑(層)為較理想。關於附著異物,亦與來自紫外線吸收劑的異物同樣地,可抑制形成於液晶面板的正交尼科爾(Cross Nicol)中含有異物,可有效防止液晶顯示裝置的黑色顯示時產生漏光等的 辨識性的降低。 Regarding the (meth) acrylic resin constituting the second (meth) acrylic resin film 22, the type when the ultraviolet absorber is contained, the thickness of the film, and other additives (such as rubber particles) blended in the film, the first The above description of the (meth) acrylic resin film 21. In particular, (meth) acrylic resin is easy to be charged, and it is easy to attach environmental foreign matter. Therefore, the second (meth) acrylic resin film 22 or the second (meth) acrylic resin film 22 is added in an amount of 0.01 to 10 weight. A part of the antistatic agent (layer) is preferable. Regarding the adhesion of foreign matter, similar to the foreign matter derived from the ultraviolet absorber, it can suppress the inclusion of foreign matter in the cross nicol formed on the liquid crystal panel, and can effectively prevent light leakage during the black display of the liquid crystal display device. Reduced visibility.
第1(甲基)丙烯酸系樹脂膜21與第2(甲基)丙烯酸系樹脂膜22,在有無其他添加劑之使用、種類及調配量、紫外線吸收劑的種類、(甲基)丙烯酸系樹脂的種類以及膜的厚度中,可為相同,於任一點以上可為不同。 Whether the first (meth) acrylic resin film 21 and the second (meth) acrylic resin film 22 are used, the types and blending amounts of other additives, the types of ultraviolet absorbers, the (meth) acrylic resin The kind and the thickness of the film may be the same, and may be different at any one point or more.
(4)第1及第2接著劑層 (4) First and second adhesive layers
第1及第2(甲基)丙烯酸系樹脂膜21、22與偏光片10貼合,通常使用接著劑來進行(第1圖的第1及第2接著劑層15、25)。形成第1及第2接著劑層15、25的接著劑,較理想為紫外線硬化性接著劑,更理想為感應260至320nm的波長區域的紫外線而硬化的接著劑。所以,第1及第2接著劑層15、25較理想為該接著劑的硬化物層。 The first and second (meth) acrylic resin films 21 and 22 are bonded to the polarizer 10 and usually performed using an adhesive (the first and second adhesive layers 15 and 25 in FIG. 1). The adhesive for forming the first and second adhesive layers 15 and 25 is more preferably an ultraviolet curable adhesive, and more preferably an adhesive that is cured by sensing ultraviolet rays in a wavelength range of 260 to 320 nm. Therefore, the first and second adhesive layers 15 and 25 are preferably hardened layers of the adhesive.
構成紫外線硬化性接著劑之藉由紫外線的照射而硬化的成分(以下也只稱為「硬化性成分」),可為環氧化合物、氧雜環丁烷(oxetane)化合物、(甲基)丙烯酸系化合物等。其中,作為上述接著劑,較宜使用藉由陽離子聚合而硬化的環氧系化合物作為硬化性成分的紫外線硬化性接著劑。此處所謂之環氧系化合物,係指於分子內具有平均1個以上,較理想為2個以上的環氧基之化合物。環氧系化合物可使用單獨1種,或亦可併用2種以上。 The component (hereinafter also simply referred to as a "curable component") that constitutes an ultraviolet curable adhesive and is cured by irradiation of ultraviolet rays may be an epoxy compound, an oxetane compound, or (meth) acrylic acid. Department of compounds and so on. Among these, as the above-mentioned adhesive, an ultraviolet-curable adhesive having an epoxy-based compound hardened by cationic polymerization is preferably used as a hardening component. The epoxy-based compound herein refers to a compound having an average of one or more, and preferably two or more epoxy groups in the molecule. The epoxy-based compound may be used singly or in combination of two or more kinds.
可適合使用的環氧系化合物的例,包括:於芳香族聚醇的芳香環進行氫化反應所得之脂環式聚醇,使環氧氯丙烷反應所得之氫化環氧化合物(具有脂環式環的聚醇的環氧丙基醚);如脂肪族多元醇或其環氧烷加成物 的聚環氧丙基醚之脂肪族環氧系化合物;於分子內具有1個以上的鍵結於脂環式環的環氧基之環氧系化合物之脂環式環氧系化合物。 Examples of suitable epoxy-based compounds include alicyclic polyols obtained by hydrogenating an aromatic ring of an aromatic polyol, and hydrogenated epoxy compounds (having an alicyclic ring) obtained by reacting epichlorohydrin. Epoxy propylene ether of polyalcohols); such as aliphatic polyols or alkylene oxide adducts thereof Aliphatic epoxy compounds of poly (glycidyl ether); alicyclic epoxy compounds of epoxy compounds having one or more epoxy groups bonded to alicyclic rings in the molecule.
環氧化合物係可容易取得其市售品,例如分別以商品名,日本環氧樹脂公司販售的「EPICOTE」系列、DIC公司販售的「EPICLON」系列、東都化成公司販售的「EPOTOT」系列、ADEKA公司販售的「ADEKARESIN」系列、長瀨化學公司販售的「DENACOL」系列、道氏化學公司販售的「DOW EPOXY」系列、日產化學工業公司販售的「DEPIKU」等。 Epoxy compounds are easily available on the market, such as the "EPICOTE" series sold by the Japanese epoxy resin company, the "EPICLON" series sold by the DIC company, and the "EPOTOT" sold by Tohto Kasei Co. Series, "ADEKARESIN" series sold by ADEKA, "DENACOL" series sold by Nagase Chemical Co., "DOW EPOXY" series sold by Dow Chemical Co., and "DEPIKU" sold by Nissan Chemical Industries.
上述脂環式環氧化合物也可容易取得其市售品,例如分別以商品名,DAICEL化學工業公司販售的「CELLOXIDE」系列及「CYCLOMER」系列、道氏化學公司販售的「CYRACURE」系列等。 The above-mentioned alicyclic epoxy compounds can also be easily obtained in commercial products, such as the "CELLOXIDE" series and "CYCLOMER" series sold under the brand name, DAICEL Chemical Industry Co., and "CYRACURE" series sold by Dow Chemical Co. Wait.
紫外線硬化性接著劑係取代藉由陽離子聚合而硬化的環氧系化合物,或與其同時地含有自由基聚合性之(甲基)丙烯酸系化合物作為硬化性成分。作為(甲基)丙烯酸系化合物係例如於分子內具有至少1個(甲基)丙烯醯氧基的(甲基)丙烯酸酯單體等的分子內具有至少1個(甲基)丙烯醯基的(甲基)丙烯酸單體;於分子內具有至少1個(甲基)丙烯醯基及醯胺鍵結的(甲基)丙烯醯胺單體;使2種以上的含有官能基的化合物反應所得之於分子內具有至少2個(甲基)丙烯醯基的(甲基)丙烯酸寡聚物等的含有(甲基)丙烯醯基的化合物。(甲基)丙烯酸寡聚物較理想為於分 子內具有至少2個(甲基)丙烯醯氧基的(甲基)丙烯酸酯寡聚物。(甲基)丙烯酸系化合物係可使用單獨1種,亦可併用2種以上。(甲基)丙烯酸系化合物較理想為包含(甲基)丙烯醯胺單體。 The ultraviolet-curable adhesive is used instead of an epoxy-based compound that is hardened by cation polymerization, or a radically polymerizable (meth) acrylic compound is used as a hardening component at the same time. The (meth) acrylic compound is, for example, a (meth) acrylic acid ester monomer having at least one (meth) acryloxy group in the molecule and having at least one (meth) acrylfluorene group in the molecule. (Meth) acrylic acid monomer; (meth) acrylamide monomer having at least one (meth) acrylfluorene group and amidine bond in the molecule; obtained by reacting two or more kinds of compounds containing a functional group This is for compounds containing (meth) acrylfluorenyl groups, such as (meth) acrylic acid oligomers having at least two (meth) acrylfluorenyl groups in the molecule. (Meth) acrylic acid oligomers A (meth) acrylate oligomer having at least two (meth) acrylic alkoxy groups in the daughter. The (meth) acrylic compound may be used alone or in combination of two or more. The (meth) acrylic compound preferably contains a (meth) acrylamide monomer.
作為於分子內具有至少1個(甲基)丙烯醯基及醯胺鍵結的(甲基)丙烯醯胺單體,更理想為下述通式(vi):CH2=C(R28)-CONH(2-i)-(L-O-R29)i 通式(vi)所示的N-取代醯胺系單體。式中,R28表示氫原子或甲基,L表示亞甲基或伸乙基,R29表示氫原子、甲基或乙基,i表示1或2。 As the (meth) acrylamide monomer having at least one (meth) acrylfluorenyl group and amidine bond in the molecule, the following general formula (vi) is more preferable: CH 2 = C (R 28 ) -CONH (2-i) -(LOR 29 ) i is an N-substituted fluorene-based monomer represented by general formula (vi). In the formula, R 28 represents a hydrogen atom or a methyl group, L represents a methylene group or an ethyl group, R 29 represents a hydrogen atom, a methyl group, or an ethyl group, and i represents 1 or 2.
作為上述通式(vi)所示的N-取代醯胺系單體的具體例,可舉例如N-羥基乙基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-甲氧基甲基(甲基)丙烯醯胺、N-乙氧基甲基(甲基)丙烯醯胺、N-甲氧基乙基(甲基)丙烯醯胺、N-乙氧基乙基(甲基)丙烯醯胺等。該等N-取代醯胺系單體係可使用單獨1種,亦可使用2種以上的組合。 Specific examples of the N-substituted amidoamine-based monomer represented by the general formula (vi) include N-hydroxyethyl (meth) acrylamidonium and N-hydroxymethyl (meth) acrylamidoamine. , N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-ethoxy Ethyl (meth) acrylamide and the like. These N-substituted amidoamine-based monosystems may be used alone or in combination of two or more.
上述通式(vi)所示的N-取代醯胺系單體,對於低水分率的偏光片、使用透濕度低的材料之保護膜,亦顯示良好的接著性,所以較理想。例示的單體中,N-羥基乙基(甲基)丙烯醯胺,由於顯示特別良好的接著性,所以更理想。 The N-substituted fluorene amine-based monomer represented by the general formula (vi) is preferable because it exhibits good adhesion to polarizers with low moisture content and protective films using materials with low moisture permeability. Among the exemplified monomers, N-hydroxyethyl (meth) acrylamide is more preferable because it exhibits particularly good adhesion.
自由基聚合性化合物亦可含有除上述通式(vi)所示的N-取代醯胺系單體以外的(甲基)丙烯酸系化合 物,亦即上述通式(vi)所示的N-取代醯胺系單體以外的N-取代醯胺系單體、具有芳香環及羥基的各種單官能基(甲基)丙烯酸酯、胺基甲酸酯(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、各種具有(甲基)丙烯醯基的化合物等。但是,考慮接著劑層的接著性及耐水性時,相對於自由基聚合性化合物的合計量,上述通式(vi)所示的N-取代醯胺系單體的比例為以50至99重量%較理想,以60至90重量%更理想。 The radically polymerizable compound may contain a (meth) acrylic compound other than the N-substituted amidoamine-based monomer represented by the general formula (vi). Substances, that is, N-substituted fluorene-amine monomers other than the N-substituted fluoramine-based monomers represented by the general formula (vi), various monofunctional (meth) acrylates, amines having an aromatic ring and a hydroxyl group, and amines Carbamate (meth) acrylate, polyester (meth) acrylate, various compounds having a (meth) acrylfluorenyl group, and the like. However, in consideration of the adhesiveness and water resistance of the adhesive layer, the ratio of the N-substituted amidoamine-based monomer represented by the general formula (vi) is 50 to 99 weight based on the total amount of the radical polymerizable compound. % Is more preferable, and 60 to 90% by weight is more preferable.
作為上述通式(vi)所示的N-取代醯胺系單體以外的N-取代醯胺系單體,可舉例如N-甲基(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-己基(甲基)丙烯醯胺、胺基甲基(甲基)丙烯醯胺、胺基乙基(甲基)丙烯醯胺、硫醇基甲基(甲基)丙烯醯胺、硫醇基乙基(甲基)丙烯醯胺、N-丙烯醯基嗎啉、N-丙烯醯基哌啶、N-甲基丙烯醯基哌啶、N-丙烯醯基吡咯烷(Pyrrolidine)等。 Examples of the N-substituted fluorene-amine monomer other than the N-substituted fluoramine-based monomer represented by the general formula (vi) include N-methyl (meth) acrylamide and N, N-dimethylamine. (Meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N -Hexyl (meth) acrylamide, aminomethyl (meth) acrylamide, aminoethyl (meth) acrylamide, thiol methyl (meth) acrylamine, thiol Ethyl (meth) acrylamidonium, N-acrylamidomorpholine, N-acrylamidopiperidine, N-methacrylamidopiperidine, N-acrylamidopyrrolidine (Pyrrolidine), and the like.
作為具有芳香環及羥基的單官能基(甲基)丙烯酸酯,可使用具有芳香環及羥基的各種單官能基(甲基)丙烯酸酯。羥基係可存在作為芳香環的取代基,存在作為芳香環與(甲基)丙烯酸酯鍵結的有機基(烴基、特別是伸烷基)的取代基較理想。 As the monofunctional (meth) acrylate having an aromatic ring and a hydroxyl group, various monofunctional (meth) acrylates having an aromatic ring and a hydroxyl group can be used. A hydroxyl group may exist as a substituent of an aromatic ring, and it is preferable to exist as a substituent of an organic group (hydrocarbon group, especially an alkylene group) in which an aromatic ring is bonded to a (meth) acrylate.
作為上述具有芳香環及羥基的單官能基(甲基)丙烯酸酯,可舉例如具有芳香環的單官能基的環氧化合物與(甲基)丙烯酸的反應物。作為具有芳香環的單官能基的環氧化合物,可舉例如苯基環氧丙基醚、第三丁基苯基 環氧丙基醚、苯基聚乙二醇環氧丙基醚等。具有芳香環及羥基的單官能基(甲基)丙烯酸酯的具體例,例如(甲基)丙烯酸2-羥基-3-苯氧基丙酯、(甲基)丙烯酸2-羥基-3-第三丁基苯氧基丙酯、2-羥基-3-苯基聚乙二醇丙基(甲基)丙烯酸酯等。 Examples of the monofunctional (meth) acrylate having an aromatic ring and a hydroxyl group include a reaction product of a monofunctional epoxy compound having an aromatic ring and (meth) acrylic acid. Examples of the monofunctional epoxy compound having an aromatic ring include a phenylepoxypropyl ether and a third butylphenyl group. Glycidyl ether, phenyl polyethylene glycol glycidyl ether and the like. Specific examples of the monofunctional (meth) acrylate having an aromatic ring and a hydroxyl group, such as 2-hydroxy-3-phenoxypropyl (meth) acrylate and 2-hydroxy-3-third (meth) acrylate Butylphenoxypropyl, 2-hydroxy-3-phenyl polyethylene glycol propyl (meth) acrylate, and the like.
而且,作為上述胺基甲酸酯(甲基)丙烯酸酯係例如具有異氰酸酯基的(甲基)丙烯酸酯與二醇化合物的單末端的羥基之反應物等。作為二醇化合物係例如聚胺基甲酸酯二醇、聚酯二醇、聚醚二醇、聚乙二醇、聚丙二醇等的聚烷二醇等。 The urethane (meth) acrylate is, for example, a reaction product between a (meth) acrylate having an isocyanate group and a single-terminal hydroxyl group of a diol compound. Examples of the diol compound include polyalkylene glycols such as polyurethane diol, polyester diol, polyether diol, polyethylene glycol, and polypropylene glycol.
作為具有(甲基)丙烯醯基的化合物係例如(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2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯及(甲基)丙烯酸月桂酯等的(甲基)丙烯酸碳數1至12的烷酯;(甲基)丙烯酸甲氧基乙酯及(甲基)丙烯酸乙氧基乙酯等的(甲基)丙烯酸烷氧基烷酯系單體;(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(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、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯及(4-羥基甲基環己基)-丙烯酸甲酯等的含有羥基的單體;順丁烯二酸酐及亞甲基丁二酸酐等的含有酸酐基的單體;丙烯酸的己內酯加成物;苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙烷磺酸、(甲基)丙烯醯胺丙烷磺酸、(甲基)丙烯酸磺丙酯及(甲基)丙烯醯氧 基萘磺酸等的含有磺酸基的單體;2-羥基乙基丙烯醯基磷酸酯等的含有磷酸基的單體等。而且,例如包含馬來醯亞胺、N-環己基馬來醯亞胺及N-苯基馬來醯亞胺等的含有馬來醯亞胺基的單體;(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸胺基丙酯、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸第三丁基胺基乙酯及(甲基)丙烯酸3-(3-吡啶基)丙酯等的(甲基)丙烯酸烷基胺基烷酯系單體;N-(甲基)丙烯醯氧基亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-6-氧基六亞甲基琥珀醯亞胺及N-(甲基)丙烯醯基-8-氧基八亞甲基琥珀醯亞胺等的琥珀醯亞胺系單體之含有氮的單體。 Examples of the compound having a (meth) acrylfluorenyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Alkyl (meth) acrylate having 1 to 12 carbons, such as isooctyl (meth) acrylate, isononyl (meth) acrylate, and lauryl (meth) acrylate; methoxyethyl (meth) acrylate (Meth) acrylate alkoxyalkyl ester-based monomers such as esters and ethoxyethyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12 (meth) acrylate -Hydroxylauryl esters and (4-hydroxymethylcyclohexyl) -methyl acrylate-containing monomers; maleic anhydride-containing monomers such as maleic anhydride and methylene succinic anhydride; acrylic acid Lactone adducts; styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, (meth) Sulfopropyl acrylate and (meth) propylene Oxygen Sulfonic acid group-containing monomers such as naphthalenesulfonic acid; phosphate group-containing monomers such as 2-hydroxyethylpropenyl phosphonium phosphate; and the like. Further, for example, a maleimide group-containing monomer including maleimide, N-cyclohexylmaleimide, and N-phenylmaleimide; and (meth) acrylamidoethyl Ester, aminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, tertiary butylaminoethyl (meth) acrylate, and 3- (meth) acrylate 3- Alkyl (meth) acrylic alkylamino alkyl monomers such as (3-pyridyl) propyl; N- (meth) acryloxymethyleneoxysuccinimide, N- (meth) propylene Nitrogen containing succinimide-based monomers such as fluorenyl-6-oxyhexamethylene succinimide and N- (meth) acrylfluorenyl-8-oxyoctamethylene succinimide, etc. Monomer.
就使2種以上的含有官能基的化合物反應所得之於分子內具有至少2個(甲基)丙烯醯氧基的(甲基)丙烯酸寡聚物等的含有(甲基)丙烯醯氧基的化合物,亦即含有二(甲基)丙烯醯氧基的化合物,為了提高接著劑層的耐水性,以多官能基者較理想。於考量接著劑層的耐水性時,含有二(甲基)丙烯醯氧基的化合物為疏水性更理想。作為疏水性的含有二(甲基)丙烯醯氧基的化合物,特別是疏水性的多官能基含有二(甲基)丙烯醯氧基的化合物,例如三環癸烷二甲醇二丙烯酸酯、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、丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(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、1,9-壬二醇二(甲基)丙烯酸酯、丙三醇二(甲基)丙烯酸酯、環氧乙烷改性丙三醇三(甲基)丙烯酸酯、環氧乙烷改性二丙三醇四(甲基)丙烯酸酯、(甲基)丙烯酸2-(2-乙烯氧基乙氧基)乙酯、雙酚A-環氧乙烷加成物二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、羥基特戊酸新戊二醇(甲基)丙烯酸加成物、環氧乙烷改性三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、異氰脲酸環氧乙烷改性三(甲基)丙烯酸酯、ε-己內酯改性三((甲基)丙烯醯氧基乙基)異氰脲酸酯、1,1-雙((甲基)丙烯醯氧基甲基)乙基異氰酸酯、(甲基)丙烯酸2-羥基乙酯與1,6-二異氰酸酯己烷的聚合物、9,9-雙[4-(2-(甲基)丙烯醯氧基乙氧基)苯基]茀(fluorene)等。 (Meth) acryloxy group-containing (meth) acryloxy group-containing oligomers having at least two (meth) acryloxy groups in the molecule obtained by reacting two or more types of functional group-containing compounds A compound, that is, a compound containing a bis (meth) acryloxy group, is preferably a polyfunctional group in order to improve the water resistance of the adhesive layer. In consideration of the water resistance of the adhesive layer, a compound containing a bis (meth) acryloxy group is more preferably hydrophobic. As the hydrophobic di (meth) acryloxy group-containing compound, particularly the hydrophobic polyfunctional compound containing the di (meth) acryloxy group, such as tricyclodecane dimethanol diacrylate, ethyl Diethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) Base) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) propylene Acrylates, 1,9-nonanediol di (meth) acrylate, glycerol di (meth) acrylate, ethylene oxide modified glycerol tri (meth) acrylate, ethylene oxide Alkane-modified diglycerol tetra (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, bisphenol A-ethylene oxide adduct bis (methyl) ) Acrylate, trimethylolpropane tri (meth) acrylate, neopentyl glycol (meth) acrylic acid adduct of hydroxypivalic acid, ethylene oxide modified trimethylolpropane tri (methyl) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isocyanurate ethylene oxide modified tri (meth) acrylate, ε -Caprolactone modified tri ((meth) acryloxyethyl) isocyanurate, 1,1-bis ((meth) acryloxymethyl) ethyl isocyanate, (methyl) Polymer of 2-hydroxyethyl acrylate and 1,6-diisocyanate hexane, 9,9-bis [4- (2- (meth) acryloxyethoxy) phenyl] fluorene, etc. .
相對於自由基聚合性化合物的合計量,含有二(甲基)丙烯醯氧基的化合物之比例為5至50重量%較理想,以9至40重量%更理想。該比例未達5重量%時,有時無法得到充分的耐水性提高的效果,另一方面,超過50重量%時,有時無法得到充分的接著性提高的效果。 The proportion of the compound containing a di (meth) propenyloxy group is preferably 5 to 50% by weight, and more preferably 9 to 40% by weight based on the total amount of the radical polymerizable compound. When the proportion is less than 5% by weight, a sufficient effect of improving water resistance may not be obtained. On the other hand, when it exceeds 50% by weight, a sufficient effect of improving adhesion may not be obtained.
而且,紫外線硬化性接著劑係除上述外,亦可包含含有其他官能基的化合物作為自由基聚合性化合物。作為含有其他官能基的化合物,例如二乙烯基苯、N,N-亞甲基雙丙烯醯胺等。 In addition, the ultraviolet-curable adhesive agent may contain a compound containing other functional groups as a radical polymerizable compound in addition to the above. Examples of compounds containing other functional groups include divinylbenzene and N, N-methylenebispropenamide.
紫外線硬化性接著劑係與環氧系化合物及/或(甲基)丙烯酸系化合物一起或取代該等,亦可含有氧雜 環丁烷化合物。氧雜環丁烷化合物也可容易地取得其市售品,例如分別以商品名,東亞合成公司販售的「ARON OXETANE」系列、宇部興產公司販售的「ETERNACOLL」系列等。 The ultraviolet-curable adhesive may contain an oxa compound together with or instead of an epoxy compound and / or a (meth) acrylic compound. Cyclobutane compounds. The oxetane compound can also be easily obtained from commercial products, such as the "ARON OXETANE" series sold by Toa Kosei Co., Ltd., and the "ETERNACOLL" series sold by Ube Kosan Co., Ltd. under the trade names.
紫外線硬化性接著劑包含如環氧系化合物的藉由陽離子聚合而硬化的硬化性成分時,含有光陽離子聚合引發劑較理想。作為光陽離子聚合引發劑,例如芳香族重氮鎓鹽;芳香族碘鎓鹽、芳香族硫鎓鹽等的鎓鹽;鐵-芳烴錯合物等。而且,於紫外線硬化性接著劑包含如(甲基)丙烯酸系化合物的自由基聚合性硬化性成分時,含有光自由基聚合引發劑較理想。作為光自由基聚合引發劑,例如氫拔去型或開裂型,例如苯乙酮系引發劑、二苯甲酮系引發劑、安息香醚系引發劑、硫雜蒽酮系引發劑、氧雜蒽酮、茀酮、樟腦醌、苯甲醛、蒽醌等。該等引發劑係依據需要,可包含2種以上彼此不同的光陽離子聚合引發劑、光自由基聚合引發劑,亦可併用光陽離子聚合引發劑與光自由基聚合引發劑。光聚合引發劑感應的波長區域大多為260至380nm,特別是大多具有320nm附近的譜峰。 When the ultraviolet curable adhesive contains a curable component such as an epoxy-based compound that is cured by cation polymerization, it is preferable to include a photocationic polymerization initiator. Examples of the photocationic polymerization initiator include an aromatic diazonium salt; an onium salt such as an aromatic iodonium salt and an aromatic sulfonium salt; an iron-aromatic hydrocarbon complex; and the like. When the ultraviolet curable adhesive contains a radical polymerizable curable component such as a (meth) acrylic compound, it is preferable to include a photoradical polymerization initiator. As the photoradical polymerization initiator, for example, a hydrogen extraction type or a cracking type, such as an acetophenone-based initiator, a benzophenone-based initiator, a benzoin-ether-based initiator, a thioanthrone-based initiator, and an xanthracene Ketones, fluorenone, camphor quinone, benzaldehyde, anthraquinone, etc. These initiators may include two or more different types of photocationic polymerization initiators and photoradical polymerization initiators, or a combination of photocationic polymerization initiators and photoradical polymerization initiators may be used as necessary. The wavelength region induced by the photopolymerization initiator is mostly 260 to 380 nm, and in particular, it has a spectral peak near 320 nm.
陽離子聚合引發劑亦可容易取得其市售品,例如分別以商品名,日本化藥公司販售的「KAYARAD」系列、聯合碳化物公司販售的「CYRACURE」系列、SAN-APRO公司販售的光酸產生劑「CPI」系列、綠化學公司販售的光酸產生劑「TAZ」、「BBI」及「DTS」、ADEKA公司販售的「ADEKA OPTOMER」系列、Rhodia公司販售 的「RHODORSIL」系列等。 Cationic polymerization initiators can also easily obtain commercially available products, such as the "KAYARAD" series sold by Nippon Kayakusho, the "CYRACURE" series sold by Union Carbide, and the ones sold by SAN-APRO, respectively. Photoacid generator "CPI" series, photoacid generators "TAZ", "BBI" and "DTS" sold by Green Chemical Company, "ADEKA OPTOMER" series sold by ADEKA company, and Rhodia company sold "RHODORSIL" series, etc.
紫外線硬化性接著劑依據需要可含有聚醇類等的陽離子聚合促進劑、光增感劑、離子捕捉劑、抗氧化劑、鏈轉移劑、增黏劑、熱塑性樹脂、填充劑、流動調整劑、可塑劑、消泡劑、抗靜電劑、調平劑、溶劑等的添加劑。 The ultraviolet-curing adhesive may contain a cationic polymerization accelerator such as a polyhydric alcohol, a photosensitizer, an ion trapping agent, an antioxidant, a chain transfer agent, a tackifier, a thermoplastic resin, a filler, a flow modifier, and a plasticizer, if necessary. Additives, defoamers, antistatic agents, leveling agents, solvents and other additives.
第1及第2接著劑層15、25的厚度,分別獨立例如為0.01至10μm的程度,較理想為0.01至5μm的程度,更理想為4μm以下(例如3μm以下)。 The thicknesses of the first and second adhesive layers 15 and 25 are independently, for example, about 0.01 to 10 μm, more preferably about 0.01 to 5 μm, and even more preferably 4 μm or less (for example, 3 μm or less).
於偏光片10的貼合面或第1及第2(甲基)丙烯酸系樹脂膜21、22的貼合面塗佈紫外線硬化性接著劑,隔著該塗佈的紫外線硬化性接著劑層,重疊膜後,照射紫外線,藉由使接著劑層硬化,可得到偏光板。該貼合操作係於偏光片10與第1(甲基)丙烯酸系樹脂膜21先貼合後,再貼合第2(甲基)丙烯酸系樹脂膜22,亦可3片同時對準重疊,照射紫外線而貼合。紫外線以1次以上從第2(甲基)丙烯酸系樹脂膜22側照射,從接著劑硬化的觀點,係較理想。作為紫外線光源,可使用低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、化學燈、黑光燈、微波激發水銀燈、金屬鹵化物燈等。 Applying a UV-curable adhesive to the bonding surface of the polarizer 10 or the bonding surfaces of the first and second (meth) acrylic resin films 21 and 22, and via the applied UV-curable adhesive layer, After the films are laminated, ultraviolet rays are irradiated and the adhesive layer is hardened to obtain a polarizing plate. This bonding operation is performed after the polarizer 10 and the first (meth) acrylic resin film 21 are bonded together, and then the second (meth) acrylic resin film 22 is bonded, and three sheets can be aligned and overlapped at the same time. Bonded by irradiating ultraviolet rays. The ultraviolet rays are preferably irradiated at least once from the second (meth) acrylic resin film 22 side, and are preferably from the viewpoint of curing the adhesive. As the ultraviolet light source, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, a metal halide lamp, and the like can be used.
在貼合前,第1及第2(甲基)丙烯酸系樹脂膜21、22的與偏光片10的貼合面及偏光片10的與第1及第2(甲基)丙烯酸系樹脂膜21、22的貼合面中至少一者,可實施電暈放電處理、電漿照射處理、電子線照射處理、 其他表面活性化處理。 Before bonding, the first and second (meth) acrylic resin films 21 and 22 are bonded to the polarizer 10 and the polarizer 10 and the first and second (meth) acrylic resin film 21 At least one of the bonding surfaces of 22 and 22 can be subjected to a corona discharge treatment, a plasma irradiation treatment, an electron beam irradiation treatment, Other surface activation treatments.
(5)黏著劑層 (5) Adhesive layer
本發明的偏光板,於第2(甲基)丙烯酸系樹脂膜22的外面(與偏光片10相反側的表面),可具備用以貼合該偏光板於液晶胞等的其他構件的黏著劑層30。黏著劑層30所使用的黏著劑,例如(甲基)丙烯酸系黏著劑、胺基甲酸酯系黏著劑、聚矽氧系黏著劑、聚酯系黏著劑、聚醯胺系黏著劑、聚醚系黏著劑、氟系黏著劑、橡膠系黏著劑等,其中,從透明性、黏著力、信賴性、重工性等的觀點,使用(甲基)丙烯酸系黏著劑較理想。 The polarizing plate of the present invention may be provided with an adhesive on the outer surface of the second (meth) acrylic resin film 22 (the surface opposite to the polarizing plate 10) for bonding the polarizing plate to other members such as a liquid crystal cell. Layer 30. The adhesive used in the adhesive layer 30 is, for example, a (meth) acrylic adhesive, a urethane adhesive, a polysiloxane adhesive, a polyester adhesive, a polyamide adhesive, a Among the ether-based adhesives, fluorine-based adhesives, and rubber-based adhesives, a (meth) acrylic-based adhesive is preferably used from the viewpoints of transparency, adhesion, reliability, and reworkability.
黏著劑層30可藉由以有機溶劑溶液的形態使用黏著劑,將其塗佈於第2(甲基)丙烯酸系樹脂膜22上,使其乾燥的方法設置外,將形成於施有離型處理的塑膠膜(亦稱為離型膜)上的薄片狀黏著劑轉印至第2(甲基)丙烯酸系樹脂膜22的方法也可設置。於任一種方法,積層於第2(甲基)丙烯酸系樹脂膜22後的黏著劑層30的外面,貼附保護表面用的離型膜較理想。黏著劑層30的厚度,通常為2至40μm。 The adhesive layer 30 can be formed on the second (meth) acrylic resin film 22 by applying the adhesive in the form of an organic solvent solution, and drying it. A method for transferring the sheet-shaped adhesive on the processed plastic film (also referred to as a release film) to the second (meth) acrylic resin film 22 may be provided. In either method, it is preferable to laminate the outer surface of the adhesive layer 30 behind the second (meth) acrylic resin film 22 and attach a release film for protecting the surface. The thickness of the adhesive layer 30 is usually 2 to 40 μm.
離型膜可為聚乙烯等聚乙烯系樹脂、聚丙烯等聚丙烯系樹脂、聚對苯二甲酸乙二酯等的聚酯系樹脂等所構成的膜。其中,聚對苯二甲酸乙二酯的延伸膜較理想。 The release film may be a film composed of a polyethylene-based resin such as polyethylene, a polypropylene-based resin such as polypropylene, or a polyester-based resin such as polyethylene terephthalate. Among them, a stretched film of polyethylene terephthalate is preferable.
(6)塗佈層 (6) Coating layer
本發明的偏光板,為了賦予偏光板所期望的光學特性 或其他特徵,於第1(甲基)丙烯酸系樹脂膜21的外面(與偏光片10相反側的表面)上,可具有塗佈層。塗佈層的具體例,包括硬塗層、抗眩層、抗反射層、抗靜電層、防污層。於第1(甲基)丙烯酸系樹脂膜21的表面形成表面處理層之方法,無特別限制,可使用習知的方法 The polarizing plate of the present invention is for imparting desired optical characteristics to the polarizing plate. Or other characteristics, the 1st (meth) acrylic-type resin film 21 may have a coating layer on the outer surface (surface on the opposite side to the polarizer 10). Specific examples of the coating layer include a hard coat layer, an antiglare layer, an antireflection layer, an antistatic layer, and an antifouling layer. The method for forming a surface treatment layer on the surface of the first (meth) acrylic resin film 21 is not particularly limited, and a conventional method can be used.
〈液晶面板〉 <LCD panel>
關於本發明的液晶面板,包括:液晶胞以及配置於其至少一側的面上的關於本發明的偏光板。關於本發明的液晶面板的層構成的一例表示於第2圖。第2圖所示的液晶面板2,配置於液晶胞40的兩面之偏光板,係使用第1圖所示的偏光板1,或如上述只任一偏光板使用關於本發明的偏光板。較理想為至少辨識側的偏光板,使用關於本發明的偏光板。 The liquid crystal panel of the present invention includes a liquid crystal cell and a polarizing plate of the present invention arranged on at least one side of the liquid crystal cell. An example of the layer structure of the liquid crystal panel of this invention is shown in FIG. The liquid crystal panel 2 shown in FIG. 2 is a polarizing plate disposed on both sides of the liquid crystal cell 40. The polarizing plate 1 shown in FIG. 1 is used, or as described above, only one of the polarizing plates is used in the present invention. It is preferable to use at least the polarizing plate on the identification side, and use the polarizing plate of the present invention.
於液晶面板2中偏光板1係配置成其第2(甲基)丙烯酸系樹脂膜22成為液晶胞40側。藉此,一邊維持液晶面板2的耐光性,一邊可抑制正交尼科爾中含有異物。 The polarizing plate 1 is arranged in the liquid crystal panel 2 such that the second (meth) acrylic resin film 22 becomes the liquid crystal cell 40 side. Thereby, while maintaining the light resistance of the liquid crystal panel 2, it is possible to suppress the inclusion of foreign substances in the crossed Nicols.
液晶胞40的驅動模式,可為IPS模式、VA(垂直配向)模式、TN(扭曲向列)模式等的傳統習知的一切模式,如上述,較理想為IPS模式。IPS模式在不存在電場的狀態下均勻配向的向列型液晶,藉橫向電場驅動而進行圖像顯示者,其優點為與其他驅動模式比較時有視角寬的點。因觀察畫面的角度之圖像的顏色變化(亦謂斜方向的彩色偏離)較大,該點係可藉由使用包含實質上不具有光學異 向性的第2(甲基)丙烯酸系樹脂膜22的偏光板而改善。 The driving mode of the liquid crystal cell 40 may be any conventionally known mode such as an IPS mode, a VA (vertical alignment) mode, and a TN (twisted nematic) mode. As described above, the IPS mode is more preferable. In the IPS mode, a nematic liquid crystal that is uniformly aligned in the absence of an electric field, and is driven by a lateral electric field to display an image, has the advantage of having a wider viewing angle when compared with other driving modes. Because the color change of the image at the angle of the observation screen (also known as the color deviation in the oblique direction) is large, this point can be achieved by using The polarizing plate of the directional second (meth) acrylic resin film 22 is improved.
以下,顯示實施例及比較例而更具體地說明本發明,但本發明不限於該等例。再者,(甲基)丙烯酸系樹脂膜及偏光板的穿透率,根據以下方法測定。 Hereinafter, the present invention will be described more specifically by showing examples and comparative examples, but the present invention is not limited to these examples. The transmittance of the (meth) acrylic resin film and the polarizing plate was measured by the following method.
[(甲基)丙烯酸系樹脂膜的穿透率測定] [Measurement of transmittance of (meth) acrylic resin film]
(甲基)丙烯酸系樹脂膜的紫外線區域(190至380nm)的穿透率,係使用公司島津製作所製的分光光度計「UV-2450」測定。 The transmittance in the ultraviolet region (190 to 380 nm) of the (meth) acrylic resin film was measured using a spectrophotometer "UV-2450" manufactured by Shimadzu Corporation.
[偏光板的穿透率測定] [Measurement of transmittance of polarizing plate]
偏光板的紫外線區域(260至380nm)的穿透率,係使用日本分光(股)製的紫外線可見光分光光度計「V7100」測定。測定係在格蘭湯姆森偏光片(Glan-Thompson)移除的狀態下的光譜測定模式進行,以某任意樣品角度測定穿透率後,再將樣品旋轉90度,測定穿透率,以該等的平均值,算出偏光板的穿透率。 The transmittance in the ultraviolet region (260 to 380 nm) of the polarizing plate was measured using a UV-visible spectrophotometer "V7100" manufactured by JASCO Corporation. The measurement is performed in the spectrometry mode with the Glan-Thompson polarizer removed. After measuring the transmittance at an arbitrary sample angle, the sample is rotated 90 degrees to determine the transmittance. The average value was calculated to calculate the transmittance of the polarizing plate.
〈實施例1〉 <Example 1>
就(甲基)丙烯酸系樹脂而言,準備甲基丙烯酸甲酯/丙烯酸甲酯=96%/4%(重量比)的共聚物。而且,就橡膠粒子而言,準備最內層為於甲基丙烯酸甲酯使用少量甲基丙烯酸烯丙酯所聚合的硬質聚合物所構成,中間層為以丙烯酸丁酯作為主成分,再使用苯乙烯及少量甲基丙烯酸烯丙酯所聚合的軟質彈性體所構成,最外層為於甲基丙烯酸甲酯使 用少量丙烯酸乙酯所聚合的硬質聚合物所構成的三層構造的彈性體粒子,至中間層的彈性體為止的平均粒徑為240nm者,再者,於該橡膠粒子,最內層與中間層的合計重量為粒子全部的70%。 For the (meth) acrylic resin, a copolymer of methyl methacrylate / methyl acrylate = 96% / 4% (weight ratio) was prepared. In addition, for the rubber particles, the innermost layer is prepared by using a hard polymer polymerized with a small amount of allyl methacrylate in methyl methacrylate. The intermediate layer is made of butyl acrylate as the main component, and then benzene is used. It consists of a soft elastomer polymerized by ethylene and a small amount of allyl methacrylate. The outermost layer is made of methyl methacrylate. An elastomer particle having a three-layer structure composed of a hard polymer polymerized with a small amount of ethyl acrylate has an average particle diameter of 240 nm up to the elastomer of the intermediate layer, and the innermost layer and the middle of the rubber particle The total weight of the layers is 70% of the total particles.
將上述(甲基)丙烯酸系樹脂68.5重量%、上述橡膠粒子29.6重量%以及ADEKA公司製的紫外線吸收劑「ADEKA STAB LA31」1.9重量%以超級攪拌機混合,以二軸擠出機熔融混練成為顆粒。將該顆粒投入65mm 的一軸擠出機,經由設定溫度為275℃的T型模頭擠出,夾持具有鏡面的二根拋光滾輪膜的兩面而冷卻,得到厚度40μm的第1(甲基)丙烯酸系樹脂膜。 68.5% by weight of the (meth) acrylic resin, 29.6% by weight of the rubber particles, and 1.9% by weight of the ultraviolet absorber "ADEKA STAB LA31" manufactured by ADEKA were mixed with a super mixer and melt-kneaded with a biaxial extruder to form pellets . Put the particles into 65mm A 1-axis extruder was extruded through a T-die at a set temperature of 275 ° C, and cooled by sandwiching both sides of two polishing roller films having a mirror surface to obtain a first (meth) acrylic resin film having a thickness of 40 μm.
於上述熔融擠出成形中,從擠出樹脂開始經過100小時之T型模頭附近的蒸發物,以目視確認時,可見到蒸發物累積很多,於所得之第1(甲基)丙烯酸系樹脂膜恐會有蒸發物的附著/混入。而且,所得之第1(甲基)丙烯酸系樹脂膜的190至380nm的波長區域的最大穿透率(%)為15.9%。所得之第1(甲基)丙烯酸系樹脂膜在190至380nm的波長區域的穿透率表示於第3圖。 In the above-mentioned melt extrusion molding, the evaporate near the T-die after 100 hours from the extrusion of the resin, when visually confirmed, it was found that the evaporate accumulated a lot, and the obtained first (meth) acrylic resin There is a risk that vapors will adhere to the film. The maximum transmittance (%) in the wavelength range of 190 to 380 nm of the obtained first (meth) acrylic resin film was 15.9%. The transmittance of the obtained first (meth) acrylic resin film in a wavelength region of 190 to 380 nm is shown in FIG. 3.
除不混合紫外線吸收劑外,與上述(1)同樣地製作厚度40μm的第2(甲基)丙烯酸系樹脂膜。 A second (meth) acrylic resin film having a thickness of 40 μm was prepared in the same manner as in (1) above except that the ultraviolet absorber was not mixed.
從擠出樹脂開始經過100小時之T型模頭附近的蒸發物,以目視確認時,沒有見到蒸發物的累積,故可判斷於所得之第2(甲基)丙烯酸系樹脂膜不會有蒸發物的附著/混 入之虞。而且,所得之第2(甲基)丙烯酸系樹脂膜在260至320nm的波長區域的最大穿透率(%),於316nm為78.7%。所得之第2(甲基)丙烯酸系樹脂膜在190至380nm的波長區域的穿透率表示於第4圖。 Evaporation near the T-die after 100 hours from the extrusion of the resin. When visually confirmed, no evaporation was observed. Therefore, it can be judged that the second (meth) acrylic resin film obtained will not have Adhesion / mixing of vapors Into the risk. The maximum transmittance (%) of the obtained second (meth) acrylic resin film in the wavelength region of 260 to 320 nm was 78.7% at 316 nm. The transmittance of the obtained second (meth) acrylic resin film in a wavelength region of 190 to 380 nm is shown in FIG. 4.
將平均聚合度約2400、皂化度99.9莫耳%以上且厚度75μm的聚乙烯醇膜浸漬於30℃的純水後,以30℃浸漬於碘/碘化鉀/水的重量比為0.02/2/100的水溶液。然後,以56.5℃浸漬於碘化鉀/硼酸/水的重量比為12/5/100的水溶液。接著,以8℃的純水洗淨後,以65℃進行乾燥,得到碘吸附配向於聚乙烯醇膜之偏光膜。延伸主要在碘染色及硼酸處理的步驟進行,全部延伸倍率為5.3倍,所得之偏光膜的厚度為27μm。 A polyvinyl alcohol film having an average degree of polymerization of about 2400, a degree of saponification of 99.9 mol% or more, and a thickness of 75 μm was immersed in pure water at 30 ° C, and then the weight ratio of iodine / potassium iodide / water was 0.02 / 2/100 at 30 ° C. Water solution. Then, it was immersed in an aqueous solution having a weight ratio of potassium iodide / boric acid / water of 12/5/100 at 56.5 ° C. Next, it was washed with pure water at 8 ° C, and then dried at 65 ° C to obtain a polarizing film having iodine adsorbed and aligned on the polyvinyl alcohol film. The stretching is mainly performed in the steps of iodine dyeing and boric acid treatment, and the total stretching ratio is 5.3 times. The thickness of the obtained polarizing film is 27 μm.
於上述(1)所得之第1(甲基)丙烯酸系樹脂膜的貼合面,實施電暈處理後,於該電暈處理面塗佈在260至320nm的波長區域引發聚合的紫外線硬化接著劑(東亞合成(股)製「ARONIX」)。同樣地,於上述(2)所得之第2(甲基)丙烯酸系樹脂膜的貼合面實施電暈處理後,於該電暈處理面塗佈相同的紫外線硬化接著劑。然後,使用貼合滾輪,將塗有紫外線硬化接著劑的第1(甲基)丙烯酸系樹脂膜,以其紫外線硬化接著劑層側貼合於上述(3)所得之偏光膜的一側的面,並將塗有紫外線硬化接著劑的第2(甲基)丙烯酸系樹脂膜,於其紫外線硬化接著劑層側貼合於另一側的面。然 後,從第2(甲基)丙烯酸系樹脂膜側照射紫外線,使兩面的紫外線硬化接著劑層硬化,得到偏光板。進行紫外線照射係使260至320nm的波長區域的累積光量成為200mJ/cm2。所得之偏光板在260至380nm的波長區域的最大穿透率(%)為2.3%。而且,所得之偏光板即使以剪刀裁切時,不會產生(甲基)丙烯酸系樹脂膜從偏光膜剝離的缺陷,確認出兩面的接著劑層充分地硬化。 After the corona treatment is performed on the bonding surface of the first (meth) acrylic resin film obtained in (1) above, the corona-treated surface is coated with an ultraviolet curing adhesive that initiates polymerization in a wavelength region of 260 to 320 nm. ("ARONIX" made by Toa Gosei Co., Ltd.). Similarly, after the corona treatment is performed on the bonding surface of the second (meth) acrylic resin film obtained in the above (2), the same ultraviolet curing adhesive is applied to the corona treatment surface. Then, using a bonding roller, the first (meth) acrylic resin film coated with the ultraviolet curing adhesive was bonded to the side of one side of the polarizing film obtained in the above (3) with the ultraviolet curing adhesive layer side. The second (meth) acrylic resin film coated with the ultraviolet curing adhesive is bonded to the surface of the other side on the ultraviolet curing adhesive layer side. Then, ultraviolet rays were irradiated from the second (meth) acrylic resin film side, and the ultraviolet curing adhesive layers on both sides were cured to obtain a polarizing plate. The ultraviolet irradiation is performed so that the cumulative light amount in the wavelength region of 260 to 320 nm becomes 200 mJ / cm 2 . The maximum transmittance (%) of the obtained polarizing plate in the wavelength region of 260 to 380 nm was 2.3%. In addition, even when the obtained polarizing plate was cut with scissors, no defect of peeling of the (meth) acrylic resin film from the polarizing film was generated, and it was confirmed that the adhesive layers on both sides were sufficiently hardened.
〈實施例2〉 <Example 2>
除使厚度為80μm以外,與實施例1的(1)同樣地製作第1(甲基)丙烯酸系樹脂膜。於上述熔融擠出成形中,從擠出樹脂開始至經過100小時之T型模頭附近的蒸發物,以目視確認時,可見到蒸發物累積很多,故於所得之第1(甲基)丙烯酸系樹脂膜恐會有蒸發物的附著/混入。而且,所得之第1(甲基)丙烯酸系樹脂膜在190至380nm的波長區域的最大穿透率(%)為3.5%。 A first (meth) acrylic resin film was produced in the same manner as in (1) of Example 1 except that the thickness was 80 μm. In the above-mentioned melt extrusion molding, the evaporation near the T-die from the time when the resin was extruded until 100 hours elapsed, when it was visually confirmed that the evaporation accumulated a lot, so the first (meth) acrylic acid obtained Resin film may adhere or mix with vapors. The maximum transmittance (%) of the obtained first (meth) acrylic resin film in the wavelength region of 190 to 380 nm was 3.5%.
除使厚度為80μm以外,係與實施例1的(2)同樣地製作第2(甲基)丙烯酸系樹脂膜。從擠出樹脂開始到經過100小時之T型模頭附近的蒸發物,以目視確認時,由於沒有見到蒸發物的累積,故可判斷於所得之第2(甲基)丙烯酸系樹脂膜無蒸發物附著/混入之虞。而且,所得之第2(甲基)丙烯酸系樹脂膜在260至320nm的波長區域的最大穿透率(%),於316nm為75.1%。 A second (meth) acrylic resin film was produced in the same manner as in (2) of Example 1 except that the thickness was 80 μm. From the time when the resin was extruded until the evaporate near the T-die for 100 hours, it was visually confirmed that there was no accumulation of the evaporate. Therefore, it can be judged that the second (meth) acrylic resin film obtained had no Evaporation may be attached / mixed. The maximum transmittance (%) of the obtained second (meth) acrylic resin film in the wavelength region of 260 to 320 nm was 75.1% at 316 nm.
除使用上述(1)及(2)製作的第1及第2(甲基)丙烯酸系樹脂膜外,與實施例1的(4)同樣地製作偏光板。所得之偏光板在260至380nm的波長區域的最大穿透率(%)為0.3%。而且,所得之偏光板即使以剪刀裁切時,亦不會產生(甲基)丙烯酸系樹脂膜從偏光膜剝離的缺陷,確認出兩面的接著劑層充分地硬化。 A polarizing plate was produced in the same manner as in (4) of Example 1 except that the first and second (meth) acrylic resin films produced in the above (1) and (2) were used. The maximum transmittance (%) of the obtained polarizing plate in the wavelength region of 260 to 380 nm was 0.3%. In addition, even when the obtained polarizing plate was cut with scissors, no defect of peeling of the (meth) acrylic resin film from the polarizing film was generated, and it was confirmed that the adhesive layers on both sides were sufficiently hardened.
〈實施例3〉 <Example 3>
除使厚度為80μm以外,係與實施例1的(1)同樣地製作第1(甲基)丙烯酸系樹脂膜。於上述熔融擠出成形中,從擠出樹脂開始到經過100小時之T型模頭附近的蒸發物,以目視確認時,因可見到蒸發物累積很多,故於所得之第1(甲基)丙烯酸系樹脂膜恐有蒸發物附著/混入。而且,所得之第1(甲基)丙烯酸系樹脂膜在190至380nm的波長區域的最大穿透率(%)為3.5%。 A first (meth) acrylic resin film was produced in the same manner as in (1) of Example 1 except that the thickness was 80 μm. In the above-mentioned melt extrusion molding, the evaporation near the T-die from the beginning of extruding the resin to 100 hours has elapsed. When visually confirming, it can be seen that a large amount of evaporation accumulates, so the first (methyl) obtained is The acrylic resin film is likely to cause adhesion of vapors. The maximum transmittance (%) of the obtained first (meth) acrylic resin film in the wavelength region of 190 to 380 nm was 3.5%.
除使厚度為80μm以及使用(甲基)丙烯酸系樹脂69.9重量%、上述橡膠粒子29.6重量%以及ADEKA公司製的紫外線吸收劑「ADEKA STAB LA31」0.5重量%作為膜的形成材料以外,與實施例1的(2)同樣地製作第2(甲基)丙烯酸系樹脂膜。從擠出樹脂開始到經過100小時之T型模頭附近的蒸發物,以目視確認時,蒸發物的累積僅少許,故可判斷於所得之第2(甲基)丙烯酸系樹脂膜有蒸發物附著/混 入之可能性極低。而且,所得之第2(甲基)丙烯酸系樹脂膜在260至320nm的波長區域的最大穿透率(%),於266nm為21.3%。 Except for using a thickness of 80 μm and using 69.9% by weight of a (meth) acrylic resin, 29.6% by weight of the above-mentioned rubber particles, and 0.5% by weight of an ultraviolet absorber “ADEKA STAB LA31” manufactured by ADEKA Corporation as the material for forming the film, it is the same as in the examples. (2) of 1 In the same manner, a second (meth) acrylic resin film was produced. From the beginning of the extrusion of the resin to the evaporation of the vicinity of the T-die for 100 hours, when it was visually confirmed, the accumulation of the evaporation was only a small amount, so it can be judged that the obtained second (meth) acrylic resin film has evaporation Attach / mix The probability of entry is extremely low. The maximum transmittance (%) of the obtained second (meth) acrylic resin film in the wavelength region of 260 to 320 nm was 21.3% at 266 nm.
除使用上述(1)及(2)製作的第1及第2(甲基)丙烯酸系樹脂膜外,與實施例1的(4)同樣地製作偏光板。所得之偏光板在260至380nm的波長區域的最大穿透率(%)為0.14%。而且,所得之偏光板即使以剪刀裁切時,亦不會產生(甲基)丙烯酸系樹脂膜從偏光膜剝離的缺陷,確認出兩面的接著劑層充分地硬化。 A polarizing plate was produced in the same manner as in (4) of Example 1 except that the first and second (meth) acrylic resin films produced in the above (1) and (2) were used. The maximum transmittance (%) of the obtained polarizing plate in the wavelength region of 260 to 380 nm was 0.14%. In addition, even when the obtained polarizing plate was cut with scissors, no defect of peeling of the (meth) acrylic resin film from the polarizing film was generated, and it was confirmed that the adhesive layers on both sides were sufficiently hardened.
〈實施例4〉 <Example 4>
除使厚度為60μm以外,與實施例1的(1)同樣地製作第1(甲基)丙烯酸系樹脂膜。於上述熔融擠出成形中,從擠出樹脂開始到經過100小時之T型模頭附近的蒸發物以目視確認時,因可見到蒸發物累積很多,於所得之第1(甲基)丙烯酸系樹脂膜恐有蒸發物的附著/混入。而且,所得之第1(甲基)丙烯酸系樹脂膜在190至380nm的波長區域的最大穿透率(%)為7.5%。所得之第1(甲基)丙烯酸系樹脂膜在190至380nm的波長區域的穿透率表示於第6圖。 A first (meth) acrylic resin film was produced in the same manner as in (1) of Example 1 except that the thickness was 60 μm. In the above-mentioned melt extrusion molding, when the evaporate near the T-die from the time of extruding the resin to 100 hours passed was visually confirmed, it was seen that the evaporate accumulated a lot. Resin film may adhere or mix with vapors. The maximum transmittance (%) of the obtained first (meth) acrylic resin film in the wavelength region of 190 to 380 nm was 7.5%. The transmittance of the obtained first (meth) acrylic resin film in a wavelength region of 190 to 380 nm is shown in FIG. 6.
首先,(甲基)丙烯酸系熱塑性樹脂以如下的方法製造。甲基丙烯酸甲酯(和光純藥特級)在減壓度0.01MPa、40℃下蒸餾,除去禁止劑。然後,於50L的槽內,調製包 含蒸餾的甲基丙烯酸甲酯/N-苯基馬來醯亞胺(和光純藥特級)/環己基馬來醯亞胺(和光純藥特級)/間二甲苯(和光純藥特級、以下mXy)=48.6%/4.8%/6.6%/40%(重量比)的混合單體溶液,於其中,以100mL/分的速度實施氮氣之起泡12小時,除去溶解的氧。將混合單體溶液移至氮氣取代的60L反應器,將溫度上升至130℃。然後,以相同溫度,以1kg/小時的速度添加聚合引發劑[日本油脂(股)「PERBUTYL O」]0.12重量%溶解於mXy12重量%的引發劑溶液,實施聚合,8小時後,將反應器冷卻至50℃。 First, a (meth) acrylic thermoplastic resin is manufactured by the following method. Methyl methacrylate (Wako Pure Chemical Grade) was distilled at a reduced pressure of 0.01 MPa and 40 ° C to remove the inhibitor. Then, in a 50L tank, prepare the packet Contains distilled methyl methacrylate / N-phenylmaleimide (Wako Pure Chemical Special Grade) / cyclohexylmaleimide (Wako Pure Chemical Special) / m-xylene (Wako Pure Chemical Special, below mXy ) = 48.6% / 4.8% / 6.6% / 40% (weight ratio) of the mixed monomer solution, in which nitrogen gas was bubbled at a rate of 100 mL / min for 12 hours to remove dissolved oxygen. The mixed monomer solution was moved to a nitrogen-substituted 60 L reactor, and the temperature was raised to 130 ° C. Then, at the same temperature and at a rate of 1 kg / hour, 0.12% by weight of a polymerization initiator [Nippon Oil & Fat Co., Ltd. "PERBUTYL O"] was dissolved in an mXy 12% by weight initiator solution, polymerization was performed, and after 8 hours, the reactor Cool to 50 ° C.
然後,於1m3的反應器中加入500L的甲醇,將上述聚合溶液花5小時注入,使聚合物析出。然後,再實施攪拌2小時,進行減壓過濾。於減壓過濾後的含有甲醇的聚合粉末,再注入300L的甲醇,再進行攪拌。然後,實施減壓過濾,採取含有甲醇的粉末,以0.3m3的UNICAL真空乾燥器,在減壓度0.03MPa、80℃的條件下實施乾燥。將乾燥後的粉末以250℃條件的二軸擠出機,實施造粒,得到顆粒狀的(甲基)丙烯酸系熱塑性樹脂。 Then, 500 L of methanol was charged into a 1 m 3 reactor, and the polymerization solution was injected for 5 hours to precipitate a polymer. Then, it stirred for 2 hours, and filtered under reduced pressure. 300 L of methanol was poured into the polymer powder containing methanol after filtration under reduced pressure, and the mixture was stirred. Then, the solution was filtered under reduced pressure, and a powder containing methanol was collected and dried under a condition of a pressure reduction of 0.03 MPa and 80 ° C. in a 0.3 m 3 UNICAL vacuum dryer. The dried powder was granulated in a biaxial extruder at 250 ° C. to obtain a granular (meth) acrylic thermoplastic resin.
然後,將上述顆粒狀的(甲基)丙烯酸系熱塑性樹脂投入於二軸擠出機,於260℃進行熔融混練,經由設定溫度255℃的T型模頭擠出,以鏡面冷卻滾輪進行表面轉印作為未延伸膜。再使用熔融延伸裝置,將該未延伸膜進行逐次延伸(MD延伸倍率:1.8倍、TD延伸倍率:2.5倍),得到厚度40μm的第2(甲基)丙烯酸系樹脂膜。 Then, the granular (meth) acrylic thermoplastic resin was put into a biaxial extruder, melt-kneaded at 260 ° C, extruded through a T-die at a set temperature of 255 ° C, and mirror-cooled rollers were used for surface rotation. Printed as unstretched film. Then, this unstretched film was sequentially stretched (MD stretching magnification: 1.8 times, TD stretching magnification: 2.5 times) using a melt stretching apparatus to obtain a second (meth) acrylic resin film having a thickness of 40 μm.
於上述熔融擠出成形中,從擠出樹脂開始到經過100 小時之T型模頭附近的蒸發物,以目視確認時,由於沒有見到蒸發物的累積,故可判斷於所得之第2(甲基)丙烯酸系樹脂膜不會有蒸發物的附著/混入之虞。而且,所得之第2(甲基)丙烯酸系樹脂膜在260至320nm的波長區域的最大穿透率(%),於320nm為84.2%。所得之第2(甲基)丙烯酸系樹脂膜在190至380nm的波長區域的穿透率表示於第7圖。 In the above-mentioned melt extrusion molding, from extruding the resin to 100 When the vapors near the T-die of the hour are visually confirmed, since no vapors have been accumulated, it can be judged that the second (meth) acrylic resin film obtained does not have vapors attached or mixed. Fear. The maximum transmittance (%) of the obtained second (meth) acrylic resin film in the wavelength region of 260 to 320 nm was 84.2% at 320 nm. The transmittance of the obtained second (meth) acrylic resin film in a wavelength region of 190 to 380 nm is shown in FIG. 7.
除使用上述(1)及(2)製作的第1及第2(甲基)丙烯酸系樹脂膜外,與實施例1的(4)同樣地製作偏光板。所得之偏光板在260至380nm的波長區域的最大穿透率(%)為1.0%。而且,所得之偏光板即使以剪刀裁切時,亦不會產生(甲基)丙烯酸系樹脂膜從偏光膜剝離的缺陷,確認出兩面的接著劑層充分地硬化。 A polarizing plate was produced in the same manner as in (4) of Example 1 except that the first and second (meth) acrylic resin films produced in the above (1) and (2) were used. The maximum transmittance (%) of the obtained polarizing plate in the wavelength region of 260 to 380 nm was 1.0%. In addition, even when the obtained polarizing plate was cut with scissors, no defect of peeling of the (meth) acrylic resin film from the polarizing film was generated, and it was confirmed that the adhesive layers on both sides were sufficiently hardened.
〈比較例1〉 <Comparative Example 1>
作為第1及第2(甲基)丙烯酸系樹脂膜,皆使用實施例2的(1)製作的(甲基)丙烯酸系樹脂膜以外,與實施例1的(4)同樣地製作偏光板。所得之偏光板在260至380nm的波長區域的最大穿透率(%)為0.1%。所得之偏光板係接著劑層的硬化不足,使用剪刀裁切偏光板時,產生(甲基)丙烯酸系樹脂膜從偏光膜剝離的缺陷。 As the first and second (meth) acrylic resin films, a polarizing plate was produced in the same manner as in (4) of Example 1 except that the (meth) acrylic resin film produced in (1) of Example 2 was used. The obtained polarizing plate had a maximum transmittance (%) in a wavelength range of 260 to 380 nm of 0.1%. The obtained polarizing plate-based adhesive layer had insufficient hardening, and when the polarizing plate was cut with scissors, a defect in which the (meth) acrylic resin film was peeled from the polarizing film occurred.
〈比較例2〉 <Comparative Example 2>
於具備攪拌裝置、溫度感測器、冷卻管、氮氣導入管 的30L反應釜中,放入8000g的甲基丙烯酸甲酯(MMA)、2000g的2-(羥基甲基)丙烯酸甲酯(MHMA)、10000g的甲苯,於其中通入氮氣,升溫至105℃,回流下,添加作為引發劑的10.0g的過氧化異壬酸第三戊酯(ATOFINA吉富製「Lupasol 570」),同時花費4小時滴入20.0g引發劑與100g甲苯所成的溶液,在回流下(約105至110℃)進行溶液聚合,再花4小時進行熟成。 Equipped with a stirring device, temperature sensor, cooling tube, and nitrogen introduction tube Into a 30L reaction kettle, put 8000g of methyl methacrylate (MMA), 2000g of methyl 2- (hydroxymethyl) acrylate (MHMA), and 10,000g of toluene. Pass nitrogen gas through it, and raise the temperature to 105 ° C. Under reflux, 10.0 g of triamylperisonononanoate peroxide ("Lupasol 570" manufactured by ATOFINA Kyoto) was added as an initiator, and a solution of 20.0 g of initiator and 100 g of toluene was added dropwise over 4 hours, and the mixture was refluxed. Solution polymerization was carried out at a lower temperature (about 105 to 110 ° C), and it took 4 hours to mature.
於所得之聚合物溶液中,添加10g磷酸硬脂酯/磷酸二硬脂酯混合物(堺化學製「Phoslex A-18」),在回流下(約90至110℃)進行5小時的環化縮合反應後,將上述環化縮合反應所得之聚合物溶液,以樹脂量換算2.0kg/小時的處理速度,導入料桶溫度260℃、旋轉數100rpm、減壓度13.3至400hPa(10至300mmHg)、後排氣數1個、前排氣數4個的排氣型螺桿二軸擠出機(φ=29.75mm、L/D=30),在該擠出機內進行環化縮合反應及去揮發成分,藉由擠出,得到透明的含有內酯環的(甲基)丙烯酸系樹脂顆粒。 To the obtained polymer solution, 10 g of a stearyl phosphate / distearyl phosphate mixture ("Phoslex A-18" manufactured by Sakai Chemical Co., Ltd.) was added, and cyclic condensation was performed under reflux (approximately 90 to 110 ° C) for 5 hours. After the reaction, the polymer solution obtained by the above-mentioned cyclization condensation reaction is introduced at a processing rate of 2.0 kg / hour in terms of resin amount, and introduced into a barrel temperature of 260 ° C, a number of rotations of 100 rpm, and a pressure reduction degree of 13.3 to 400 hPa (10 to 300 mmHg) Exhaust-type screw two-shaft extruder with one rear exhaust and four front exhausts (φ = 29.75mm, L / D = 30). Cyclic condensation reaction and devolatization are performed in this extruder. As a component, transparent (meth) acrylic resin particles containing a lactone ring were obtained by extrusion.
所得之含有內酯環的(甲基)丙烯酸系樹脂顆粒的內酯環化率為97.0%,質量平均分子量為147700,熔融流動速率為11.0g/10分,Tg(玻璃轉化溫度)為130℃。 The lactone cyclization ratio of the obtained (meth) acrylic resin particles containing a lactone ring was 97.0%, the mass average molecular weight was 147700, the melt flow rate was 11.0 g / 10 minutes, and the Tg (glass transition temperature) was 130 ° C .
於擠出機,供給上述所得之含有內酯環的(甲基)丙烯酸系樹脂顆粒,對於含有內酯環的(甲基)丙烯酸系樹脂顆粒100重量%,混合日本CHIBA特殊化學公司製的紫外線吸收劑(TINUVIN1577)1重量%及ADEKA公司製的紫外線吸收劑「ADEKA STAB LA31」1重量%,以單軸擠出機, 以模頭溫度250℃從T型模頭擠出,以冷卻滾輪進行水冷而拉出,得到厚度120μm的膜。其後,以逐次二軸擠出機,實施1.8倍的縱向延伸(加熱溫度140℃),然後2.4倍的橫向延伸(加熱溫度140℃),得到厚度40μm的二軸延伸膜之含有內酯環的(甲基)丙烯酸系樹脂膜。 In the extruder, the (meth) acrylic resin particles containing the lactone ring obtained above were supplied, and 100% by weight of the (meth) acrylic resin particles containing the lactone ring were mixed with ultraviolet light manufactured by Japan's CHIBA Special Chemicals 1% by weight of absorbent (TINUVIN1577) and 1% by weight of UV absorber "ADEKA STAB LA31" manufactured by ADEKA Corporation. The film was extruded from a T-die at a die temperature of 250 ° C., and was drawn out by cooling with a cooling roller to obtain a film having a thickness of 120 μm. Thereafter, a sequential biaxial extruder was used to perform 1.8 times the longitudinal stretching (heating temperature of 140 ° C) and then 2.4 times the transverse stretching (heating temperature of 140 ° C) to obtain a biaxially stretched film having a thickness of 40 μm. (Meth) acrylic resin film.
於上述熔融擠出成形中,從擠出樹脂開始到經過100小時之T型模頭附近的蒸發物以目視確認時,因可見到蒸發物累積很多,故於所得之(甲基)丙烯酸系樹脂膜恐會有蒸發物的附著/混入。而且,所得之(甲基)丙烯酸系樹脂膜在190至380nm的波長區域的最大穿透率(%),於274nm為24.3%。所得之(甲基)丙烯酸系樹脂膜在190至380nm的波長區域的穿透率表示於第5圖。 In the above-mentioned melt extrusion molding, when the vapors near the T-die from the time of extruding the resin to 100 hours have been visually confirmed, a large amount of vapors can be accumulated, so the (meth) acrylic resin obtained There is a risk that vapors will adhere to the film. The maximum transmittance (%) of the obtained (meth) acrylic resin film in the wavelength region of 190 to 380 nm was 24.3% at 274 nm. The transmittance of the obtained (meth) acrylic resin film in a wavelength region of 190 to 380 nm is shown in FIG. 5.
於上述(1)所得之(甲基)丙烯酸系樹脂膜的貼合面,實施電暈處理後,於該電暈處理面,形成厚度100nm的易接著層。易接著層係相對於Toray Dow Silicone股份公司製的矽烷偶合劑「APZ-6601」100重量份,添加異丙醇66.7重量份所調製的溶液,以線棒#5塗佈於電暈處理面,使揮發成分蒸發來形成。 After the corona treatment was performed on the bonding surface of the (meth) acrylic resin film obtained in the above (1), an easy-adhesion layer with a thickness of 100 nm was formed on the corona-treated surface. The easy-adhesive layer is based on 100 parts by weight of a silane coupling agent "APZ-6601" manufactured by Toray Dow Silicone Co., Ltd., and a solution prepared by adding 66.7 parts by weight of isopropyl alcohol is applied to the corona treated surface with wire rod # 5. Volatile components are formed by evaporation.
然後,除使用具有易接著層的上述(甲基)丙烯酸系樹脂膜作為第1及第2(甲基)丙烯酸系樹脂膜以外,與實施例1的(4)同樣地製作偏光板。所得之偏光板在260至380nm的波長區域的最大穿透率(%)為1.5%。 Then, a polarizing plate was produced in the same manner as in (4) of Example 1 except that the (meth) acrylic resin film having the easily-adhesive layer was used as the first and second (meth) acrylic resin films. The maximum transmittance (%) of the obtained polarizing plate in the wavelength region of 260 to 380 nm was 1.5%.
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JP6887222B2 (en) * | 2016-06-21 | 2021-06-16 | 住友化学株式会社 | Polarizing plate set |
JP6934296B2 (en) * | 2016-12-01 | 2021-09-15 | 日東電工株式会社 | Polarizing plate with adhesive and image display device |
KR102510750B1 (en) * | 2017-04-04 | 2023-03-15 | 스미또모 가가꾸 가부시키가이샤 | Polarizing plate with protective film, and liquid crystal panel |
KR101934448B1 (en) | 2017-10-17 | 2019-01-02 | 에스케이씨 주식회사 | Polarizing plate protective film and liquid crystal display comprising same |
CN109468080A (en) * | 2018-09-03 | 2019-03-15 | 昆山倬跃蓝天电子科技有限公司 | A kind of high transparency film protective film |
CN109585512B (en) * | 2018-12-06 | 2021-09-21 | 京东方科技集团股份有限公司 | Display substrate, manufacturing method thereof and display device |
CN113156696A (en) * | 2021-04-14 | 2021-07-23 | 武汉华星光电半导体显示技术有限公司 | Display device |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008225452A (en) * | 2007-02-14 | 2008-09-25 | Asahi Kasei Chemicals Corp | Molding for optical element |
CN101460306A (en) * | 2006-03-31 | 2009-06-17 | 日本瑞翁株式会社 | Polarizing plate, liquid crystal display and protective film |
CN101512399A (en) * | 2006-09-01 | 2009-08-19 | 日东电工株式会社 | Protective film for polarizer, polarizing plate, and image display device |
CN102012535A (en) * | 2009-09-04 | 2011-04-13 | 东洋油墨制造株式会社 | Polarizing plate and photocurable adhesive for forming polarizing plate |
WO2012077317A1 (en) * | 2010-12-10 | 2012-06-14 | コニカミノルタオプト株式会社 | Optical film production method, optical film, polarizing plate, and liquid crystal display device |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2006112223A1 (en) * | 2005-03-31 | 2008-12-04 | 株式会社日本触媒 | Polarizer protective film, polarizing plate, and image display device |
JP4974971B2 (en) * | 2007-06-14 | 2012-07-11 | 株式会社日本触媒 | Thermoplastic resin composition, resin molded article and polarizer protective film using the same, and method for producing resin molded article |
JP2009036797A (en) * | 2007-07-31 | 2009-02-19 | Nitto Denko Corp | Optical film, polarizing plate, and image display device |
KR200462615Y1 (en) * | 2011-02-22 | 2012-09-19 | (주)지티씨코퍼레이션 | An electric resisting type sensor of fixing structure for a steel pipe |
JP5536015B2 (en) * | 2011-11-21 | 2014-07-02 | シャープ株式会社 | Photoelectric conversion element and photoelectric conversion element module |
JP6403936B2 (en) * | 2012-08-08 | 2018-10-10 | 住友化学株式会社 | Polarizing plate and liquid crystal display panel using the same |
JP2014206725A (en) * | 2013-03-19 | 2014-10-30 | 富士フイルム株式会社 | Polarizing plate and liquid crystal display device |
KR101576333B1 (en) * | 2013-06-17 | 2015-12-11 | 주식회사 엘지화학 | A display device having an excellent uv-ray absorbance property |
-
2015
- 2015-03-11 JP JP2015048285A patent/JP2016066047A/en active Pending
- 2015-03-13 TW TW104108051A patent/TWI656971B/en active
- 2015-03-19 KR KR1020150038129A patent/KR101996836B1/en active IP Right Grant
- 2015-03-24 CN CN201510130197.5A patent/CN104950370A/en active Pending
- 2015-12-14 JP JP2015242980A patent/JP2016105175A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101460306A (en) * | 2006-03-31 | 2009-06-17 | 日本瑞翁株式会社 | Polarizing plate, liquid crystal display and protective film |
CN101512399A (en) * | 2006-09-01 | 2009-08-19 | 日东电工株式会社 | Protective film for polarizer, polarizing plate, and image display device |
JP2008225452A (en) * | 2007-02-14 | 2008-09-25 | Asahi Kasei Chemicals Corp | Molding for optical element |
CN102012535A (en) * | 2009-09-04 | 2011-04-13 | 东洋油墨制造株式会社 | Polarizing plate and photocurable adhesive for forming polarizing plate |
WO2012077317A1 (en) * | 2010-12-10 | 2012-06-14 | コニカミノルタオプト株式会社 | Optical film production method, optical film, polarizing plate, and liquid crystal display device |
Also Published As
Publication number | Publication date |
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KR20150111291A (en) | 2015-10-05 |
TW201538323A (en) | 2015-10-16 |
JP2016066047A (en) | 2016-04-28 |
JP2016105175A (en) | 2016-06-09 |
CN104950370A (en) | 2015-09-30 |
KR101996836B1 (en) | 2019-07-05 |
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