TW202104448A - Optical film, polarizing plate and liquid crystal display device providing an optical film with excellent sticking resistance and transparency between the films and a polarizing plate and a liquid crystal display device comprising the optical film - Google Patents
Optical film, polarizing plate and liquid crystal display device providing an optical film with excellent sticking resistance and transparency between the films and a polarizing plate and a liquid crystal display device comprising the optical film Download PDFInfo
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- 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
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- 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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- 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
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- 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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Abstract
Description
本發明係有關於一種光學薄膜、偏光板及液晶顯示裝置。更詳而言之，本發明係有關於一種薄膜彼此之貼附耐性與透明性優良的光學薄膜、具備該光學薄膜的偏光板及液晶顯示裝置。The invention relates to an optical film, a polarizing plate and a liquid crystal display device. More specifically, the present invention relates to an optical film having excellent adhesion resistance and transparency between films, a polarizing plate and a liquid crystal display device provided with the optical film.
近年來隨著顯示裝置的發展，液晶顯示裝置或有機EL顯示裝置等平板顯示裝置的需要增加。而且，為提升耐透濕性，作為光學薄膜係逐漸使用環烯烴系樹脂或(甲基)丙烯酸系樹脂。With the development of display devices in recent years, the demand for flat panel display devices such as liquid crystal display devices or organic EL display devices has increased. Furthermore, in order to improve moisture permeability resistance, cycloolefin resins or (meth)acrylic resins are gradually used as optical film systems.
然而，另一方面，包含此種樹脂的光學薄膜有滑動性或貼附耐性較差的問題。因此，在光學薄膜的製造時，便有捲繞薄膜時發生薄膜彼此的貼附、劃傷，甚而於捲繞時光學薄膜破裂的問題。However, on the other hand, optical films containing such resins have the problem of poor sliding properties or sticking resistance. Therefore, when the optical film is manufactured, there are problems that the films stick to each other and scratches when the film is wound, and even the optical film is broken when the film is wound.
尤其是在薄膜化時，俗稱的膜殘餘消失，而使滑動性或貼附耐性進一步劣化，而不易操作處理光學薄膜，致其應用受限。Especially when the film is thinned, the commonly known film residue disappears, which further deteriorates the sliding properties or adhesion resistance, and it is difficult to handle the optical film, which limits its application.
作為光學薄膜的滑動性、貼附耐性之改良方法，有人提出使表面形成凹凸的方法、對表面塗布抗靜電層等薄膜的方法、或貼合保護薄膜並於該薄膜形成凹凸的方法等。As a method for improving the sliding properties and adhesion resistance of an optical film, a method of forming irregularities on the surface, a method of coating the surface with a film such as an antistatic layer, or a method of laminating a protective film and forming irregularities on the film, etc. have been proposed.
例如，專利文獻1及引用文獻2中提出在含有降莰烯系樹脂之光學薄膜中含有二氧化矽粒子等的微粒子。然而，僅添加此等所記載之微粒子，仍無法充分改善含有環烯烴系樹脂或(甲基)丙烯酸系樹脂之光學薄膜彼此的貼附性，而且，如欲改善此貼附耐性而使其含有大量的微粒子時，則會發生光學薄膜的霧度增加而導致透明性降低的問題。從而，實際上並不易使包含含有環烯烴系樹脂或(甲基)丙烯酸系樹脂之光學薄膜的薄膜的霧度不增加而改善貼附耐性。
[先前技術文獻]
[專利文獻]For example,
[專利文獻1]日本特開2018-112577號公報 [專利文獻2]日本特開2017-122855號公報[Patent Document 1] Japanese Patent Application Publication No. 2018-112577 [Patent Document 2] JP 2017-122855 A
[發明所欲解決之課題][The problem to be solved by the invention]
本發明係有鑑於上述問題、情況而完成者，其解決課題在於提供一種薄膜彼此之貼附耐性與透明性優良的光學薄膜。又，本發明課題在於提供一種具備該光學薄膜的偏光板及液晶顯示裝置。 [解決課題之手段]The present invention was completed in view of the above-mentioned problems and circumstances, and the problem to be solved is to provide an optical film having excellent adhesion resistance and transparency between films. In addition, the subject of the present invention is to provide a polarizing plate and a liquid crystal display device provided with the optical film. [Means to solve the problem]
本案發明人在為解決上述課題而針對上述問題的原因等進行研究的過程中發現，效果的顯現性會隨樹脂中所含有之微粒子的彈性模數而異，藉由使樹脂與微粒子的彈性模數的比值處於特定範圍內，可不損及光學薄膜的透明性地獲得良好的貼附耐性，而臻至完成本發明。 亦即，本發明之上述課題可藉由以下手段來解決。The inventors of the present case have studied the causes of the above-mentioned problems in order to solve the above-mentioned problems, and found that the manifestation of the effect varies with the elastic modulus of the fine particles contained in the resin. By making the elastic modulus between the resin and the fine particles The ratio of the number is within a specific range, and good adhesion resistance can be obtained without impairing the transparency of the optical film, and the present invention has been completed. That is, the above-mentioned problems of the present invention can be solved by the following means.
1. 一種光學薄膜，其係含有樹脂與有機微粒子的光學薄膜，其特徵為滿足下述要件(I)及(II)： (I)將不含有機微粒子之樹脂部分的平均彈性模數設為E1、將有機微粒子部分的平均彈性模數設為E2時，兩者的比值(E2/E1)係滿足下述式(1)： 式(1) 1.0＜E2/E1≦4.0 (II)前述樹脂係含有環烯烴系樹脂及(甲基)丙烯酸系樹脂的至少一者。1. An optical film, which is an optical film containing resin and organic microparticles, characterized by satisfying the following requirements (I) and (II): (I) When the average elastic modulus of the resin part not containing organic fine particles is set to E1 and the average elastic modulus of the organic fine particles section is set to E2, the ratio (E2/E1) of the two satisfies the following formula (1 ): Formula (1) 1.0＜E2/E1≦4.0 (II) The aforementioned resin system contains at least one of cycloolefin resin and (meth)acrylic resin.
2. 如第1項之光學薄膜，其中前述有機微粒子的平均一次粒徑為50～300nm的範圍內。2. The optical film according to
3. 如第1項或第2項之光學薄膜，其中前述比值(E2/E1)係滿足下述式(2)：
式(2) 2.0＜E2/E1≦3.0。3. For the optical film of
4. 一種偏光板，其特徵為具備如第1項至第3項中任一項之光學薄膜。4. A polarizing plate, which is characterized by having an optical film as in any one of
5. 一種液晶顯示裝置，其特徵為具備如第1項至第3項中任一項之光學薄膜。
[發明之效果]5. A liquid crystal display device characterized by having the optical film as in any one of
根據本發明之上述手段，可提供一種薄膜彼此之貼附耐性與透明性優良的光學薄膜。又，可提供一種具備該光學薄膜的偏光板及液晶顯示裝置。According to the above-mentioned means of the present invention, it is possible to provide an optical film having excellent adhesion resistance and transparency between films. Furthermore, a polarizing plate and a liquid crystal display device provided with the optical film can be provided.
就本發明之效果的顯現機構或作用機構尚不明確，但之所以藉由使樹脂與微粒子的彈性模數的比值處於特定範圍內，可獲得良好的貼附耐性的原因可如下推斷。The display mechanism or the action mechanism of the effect of the present invention is not clear, but the reason why good adhesion resistance can be obtained by setting the ratio of the elastic modulus of the resin to the fine particles within a specific range can be inferred as follows.
若對光學薄膜施加負載，則起初會對薄膜表面的微粒子以點形式施予能量。此時，微粒子不會壓碎而增加接觸面積，且微粒子某種程度需吸收能量。If a load is applied to the optical film, energy is initially applied to the fine particles on the surface of the film in the form of dots. At this time, the particles will not be crushed to increase the contact area, and the particles need to absorb energy to a certain extent.
藉由使有機微粒子的彈性模數與樹脂的彈性模數的比值處於特定範圍內，在疊合光學薄膜並施加負載時，不易發生因有機微粒子的彈性模數過低所引起的壓潰，貼附耐性良好。同時，藉由有機微粒子某種程度吸收能量，亦不易發生因彈性模數過高所引起之光學薄膜層的裂痕產生，透明性不易劣化。其結果，推斷可兼具貼附耐性與優良的透明性。By keeping the ratio of the elastic modulus of the organic fine particles to the elastic modulus of the resin within a specific range, when the optical film is laminated and a load is applied, crushing caused by the too low elastic modulus of the organic fine particles will not easily occur. Good patience. At the same time, the organic fine particles absorb energy to a certain extent, and it is not easy to cause cracks in the optical film layer caused by the excessively high elastic modulus, and the transparency is not easy to deteriorate. As a result, it is inferred that adhesion resistance and excellent transparency can be combined.
[實施發明之形態][The form of implementing the invention]
本發明之光學薄膜係含有樹脂與有機微粒子的光學薄膜，其特徵為滿足前述要件(I)及(II)。The optical film of the present invention is an optical film containing resin and organic fine particles, and is characterized by satisfying the aforementioned requirements (I) and (II).
此特徵為下述各實施樣態(形態)共通或對應的技術特徵。 就本發明實施樣態，由可獲得充分的貼附耐性而言，有機粒子的平均一次粒徑較佳為50nm以上；為防止光散射所致之透明性的劣化，較佳為300nm以下。 又，基於顯現本發明之效果的觀點，前述比值(E2/E1)較佳滿足前述式(2)。 再者，本發明之光學薄膜可較佳具備於偏光板及液晶顯示裝置。This feature is a common or corresponding technical feature of the following implementation modes (forms). In terms of implementation of the present invention, in order to obtain sufficient adhesion resistance, the average primary particle size of the organic particles is preferably 50 nm or more; in order to prevent the deterioration of transparency caused by light scattering, it is preferably 300 nm or less. In addition, from the viewpoint of exhibiting the effect of the present invention, the aforementioned ratio (E2/E1) preferably satisfies the aforementioned formula (2). Furthermore, the optical film of the present invention can preferably be provided in a polarizing plate and a liquid crystal display device.
以下就本發明與其構成要素、及實施本發明之形態、樣態進行詳細的說明。此外，本案中「～」係以包含其前後所記載之數值作為下限值及上限值的意義使用。 又，本發明中(甲基)丙烯酸系樹脂係以意指丙烯酸系樹脂與甲基丙烯系樹脂此兩種樹脂的總稱來使用。Hereinafter, the present invention, its constituent elements, and the forms and aspects of implementing the present invention will be described in detail. In addition, in this case, "~" is used to include the numerical value described before and after it as the lower limit and the upper limit. In addition, in the present invention, the (meth)acrylic resin is used as a general term that means two resins of acrylic resin and methacrylic resin.
《光學薄膜的概要》 本發明之光學薄膜係含有樹脂與有機微粒子的光學薄膜，其特徵為滿足下述要件(I)及(II)： (I) 將不含有機微粒子之樹脂部分的平均彈性模數設為E1、將有機微粒子部分的平均彈性模數設為E2時，兩者的比值(E2/E1)係滿足下述式(1)： 式(1) 1.0＜E2/E1≦4.0 (II) 前述樹脂係含有環烯烴系樹脂及(甲基)丙烯酸系樹脂的至少一者。"Overview of Optical Films" The optical film of the present invention is an optical film containing resin and organic microparticles, and is characterized by satisfying the following requirements (I) and (II): (I) When the average elastic modulus of the resin part not containing organic fine particles is set to E1 and the average elastic modulus of the organic fine particles section is set to E2, the ratio of the two (E2/E1) satisfies the following formula (1 ): Formula (1) 1.0＜E2/E1≦4.0 (II) The aforementioned resin system contains at least one of cycloolefin resin and (meth)acrylic resin.
藉由如此控制彈性模數，即使為含有環烯烴系樹脂及(甲基)丙烯酸系樹脂的至少一者的光學薄膜，仍可獲得兼具透明性與良好的貼附耐性的光學薄膜。By controlling the elastic modulus in this way, even if it is an optical film containing at least one of a cycloolefin resin and a (meth)acrylic resin, an optical film having both transparency and good adhesion resistance can be obtained.
將不含有機微粒子之樹脂部分的平均彈性模數設為E1、將有機微粒子部分的平均彈性模數設為E2時，兩者的比值(E2/E1)需滿足下述式(1)。較佳為兩者的比值(E2/E1)係滿足下述式(2)： 式(1) 1.0＜E2/E1≦4.0 式(2) 2.0＜E2/E1≦3.0。When the average elastic modulus of the resin portion not containing organic fine particles is set to E1 and the average elastic modulus of the organic fine particle portion is set to E2, the ratio (E2/E1) of the two must satisfy the following formula (1). Preferably, the ratio of the two (E2/E1) satisfies the following formula (2): Formula (1) 1.0＜E2/E1≦4.0 Formula (2) 2.0<E2/E1≦3.0.
當兩者的比值(E2/E1)為1.0以下時，亦即光學薄膜中之有機微粒子部分的彈性模數相對於樹脂部分的彈性模數為1以下時，在疊合光學薄膜彼此並施加負載時，有機微粒子會因負載而變形，而導致光學薄膜彼此的接觸面積增加。因此，對於貼附耐性無法獲得充分的效果。When the ratio of the two (E2/E1) is 1.0 or less, that is, when the elastic modulus of the organic fine particles in the optical film is less than 1 relative to the elastic modulus of the resin portion, the optical films are laminated and a load is applied. At this time, the organic particles will be deformed by the load, resulting in an increase in the contact area between the optical films. Therefore, a sufficient effect cannot be obtained for the sticking resistance.
另一方面，當兩者的比值(E2/E1)超過4.0時，亦即有機微粒子部分的彈性模數相對於樹脂部分的彈性模數過高時，有機微粒子會因負載而壓入至光學薄膜層中，研判會產生裂痕而導致薄膜的透明性劣化。 從而，樹脂部分與有機微粒子部分的彈性模數的比值若為本案所記載的範圍，則推斷可兼具光學薄膜彼此的貼附耐性與透明性。On the other hand, when the ratio of the two (E2/E1) exceeds 4.0, that is, when the elastic modulus of the organic fine particles part is too high relative to the elastic modulus of the resin part, the organic fine particles will be pressed into the optical film due to the load. In the layer, it is believed that cracks will occur and the transparency of the film will deteriorate. Therefore, if the ratio of the elastic modulus of the resin part and the organic fine particle part is in the range described in this case, it is inferred that the adhesion resistance and transparency of the optical films can be combined.
[彈性模數的測定] 於本發明中係測定光學薄膜中之有機微粒子部分與不含有機微粒子之樹脂部分的彈性模數。測定彈性模數之方法宜為透過與試料表面接觸來測定彈性模數的方法，不僅可舉出如原子力顯微鏡，尚可舉出掃描型力顯微鏡、奈米壓痕測試儀等。如此藉由接觸試料表面來進行測定，可測得奈米～微米級。[Determination of Elastic Modulus] In the present invention, the elastic modulus of the organic fine particles part and the resin part not containing organic fine particles in the optical film is measured. The method of measuring the modulus of elasticity is preferably a method of measuring the modulus of elasticity through contact with the sample surface. Not only an atomic force microscope, but also a scanning force microscope, a nanoindentation tester, etc. can be cited. In this way, the measurement is performed by touching the surface of the sample, and it can be measured in the nanometer to micrometer range.
本發明中的彈性模數係能以原子力顯微鏡(AFM)測得的彈性模數。藉由將力量-體積測定中所得之力曲線，以Hertz、DMT或JKR等力學模型進行擬合，能以楊氏模數算出彈性模數。The elastic modulus in the present invention can be measured with an atomic force microscope (AFM). By fitting the force curve obtained in the force-volume measurement with a mechanical model such as Hertz, DMT or JKR, the elastic modulus can be calculated by Young's modulus.
原子力顯微鏡(AFM)係具備前端安裝有探針的懸臂，要藉由AFM觀察試料時，係使掃描探針試料的表面。探針係沿著試料的表面移動。探針的動作可藉由懸臂檢測出來。The atomic force microscope (AFM) is equipped with a cantilever with a probe attached to the tip. When the sample is to be observed by AFM, the surface of the probe is scanned. The probe system moves along the surface of the sample. The movement of the probe can be detected by the cantilever.
進而，可透過適宜選擇AFM中的適當測定模式來測定彈性模數。適當的測定模式可依據聚合物的種類或供予AFM觀察之試料的表面狀態來選擇。可舉出例如可測定試料表面之(微小區域)的硬度的力調變模式(force modulation mode)、可測定試料表面之彈性模數或楊氏模數的分布的力量-體積模式，甚而可舉出力曲線測定。又，亦可舉出接觸模式、輕敲模式、非接觸模式。於本發明中係以力調變模式來測定。Furthermore, the elastic modulus can be measured by appropriately selecting an appropriate measurement mode in AFM. The appropriate measurement mode can be selected according to the type of polymer or the surface condition of the sample for AFM observation. For example, the force modulation mode (force modulation mode) that can measure the hardness of the sample surface (small area), the force-volume mode that can measure the distribution of the elastic modulus or Young's modulus of the sample surface, and even Output curve determination. In addition, contact mode, tap mode, and non-contact mode can also be cited. In the present invention, it is measured in the force modulation mode.
＜平均彈性模數E1及E2的測定＞ 使用原子力顯微鏡(AFM)「Dimension Icon」(Buruker公司製)。彈性模數的算出係使用彈簧常數3N/m的懸臂。以力量-體積模式，並以頻率5Hz、最大負載5nN、測定範圍20μm×20μm的測定條件進行觀察。測定光學薄膜的剖面，由所得彈性模數映射像算出不含有機微粒子之樹脂部分的彈性模數、及有機微粒子部分的彈性模數的平均值而分別作為E1及E2。＜Measurement of average elastic modulus E1 and E2＞ Atomic force microscope (AFM) "Dimension Icon" (manufactured by Buruker) was used. The elastic modulus is calculated using a cantilever with a spring constant of 3N/m. The observation was performed in the force-volume mode with a frequency of 5 Hz, a maximum load of 5 nN, and a measurement range of 20 μm×20 μm. The cross-section of the optical film was measured, and the average values of the elastic modulus of the resin portion containing no organic fine particles and the elastic modulus of the organic fine particles were calculated from the obtained elastic modulus mapping image, and these were used as E1 and E2, respectively.
圖1為根據具備懸臂之原子力顯微鏡之彈性模數的測定例。橫軸表示探針掃描光學薄膜的剖面的距離，縱軸表示彈性模數(GPa)。若掃描光學薄膜的剖面，可獲得例如圖1所示之彈性模數曲線1。使用另外測得之彈性模數映射像，在不含有機微粒子之樹脂部分的彈性模數曲線2及有機微粒子部分的彈性模數曲線3上各自任意選出20點，由其算術平均值算出不含有機微粒子之樹脂部分的平均彈性模數E1及有機微粒子部分的平均彈性模數E2。Figure 1 is an example of the measurement of the elastic modulus based on an atomic force microscope equipped with a cantilever. The horizontal axis represents the distance of the probe scanning the cross section of the optical film, and the vertical axis represents the modulus of elasticity (GPa). If the cross-section of the optical film is scanned, the
此外，在由有機微粒子部分的彈性模數曲線3算出平均彈性模數E2時，於各測定點，係採用有機微粒子部分的彈性模數曲線的最大值4，以其算術平均值作為有機微粒子部分的平均彈性模數E2。這是因為，有機微粒子常會凝聚，而研判貼附耐性係有機微粒子部分之顯示最大的彈性模數的部分所貢獻之故。此外，彈性模數可根據樹脂或有機微粒子中之交聯劑的量、或有機微粒子的粒徑來控制。In addition, when calculating the average elastic modulus E2 from the
《光學薄膜的構成》 本發明之光學薄膜係含有樹脂與有機微粒子的光學薄膜，其中前述樹脂係含有環烯烴系樹脂及(甲基)丙烯酸系樹脂的至少一者。進而，可視需求含有各種添加劑。 透過使用此種樹脂，可獲致耐透濕性優良的光學薄膜。"The composition of optical film" The optical film of the present invention is an optical film containing a resin and organic fine particles, wherein the resin contains at least one of a cycloolefin resin and a (meth)acrylic resin. Furthermore, various additives may be contained as needed. By using this resin, an optical film with excellent moisture permeability resistance can be obtained.
[環烯烴系樹脂] 環烯烴系樹脂較佳為下述通式(A-1)或(A-2)表示之環烯烴單體的均聚物或共聚物。 茲就通式(A-1)表示之環烯烴單體加以說明。[Cycloolefin resin] The cycloolefin resin is preferably a homopolymer or copolymer of a cycloolefin monomer represented by the following general formula (A-1) or (A-2). Now, the cycloolefin monomer represented by the general formula (A-1) will be described.
通式(A-1)之R1 ～R4 各自獨立地顯示氫原子、鹵素原子、經取代或者未取代之碳原子數1～30之烴基、或極性基。惟，排除R1 ～R4 全為氫原子的情形，不會有R1 與R2 同時為氫原子，或R3 與R4 同時為氫原子的情形。 R 1 to R 4 in the general formula (A-1) each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, or a polar group. However, excluding the case where R 1 to R 4 are all hydrogen atoms, there will be no cases where R 1 and R 2 are hydrogen atoms at the same time, or R 3 and R 4 are hydrogen atoms at the same time.
鹵素原子為氟原子、氯原子、溴原子或碘原子。碳原子數1～30之烴基的實例包含碳原子數1～30之烷基。極性基的實例包含羧基、羥基、烷氧羰基、烯丙氧羰基、胺基、醯胺基、氰基、此等基經由亞甲基等連結基鍵結而成的基、羰基、醚基、矽基醚基、硫醚基、亞胺基等具有極性之二價有機基成為連結基鍵結而成的烴基等。此等當中，較佳為羧基、羥基、烷氧羰基或烯丙氧羰基，尤以烷氧羰基或烯丙氧羰基，基於確保溶液製膜時的溶解性之觀點係較佳。The halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Examples of the hydrocarbon group having 1 to 30 carbon atoms include an alkyl group having 1 to 30 carbon atoms. Examples of polar groups include carboxyl groups, hydroxyl groups, alkoxycarbonyl groups, allyloxycarbonyl groups, amine groups, amide groups, cyano groups, groups in which these groups are bonded via linking groups such as methylene groups, carbonyl groups, ether groups, A polar divalent organic group such as a silyl ether group, a thioether group, and an imino group becomes a hydrocarbon group formed by bonding a linking group. Among these, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, or an allyloxycarbonyl group is preferable, and an alkoxycarbonyl group or an allyloxycarbonyl group is particularly preferable from the viewpoint of ensuring solubility during film formation from a solution.
R1 ～R4 中至少1個，基於確保環烯烴系樹脂之溶液製膜時的溶解性的觀點等，較佳為極性基。At least one of R 1 to R 4 is preferably a polar group from the viewpoint of ensuring the solubility during film formation of a cycloolefin-based resin from a solution, and the like.
通式(A-1)之p表示0～2之整數。基於提高光學薄膜的耐熱性之觀點，p較佳為1～2。這是因為，若p為1～2，則所得樹脂為大體積，而容易提升玻璃轉移溫度之故。 其次，就通式(A-2)表示之環烯烴單體加以說明。P in the general formula (A-1) represents an integer of 0-2. From the viewpoint of improving the heat resistance of the optical film, p is preferably 1-2. This is because if p is 1 to 2, the resulting resin has a large volume and it is easy to raise the glass transition temperature. Next, the cycloolefin monomer represented by the general formula (A-2) will be described.
通式(A-2)之R5 表示氫原子、碳原子數1～5之烴基、或具有碳原子數1～5之烷基的烷矽基。其中，R5 較佳為碳原子數1～3之烴基。 R 5 in the general formula (A-2) represents a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, or an alkylsilyl group having an alkyl group having 1 to 5 carbon atoms. Among them, R 5 is preferably a hydrocarbon group having 1 to 3 carbon atoms.
通式(A-2)之R6 表示極性基或鹵素原子。極性基較佳為羧基、羥基、烷氧羰基、烯丙氧羰基、胺基、醯胺基、或氰基。鹵素原子為氟原子、氯原子、溴原子或碘原子。其中，R6 較佳為極性基，較佳為羧基、羥基、烷氧羰基或烯丙氧羰基；尤以烷氧羰基或烯丙氧羰基，基於確保溶液製膜時的溶解性之觀點係較佳。 R 6 in the general formula (A-2) represents a polar group or a halogen atom. The polar group is preferably a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amido group, or a cyano group. The halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Among them, R 6 is preferably a polar group, preferably a carboxyl group, a hydroxyl group, an alkoxycarbonyl group or an allyloxycarbonyl group; especially an alkoxycarbonyl group or an allyloxycarbonyl group, based on the viewpoint of ensuring the solubility during solution film formation. good.
透過使用如通式(A-2)表示之環烯烴單體，可降低分子的對稱性，而容易促進溶劑揮發時之樹脂的擴散運動。 通式(A-2)中，p表示0～2之整數。 以下示出通式(A-1)及(A-2)之結構的具體例。By using the cycloolefin monomer represented by the general formula (A-2), the symmetry of the molecule can be reduced, and the diffusion of the resin when the solvent is volatilized can be easily promoted. In general formula (A-2), p represents an integer of 0-2. Specific examples of the structures of the general formulas (A-1) and (A-2) are shown below.
可與通式(A-1)或通式(A-2)表示之環烯烴單體共聚合之共聚合性單體的實例包含可與通式(A-1)或通式(A-2)表示之環烯烴單體進行開環共聚合之共聚合性單體、可與通式(A-1)或通式(A-2)表示之環烯烴單體進行加成共聚合之共聚合性單體。Examples of copolymerizable monomers that can be copolymerized with cycloolefin monomers represented by general formula (A-1) or general formula (A-2) include general formula (A-1) or general formula (A-2). ) Represents a copolymerizable monomer that undergoes ring-opening copolymerization of cycloolefin monomers, and can be copolymerized by addition copolymerization with cycloolefin monomers represented by general formula (A-1) or general formula (A-2) Sex monomer.
可與通式(A-1)或通式(A-2)表示之環烯烴單體進行開環共聚合之共聚合性單體的實例包含環丁烯、環戊烯、環庚烯、環辛烯、二環戊二烯等其他環烯烴單體。Examples of copolymerizable monomers that can be subjected to ring-opening copolymerization with cycloolefin monomers represented by general formula (A-1) or general formula (A-2) include cyclobutene, cyclopentene, cycloheptene, and cycloolefin monomers. Other cycloolefin monomers such as octene and dicyclopentadiene.
可與通式(A-1)或通式(A-2)表示之環烯烴單體進行加成共聚合之共聚合性單體的實例包含含不飽和雙鍵化合物、乙烯基系環狀烴化合物、(甲基)丙烯酸酯。含不飽和雙鍵化合物的實例為碳原子數2～12(較佳為2～8)之烯烴系化合物，其例包含乙烯、丙烯、丁烯。乙烯基系環狀烴化合物的實例包含4-乙烯基環戊烯、2-甲基-4-異丙烯基環戊烯等乙烯基環戊烯系單體。(甲基)丙烯酸酯的實例包含(甲基)丙烯酸甲酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸環己酯等碳原子數1～20之(甲基)丙烯酸烷基酯。Examples of copolymerizable monomers that can be addition copolymerized with cycloolefin monomers represented by general formula (A-1) or general formula (A-2) include unsaturated double bond-containing compounds and vinyl-based cyclic hydrocarbons Compound, (meth)acrylate. Examples of unsaturated double bond-containing compounds are olefin compounds having 2 to 12 carbon atoms (preferably 2 to 8), and examples thereof include ethylene, propylene, and butene. Examples of the vinyl-based cyclic hydrocarbon compound include vinylcyclopentene-based monomers such as 4-vinylcyclopentene and 2-methyl-4-isopropenylcyclopentene. Examples of (meth)acrylates include (meth)acrylic acid with 1 to 20 carbon atoms, such as methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and cyclohexyl (meth)acrylate. Alkyl ester.
通式(A-1)或通式(A-2)表示之環烯烴單體所衍生之結構單元的含量，相對於構成環烯烴系樹脂之結構單元的合計可定為50～100莫耳%，較佳為60～100莫耳%，更佳為70～100莫耳%。The content of the structural unit derived from the cycloolefin monomer represented by the general formula (A-1) or the general formula (A-2) can be set at 50-100 mol% relative to the total of the structural units constituting the cycloolefin resin , Preferably 60-100 mol%, more preferably 70-100 mol%.
環烯烴系樹脂係將通式(A-1)或(A-2)表示之環烯烴單體進行均聚合或共聚合而得之聚合物，可舉出例如以下者，較佳為(1)～(3)及(5)，更佳為(3)及(5)。Cycloolefin resins are polymers obtained by homopolymerizing or copolymerizing cycloolefin monomers represented by the general formula (A-1) or (A-2). Examples include the following, and preferably (1) ~ (3) and (5), more preferably (3) and (5).
(1)通式(A-1)或(A-2)表示之環烯烴單體的開環聚合物 (2)通式(A-1)或(A-2)表示之環烯烴單體與共聚合性單體的開環共聚物 (3)上述(1)或(2)之開環(共)聚合物的氫化(共)聚合物 (4)將上述(1)或(2)之開環(共)聚合物藉由夫-夸反應進行環化後經氫化而得的(共)聚合物 (5)通式(A-1)或(A-2)表示之環烯烴單體與含不飽和雙鍵化合物的共聚物 (6)通式(A-1)或(A-2)表示之環烯烴單體的加成型(共)聚合物及其氫化(共)聚合物 (7)通式(A-1)或(A-2)表示之環烯烴單體與甲基丙烯酸酯或丙烯酸酯的交替共聚物(1) Ring-opening polymer of cycloolefin monomer represented by general formula (A-1) or (A-2) (2) Ring-opening copolymer of cycloolefin monomer and copolymerizable monomer represented by general formula (A-1) or (A-2) (3) Hydrogenated (co)polymer of the ring-opening (co)polymer of (1) or (2) above (4) The (co)polymer obtained by cyclizing the ring-opening (co)polymer of the above (1) or (2) by Fu-Kwa reaction and then hydrogenating (5) Copolymer of cycloolefin monomer represented by general formula (A-1) or (A-2) and compound containing unsaturated double bond (6) Addition type (co)polymer of cycloolefin monomer represented by general formula (A-1) or (A-2) and its hydrogenated (co)polymer (7) Alternating copolymer of cycloolefin monomer and methacrylate or acrylate represented by general formula (A-1) or (A-2)
環烯烴系樹脂可舉出具有下述通式(B-1)表示之結構單元與通式(B-2)表示之結構單元中至少一者的樹脂。其中，基於所得環烯烴系樹脂的玻璃轉移溫度較高，且容易獲得高穿透率的光學薄膜之觀點，較佳為包含通式(B-2)表示之結構單元的聚合物、或具有通式(B-1)表示之結構單元與通式(B-2)表示之結構單元的共聚物。Examples of the cycloolefin resin include resins having at least one of a structural unit represented by the following general formula (B-1) and a structural unit represented by the general formula (B-2). Among them, based on the viewpoint that the obtained cycloolefin resin has a high glass transition temperature and is easy to obtain an optical film with high transmittance, a polymer containing a structural unit represented by the general formula (B-2), or a polymer having the general formula (B-2) A copolymer of the structural unit represented by the formula (B-1) and the structural unit represented by the general formula (B-2).
通式(B-1)中，X為-CH=CH-表示之基或 -CH2 CH2 -表示之基。R1 ～R4 及p係與通式(A-1)之R1 ～R4 及p各自相同。In the general formula (B-1), X is a group represented by -CH=CH- or a group represented by -CH 2 CH 2 -. R 1 ~ R 4 and R p lines general formula (A-1) of 1 ~ R 4 and p are the same.
通式(B-2)中，X為-CH=CH-表示之基或 -CH2 CH2 -表示之基。通式(B-2)之R5 、R6 及p係與通式(A-2)之R5 、R6 及p各自相同。 環烯烴系樹脂可單獨使用1種或併用2種以上。In the general formula (B-2), X is a group represented by -CH=CH- or a group represented by -CH 2 CH 2 -. Formula (B-2) of R 5, R 6 and p are based of the general formula (A-2) of R 5, R 6 and p are the same. Cycloolefin resin can be used individually by 1 type or in combination of 2 or more types.
環烯烴系樹脂的固有黏度[η]inh 為例如0.2～5cm3 /g，較佳為0.3～3cm3 /g，更佳為0.4～1.5cm3 /g。環烯烴系樹脂的數量平均分子量(Mn)為例如8000～100000，較佳為10000～80000，更佳為12000～50000；重量平均分子量(Mw)為例如20000～300000，更佳為30000～250000，再更佳為40000～200000。數量平均分子量(Mn)或重量平均分子量(Mw)可藉由凝膠滲透層析法(GPC)，以聚苯乙烯換算來測定。 固有黏度[η]inh 、數量平均分子量及重量平均分子量若處於上述範圍，則環烯烴系樹脂的耐熱性、耐水性、耐藥性、機械特性與作為薄膜之成形加工性良好。The intrinsic viscosity [η] inh of the cycloolefin resin is, for example, 0.2 to 5 cm 3 /g, preferably 0.3 to 3 cm 3 /g, and more preferably 0.4 to 1.5 cm 3 /g. The number average molecular weight (Mn) of the cycloolefin resin is, for example, 8,000 to 100,000, preferably 10,000 to 80,000, more preferably 12,000 to 50,000; the weight average molecular weight (Mw) is, for example, 20,000 to 300,000, more preferably 30,000 to 250,000, More preferably, it is 40,000 to 200,000. The number average molecular weight (Mn) or weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC) in terms of polystyrene. If the intrinsic viscosity [η] inh , number average molecular weight, and weight average molecular weight are within the above ranges, the cycloolefin resin has good heat resistance, water resistance, chemical resistance, mechanical properties, and film forming processability.
環烯烴系樹脂的玻璃轉移溫度(Tg)通常為110℃以上，較佳為110～350℃，再更佳為120～250℃，特佳為120～220℃。Tg為110℃以上時，由於可於高溫條件下使用，或不易因塗覆、印刷等二次加工而發生變形而較佳。另一方面，藉由使Tg為350℃以下，則可避免不易成形加工的情形，得以抑制因成形加工時的熱而使樹脂劣化的可能性。The glass transition temperature (Tg) of the cycloolefin resin is usually 110°C or higher, preferably 110 to 350°C, more preferably 120 to 250°C, particularly preferably 120 to 220°C. When the Tg is 110°C or higher, it is preferable because it can be used under high temperature conditions or is not easily deformed due to secondary processing such as coating and printing. On the other hand, by setting the Tg to 350° C. or less, it is possible to avoid the situation where the molding process is not easy, and it is possible to suppress the possibility of deterioration of the resin due to the heat during the molding process.
再者，環烯烴系樹脂可較佳使用市售品，作為市售品的實例，係由JSR(股)以ARTON(註冊商標)G、ARTON F、ARTON R及ARTON RX之商品名販售，可使用此等商品。Furthermore, the cycloolefin resin may preferably be a commercially available product. As an example of a commercially available product, it is sold by JSR (Stock) under the trade names of ARTON (registered trademark) G, ARTON F, ARTON R and ARTON RX. These products can be used.
[(甲基)丙烯酸系樹脂] 包含本發明之光學薄膜所含有之(甲基)丙烯酸系單體的聚合物(亦稱丙烯酸樹脂)可舉出例如聚甲基丙烯酸甲酯等聚(甲基)丙烯酸酯、甲基丙烯酸甲酯-(甲基)丙烯酸共聚物、甲基丙烯酸甲酯-(甲基)丙烯酸酯共聚物、甲基丙烯酸甲酯-丙烯酸酯-(甲基)丙烯酸共聚物、(甲基)丙烯酸甲酯-苯乙烯共聚物(MS樹脂等)、具脂環族烴基之聚合物(例如甲基丙烯酸甲酯-甲基丙烯酸環己酯共聚物、甲基丙烯酸甲酯-(甲基)丙烯酸降莰酯共聚物等)。[(Meth) acrylic resin] The polymer (also known as acrylic resin) containing the (meth)acrylic monomer contained in the optical film of the present invention includes, for example, poly(meth)acrylate such as polymethylmethacrylate, and methylmethacrylate -(Meth)acrylic acid copolymer, methyl methacrylate-(meth)acrylate copolymer, methyl methacrylate-acrylate-(meth)acrylic acid copolymer, methyl (meth)acrylate-benzene Ethylene copolymers (MS resins, etc.), polymers with alicyclic hydrocarbon groups (e.g. methyl methacrylate-cyclohexyl methacrylate copolymer, methyl methacrylate-norbornyl (meth)acrylate copolymer) Wait).
更詳而言之，係以由後述例示之單體等任意選出之組合經均聚合或共聚合之樹脂、進而對該樹脂實施環化反應、脫水縮合反應、氫化反應、保護官能基之離去反應等後反應之樹脂中具有重量比為50%以上的(甲基)丙烯酸酯者。More specifically, it is a resin that is homopolymerized or copolymerized with a combination of monomers exemplified in the following description, and then subjected to cyclization reaction, dehydration condensation reaction, hydrogenation reaction, and removal of protective functional groups. After the reaction, etc., the resin to be reacted has a weight ratio of 50% or more (meth)acrylate.
(單體物種) 前述單體可舉出例如(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)丙烯酸二級丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸二級戊酯、(甲基)丙烯酸三級戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十三酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸環己基甲酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十八酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸三環癸酯、(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3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸β-甲基環氧丙酯、(甲基)丙烯酸β-乙基環氧丙酯、(甲基)丙烯酸(3,4-環氧環己基)甲酯、(甲基)丙烯酸N,N-二甲胺基乙酯、α-羥基甲基丙烯酸甲酯、α-羥基甲基丙烯酸乙酯等(甲基)丙烯酸酯類等。(Monomer species) The aforementioned monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 2-Butyl (meth)acrylate, 3-Butyl (meth)acrylate, n-pentyl (meth)acrylate, 2-pentyl (meth)acrylate, tertiary pentyl (meth)acrylate, ( Hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth) Cyclohexyl methyl acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylate Base) isobornyl acrylate, adamantyl (meth)acrylate, tricyclodecyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylate Base) 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-methyl (meth)acrylate Oxyethyl, 2-ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, ( (Meth) acrylate β-methyl glycidyl ester, (meth) acrylate β-ethyl glycidyl ester, (3,4-epoxycyclohexyl) methyl (meth)acrylate, (meth)acrylic acid (Meth)acrylates such as N,N-dimethylaminoethyl, α-hydroxymethyl methacrylate, α-hydroxyethyl methacrylate, etc.
可舉出甲基丙烯酸異丁酯、甲基丙烯酸2-甲基丁酯、甲基丙烯酸2-乙基丁酯、甲基丙烯酸2-異丙基丁酯、甲基丙烯酸2-異丙基-4-甲基丁酯、甲基丙烯酸2,3-二甲基丁酯、甲基丙烯酸2-甲基戊酯、甲基丙烯酸2-乙基戊酯、甲基丙烯酸2-丙基戊酯、甲基丙烯酸2-異丙基戊酯；Examples include isobutyl methacrylate, 2-methylbutyl methacrylate, 2-ethylbutyl methacrylate, 2-isopropylbutyl methacrylate, 2-isopropyl methacrylate 4-methylbutyl ester, 2,3-dimethylbutyl methacrylate, 2-methylpentyl methacrylate, 2-ethylpentyl methacrylate, 2-propylpentyl methacrylate, 2-isopropylpentyl methacrylate;
甲基丙烯酸二級丁酯、甲基丙烯酸1-甲基丁酯、甲基丙烯酸1-甲基戊酯、甲基丙烯酸1,3-二甲基丁酯、甲基丙烯酸1,2-二甲基丙酯、甲基丙烯酸1,2-二甲基丁酯、甲基丙烯酸1,2-二甲基戊酯、甲基丙烯酸1,2,3-三甲基丁酯、甲基丙烯酸2-乙基-1-甲基丁酯、甲基丙烯酸2-乙基-1-甲基戊酯、甲基丙烯酸2-乙基-1,3-二甲基丁酯、甲基丙烯酸1-甲基-2-丙基戊酯、甲基丙烯酸2-異丙基-1-甲基戊酯、甲基丙烯酸2-異丙基-1,3-二甲基丁酯、甲基丙烯酸1-乙基丙酯、甲基丙烯酸1-乙基丁酯、甲基丙烯酸1-乙基戊酯、甲基丙烯酸1-乙基-3-甲基丁酯、甲基丙烯酸1-乙基-2-甲基丙酯、甲基丙烯酸1-乙基-2-甲基丁酯、甲基丙烯酸1-乙基-2-甲基戊酯、甲基丙烯酸1-乙基-2,3-二甲基丁酯、甲基丙烯酸1,2-二乙基丁酯、甲基丙烯酸1,2-二乙基戊酯、甲基丙烯酸1,2-二乙基-3-甲基丁酯、甲基丙烯酸1-乙基-2-丙基戊酯、甲基丙烯酸2-異丙基-1-乙基戊酯、甲基丙烯酸1-乙基-2-異丙基-3-甲基丁酯、甲基丙烯酸1-丙基丁酯；Secondary butyl methacrylate, 1-methylbutyl methacrylate, 1-methylpentyl methacrylate, 1,3-dimethylbutyl methacrylate, 1,2-dimethyl methacrylate Propyl acrylate, 1,2-dimethylbutyl methacrylate, 1,2-dimethylpentyl methacrylate, 1,2,3-trimethylbutyl methacrylate, 2-methacrylate Ethyl-1-methylbutyl ester, 2-ethyl-1-methylpentyl methacrylate, 2-ethyl-1,3-dimethylbutyl methacrylate, 1-methyl methacrylate -2-propylpentyl ester, 2-isopropyl-1-methylpentyl methacrylate, 2-isopropyl-1,3-dimethylbutyl methacrylate, 1-ethyl methacrylate Propyl ester, 1-ethylbutyl methacrylate, 1-ethylpentyl methacrylate, 1-ethyl-3-methylbutyl methacrylate, 1-ethyl-2-methyl methacrylate Propyl ester, 1-ethyl-2-methylbutyl methacrylate, 1-ethyl-2-methylpentyl methacrylate, 1-ethyl-2,3-dimethylbutyl methacrylate , 1,2-diethylbutyl methacrylate, 1,2-diethylpentyl methacrylate, 1,2-diethyl-3-methylbutyl methacrylate, 1-methacrylate Ethyl-2-propylpentyl ester, 2-isopropyl-1-ethylpentyl methacrylate, 1-ethyl-2-isopropyl-3-methylbutyl methacrylate, methacrylic acid 1-propyl butyl ester;
甲基丙烯酸1-丙基戊酯、甲基丙烯酸3-甲基-1-丙基丁酯、甲基丙烯酸1-異丙基丁酯、甲基丙烯酸2-甲基-1-丙基丁酯、甲基丙烯酸2-甲基-1-丙基戊酯、甲基丙烯酸2,3-二甲基-1-丙基丁酯、甲基丙烯酸2-乙基-1-丙基丁酯、甲基丙烯酸2-乙基-1-丙基戊酯、甲基丙烯酸2-乙基-3-甲基-1-丙基丁酯、甲基丙烯酸1,2-二丙基戊酯、甲基丙烯酸2-異丙基-1-丙基戊酯、甲基丙烯酸2-異丙基-3-甲基-1-丙基丁酯、甲基丙烯酸1-異丙基戊酯、甲基丙烯酸1-異丙基-3-甲基丁酯、甲基丙烯酸1-異丙基-2-甲基丙酯、甲基丙烯酸1-異丙基-2-甲基丁酯、甲基丙烯酸1-異丙基-2-甲基戊酯、甲基丙烯酸1-異丙基-2,3-二甲基丁酯、甲基丙烯酸2-乙基-1-異丙基丁酯、甲基丙烯酸2-乙基-1-異丙基戊酯、甲基丙烯酸2-二乙基-1-異丙基-3-甲基丁酯、甲基丙烯酸1-異丙基-2-丙基戊酯、甲基丙烯酸1,2-二異丙基戊酯、甲基丙烯酸1,2-異丙基-3-甲基丁酯；1-propylpentyl methacrylate, 3-methyl-1-propylbutyl methacrylate, 1-isopropylbutyl methacrylate, 2-methyl-1-propylbutyl methacrylate , 2-methyl-1-propylpentyl methacrylate, 2,3-dimethyl-1-propylbutyl methacrylate, 2-ethyl-1-propylbutyl methacrylate, methyl methacrylate 2-ethyl-1-propylpentyl acrylate, 2-ethyl-3-methyl-1-propylbutyl methacrylate, 1,2-dipropylpentyl methacrylate, methacrylic acid 2-isopropyl-1-propylpentyl ester, 2-isopropyl-3-methyl-1-propylbutyl methacrylate, 1-isopropylpentyl methacrylate, 1-isopropyl methacrylate Isopropyl-3-methylbutyl ester, 1-isopropyl-2-methylpropyl methacrylate, 1-isopropyl-2-methylbutyl methacrylate, 1-isopropyl methacrylate 2-methylpentyl ester, 1-isopropyl-2,3-dimethylbutyl methacrylate, 2-ethyl-1-isopropylbutyl methacrylate, 2-ethyl methacrylate 1-isopropylpentyl methacrylate, 2-diethyl-1-isopropyl-3-methylbutyl methacrylate, 1-isopropyl-2-propylpentyl methacrylate,
甲基丙烯酸三級丁酯、甲基丙烯酸1,1-二甲基丙酯、甲基丙烯酸1-乙基-1-甲基丙酯、甲基丙烯酸1,1-二乙基丙酯、甲基丙烯酸1,1-二甲基丁酯、甲基丙烯酸1-乙基-1-甲基丁酯、甲基丙烯酸1,1-二乙基丁酯、甲基丙烯酸1-甲基-1-丙基丁酯、甲基丙烯酸1-乙基-1-丙基丁酯、甲基丙烯酸1,1-二丙基丁酯、甲基丙烯酸1,1,2-三甲基丙酯、甲基丙烯酸1-乙基-1,2-二甲基丙酯、甲基丙烯酸1,1-二乙基-2-甲基丙酯、甲基丙烯酸1-異丙基-1-甲基丁酯、甲基丙烯酸1-乙基-1-異丙基丁酯、甲基丙烯酸1-異丙基-1-丙基丁酯、甲基丙烯酸1-異丙基-1,2-二甲基丙酯、甲基丙烯酸1,1-二異丙酯、甲基丙烯酸1,1-二異丙基丁酯、甲基丙烯酸1,1-二異丙基-2-甲基丙酯；Tertiary butyl methacrylate, 1,1-dimethylpropyl methacrylate, 1-ethyl-1-methylpropyl methacrylate, 1,1-diethylpropyl methacrylate,
甲基丙烯酸4-甲基環己酯、甲基丙烯酸2-甲基環己酯、甲基丙烯酸4-異丙基環己酯、甲基丙烯酸2-異丙基環己酯、甲基丙烯酸4-三級丁基環己酯、甲基丙烯酸2-三級丁基環己酯；4-methylcyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, 4-isopropylcyclohexyl methacrylate, 2-isopropylcyclohexyl methacrylate, 4 -Tertiary butyl cyclohexyl, 2-tertiary butyl cyclohexyl methacrylate;
甲基丙烯酸2-降莰酯、甲基丙烯酸2-甲基-2-降莰酯、甲基丙烯酸2-乙基-2-降莰酯、甲基丙烯酸2-異莰酯、甲基丙烯酸2-甲基-2-異莰酯、甲基丙烯酸2-乙基-2-異莰酯、甲基丙烯酸8-三環[5.2.1.02,6]癸酯、甲基丙烯酸8-甲基-8-三環[5.2.1.02,6]癸酯、甲基丙烯酸8-乙基-8-三環[5.2.1.02,6]癸酯、甲基丙烯酸2-金剛烷酯、甲基丙烯酸2-甲基-2-金剛烷酯、甲基丙烯酸2-乙基-2-金剛烷酯、甲基丙烯酸1-金剛烷酯、甲基丙烯酸2-葑酯、甲基丙烯酸2-甲基-2-葑酯、甲基丙烯酸2-乙基-2-葑酯、甲基丙烯酸十氫萘-1-酯、甲基丙烯酸十氫萘-2-酯等。2-Norbornyl methacrylate, 2-Methyl-2-norbornyl methacrylate, 2-Ethyl-2-norbornyl methacrylate, 2-isobornyl methacrylate, 2 -Methyl-2-isocampanate, 2-ethyl-2-isocampanate methacrylate, 8-tricyclo[5.2.1.02,6]decyl methacrylate, 8-methyl-8 methacrylate -Tricyclo[5.2.1.02,6]decyl ester, 8-ethyl-8-tricyclo[5.2.1.02,6]decyl methacrylate, 2-adamantyl methacrylate, 2-methyl methacrylate 2-ethyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl methacrylate, 1-adamantyl methacrylate, 2-fenchyl methacrylate, 2-methyl-2-fenchyl methacrylate Ester, 2-ethyl-2-fenchyl methacrylate, decahydronaphthalene-1-methacrylate, decalin-2-methacrylate, etc.
(可共聚合之單體) 可共聚合之單體可舉出N,N-二甲基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺等(甲基)丙烯醯胺類；(甲基)丙烯酸、巴豆酸、桂皮酸、乙烯基苯甲酸等不飽和單羧酸類；馬來酸、富馬酸、伊康酸、檸康酸、中康酸等不飽和多元羧酸類；琥珀酸單(2-丙烯醯氧基乙基)、琥珀酸單(2-甲基丙烯醯氧基乙基)等不飽和基與羧基之間經鏈拉伸的不飽和單羧酸類；馬來酸酐、伊康酸酐等不飽和酸酐類；苯乙烯、α-甲基苯乙烯、α-氯苯乙烯、p-三級丁基苯乙烯、p-甲基苯乙烯、p-氯苯乙烯、o-氯苯乙烯、2,5-二氯苯乙烯、3,4-二氯苯乙烯、乙烯基甲苯、甲氧基苯乙烯等芳香族乙烯基類；甲基馬來醯亞胺、乙基馬來醯亞胺、異丙基馬來醯亞胺、環己基馬來醯亞胺、苯基馬來醯亞胺、苯甲基馬來醯亞胺、萘基馬來醯亞胺等N取代馬來醯亞胺類；1,3-丁二烯、異戊二烯、氯丁二烯等共軛二烯類；乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、苯甲酸乙烯酯等乙烯酯類；甲基乙烯基醚、乙基乙烯基醚、丙基乙烯基醚、丁基乙烯基醚、2-乙基己基乙烯基醚、正壬基乙烯基醚、月桂基乙烯基醚、環己基乙烯基醚、甲氧基乙基乙烯基醚、乙氧基乙基乙烯基醚、甲氧基乙氧基乙基乙烯基醚、甲氧基聚乙二醇乙烯基醚、2-羥基乙基乙烯基醚、4-羥基丁酯乙烯基醚等乙烯基醚類；N-乙烯基吡咯烷酮、N-乙烯基己內醯胺、N-乙烯基咪唑、N-乙烯基嗎啉、N-乙烯基乙醯胺等N-乙烯基化合物類；(甲基)丙烯酸異氰酸基乙酯、異氰酸烯丙酯等不飽和異氰酸酯類；丙烯腈、甲基丙烯腈等氰化乙烯基類等。(Copolymerizable monomer) Copolymerizable monomers include (meth)acrylamides such as N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, etc.; (meth)acrylamide; Unsaturated monocarboxylic acids such as acrylic acid, crotonic acid, cinnamic acid and vinyl benzoic acid; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid; succinic acid mono(2 -Unsaturated monocarboxylic acids with chain stretching between unsaturated groups such as acryloxyethyl) and succinic acid mono(2-methacryloxyethyl) and carboxyl groups; maleic anhydride, itaconic anhydride Unsaturated acid anhydrides; styrene, α-methylstyrene, α-chlorostyrene, p-tertiary butylstyrene, p-methylstyrene, p-chlorostyrene, o-chlorostyrene, Aromatic vinyls such as 2,5-dichlorostyrene, 3,4-dichlorostyrene, vinyl toluene, and methoxystyrene; methyl maleimide, ethyl maleimide, N-substituted maleimines such as isopropyl maleimines, cyclohexyl maleimines, phenylmaleimines, benzyl maleimines, naphthylmaleimines, etc. ; Conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; methyl Vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, Methoxy ethyl vinyl ether, ethoxy ethyl vinyl ether, methoxy ethoxy ethyl vinyl ether, methoxy polyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, Vinyl ethers such as 4-hydroxybutyl vinyl ether; N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine, N-vinylacetamide, etc. N-vinyl compounds; unsaturated isocyanates such as isocyanatoethyl (meth)acrylate and allyl isocyanate; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile.
(丙烯酸樹脂之製造方法) 作為製造本發明之丙烯酸樹脂之方法，可採用例如澆鑄聚合、塊狀聚合、懸浮聚合、溶液聚合、乳化聚合、陰離子聚合等一般所進行的聚合方法。其中，在光學用途上由於可減少不必要之微小異物的混入，較佳為未使用懸浮劑或乳化劑的塊狀聚合或溶液聚合。(Method of manufacturing acrylic resin) As a method for producing the acrylic resin of the present invention, for example, casting polymerization, bulk polymerization, suspension polymerization, solution polymerization, emulsion polymerization, anionic polymerization and other generally performed polymerization methods can be used. Among them, for optical applications, since the incorporation of unnecessary fine foreign matter can be reduced, bulk polymerization or solution polymerization without using a suspending agent or emulsifier is preferred.
《溶液聚合》 進行溶液聚合時，可使用將單體的混合物溶解於甲苯、乙基苯等芳香族烴之溶劑所調製而成的溶液。藉由塊狀聚合進行聚合時，可藉由如通常所進行藉由加熱而生成之游離自由基或照射游離輻射線而起始聚合。"Solution Polymerization" When performing solution polymerization, a solution prepared by dissolving a mixture of monomers in an aromatic hydrocarbon solvent such as toluene and ethylbenzene can be used. When polymerization is performed by bulk polymerization, polymerization can be initiated by free radicals generated by heating or irradiation with ionizing radiation as usual.
作為聚合反應所使用之起始劑，可使用自由基聚合中所使用的任意起始劑，可使用例如偶氮雙異丁腈等偶氮化合物；過氧化苯甲醯、過氧化月桂醯基、三級丁基過氧-2-乙基己酸酯等有機過氧化物。As the initiator used in the polymerization reaction, any initiator used in radical polymerization can be used, such as azo compounds such as azobisisobutyronitrile; benzyl peroxide, lauryl peroxide, Organic peroxides such as tertiary butylperoxy-2-ethylhexanoate.
尤其是在90℃以上的高溫下進行聚合時，普遍為溶液聚合，因此較佳為10小時半衰期溫度為80℃以上且可溶於所用有機溶劑的過氧化物、偶氮雙起始劑等。具體而言，可舉出1,1-雙(三級丁基過氧)-3,3,5-三甲基環己烷、過氧化環己烷、2,5-二甲基-2,5-二(過氧化苯甲醯)己烷、1,1-偶氮雙(1-環己烷碳腈)、2-(胺甲醯基偶氮)異丁腈等。此等起始劑，例如相對於全部單體100質量%，較佳以0.005～5質量%的範圍使用。In particular, when the polymerization is carried out at a high temperature of 90°C or higher, it is generally a solution polymerization. Therefore, peroxides, azobis initiators, etc. that are soluble in the organic solvent used and have a 10-hour half-life temperature of 80°C or higher are preferred. Specifically, 1,1-bis(tertiary butylperoxy)-3,3,5-trimethylcyclohexane, cyclohexane peroxide, 2,5-dimethyl-2, 5-bis(benzoperoxy)hexane, 1,1-azobis(1-cyclohexanecarbonitrile), 2-(aminomethanoylazo)isobutyronitrile, etc. These initiators are preferably used in the range of 0.005 to 5% by mass relative to 100% by mass of all monomers, for example.
聚合反應中視需求所使用之分子量調節劑，可使用自由基聚合中一般所使用的任意者，可舉出例如丁硫醇、辛硫醇、十二硫醇、硫代乙醇酸2-乙基己酯等硫醇化合物作為特佳者。此等分子量調節劑係以如丙烯酸樹脂的分子量經控制於上述較佳範圍內的濃度範圍添加。The molecular weight regulator used in the polymerization reaction as required can be any one generally used in free radical polymerization, for example, butane mercaptan, octyl mercaptan, dodecane mercaptan, 2-ethylhexyl thioglycolic acid Thiol compounds such as esters are particularly preferred. These molecular weight regulators are added in a concentration range in which the molecular weight of the acrylic resin is controlled within the above-mentioned preferred range.
《塊狀聚合》 塊狀聚合係例如藉由將單體成分及聚合起始劑等連續地供給至反應容器中，同時連續抽出滯留於反應容器內既定時間而得之部分聚合物來進行，能以高生產性製造共聚物。"Lumpy Aggregation" Bulk polymerization is carried out by continuously supplying monomer components and polymerization initiators to the reaction vessel while continuously extracting part of the polymer that has been left in the reaction vessel for a predetermined period of time. It can be produced with high productivity. Copolymer.
聚合單體成分時所使用之聚合起始劑不特別限制，可使用例如偶氮雙異丁腈等偶氮化合物、1,1-二(三級丁基過氧)環己烷、過氧化苯甲醯、p-氯過氧化苯甲醯、二異丙基過氧碳酸酯、二-2-乙基己基過氧碳酸酯、三級丁基過氧特戊酸酯、三級丁基過氧(2-乙基己酸酯)等過氧化物等周知之自由基聚合起始劑。聚合起始劑可僅使用1種或組合使用2種以上。又，相對於混合物的總量，其用量通常為0.01～5質量%。熱聚合中的加熱溫度通常為40～200℃，加熱時間通常為30分鐘～8時間左右。The polymerization initiator used when polymerizing the monomer components is not particularly limited. For example, azo compounds such as azobisisobutyronitrile, 1,1-bis(tertiarybutylperoxy)cyclohexane, and benzene peroxide can be used. Formaldehyde, p-chlorobenzyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, tertiary butyl peroxy pivalate, tertiary butyl peroxy Known radical polymerization initiators such as peroxides such as (2-ethylhexanoate). The polymerization initiator can be used alone or in combination of two or more. In addition, the amount used is usually 0.01 to 5% by mass relative to the total amount of the mixture. The heating temperature in thermal polymerization is usually 40 to 200°C, and the heating time is usually about 30 minutes to 8 hours.
聚合單體成分時，可視需求使用鏈轉移劑。鏈轉移劑不特別限制，可舉出例如正丁硫醇、正辛硫醇、正十二硫醇、2-乙基己基硫乙醇酸酯等硫醇類等作為較佳者。鏈轉移劑亦可僅使用1種或組合使用2種以上。When polymerizing monomer components, a chain transfer agent can be used as needed. The chain transfer agent is not particularly limited, and preferred examples include mercaptans such as n-butane mercaptan, n-octyl mercaptan, n-dodecane mercaptan, and 2-ethylhexyl thioglycolate. The chain transfer agent can also be used only 1 type or in combination of 2 or more types.
《懸浮聚合》 採懸浮聚合時，可採用使用於一般的懸浮聚合者，可舉出有機過氧化物、偶氮化合物。 又，懸浮安定劑可使用一般所使用之習知品，可舉出有機膠體性高分子物質、無機膠體性高分子物質、無機微粒子及此等與界面活性劑之組合。"Suspension Polymerization" In the case of suspension polymerization, those used for general suspension polymerization can be used, and examples thereof include organic peroxides and azo compounds. In addition, the suspension stabilizer can use conventional products generally used, and examples thereof include organic colloidal polymer materials, inorganic colloidal polymer materials, inorganic fine particles, and combinations of these with surfactants.
供聚合單體混合物之水性介質可舉出水、或水與如醇(例如甲醇、乙醇)之水溶性溶劑的混合介質。水性介質的用量，為達交聯樹脂粒子的穩定化，通常，相對於單體混合物100質量份，為100～1000質量份。 又，為抑制乳化粒子在水系中產生，亦可使用亞硝酸鹽類、亞硫酸鹽類、氫醌類、抗壞血酸類、水溶性維生素B類、檸檬酸、多酚類等的水溶性聚合抑制劑。The aqueous medium for polymerizing the monomer mixture may include water, or a mixed medium of water and a water-soluble solvent such as alcohol (for example, methanol, ethanol). The amount of the aqueous medium used is to stabilize the crosslinked resin particles, and is usually 100 to 1000 parts by mass relative to 100 parts by mass of the monomer mixture. In addition, in order to suppress the production of emulsified particles in water systems, water-soluble polymerization inhibitors such as nitrites, sulfites, hydroquinones, ascorbic acid, water-soluble vitamin B, citric acid, and polyphenols can also be used. .
亦可進一步視需求添加其他懸浮安定劑。可舉出例如磷酸鈣、磷酸鎂、磷酸鋁、磷酸鋅等磷酸鹽、焦磷酸鈣、焦磷酸鎂、焦磷酸鋁、焦磷酸鋅等焦磷酸鹽、碳酸鈣、碳酸鎂、氫氧化鈣、氫氧化鎂、氫氧化鋁、偏矽酸鈣、硫酸鈣、硫酸鋇等難水溶性無機化合物、聚乙烯醇之分散安定劑等。Other suspension stabilizers can also be added as required. Examples include phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate, and zinc phosphate, calcium pyrophosphate, pyrophosphate such as magnesium pyrophosphate, aluminum pyrophosphate, zinc pyrophosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, hydrogen Magnesium oxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate and other poorly water-soluble inorganic compounds, dispersion stabilizers of polyvinyl alcohol, etc.
又，亦可併用上述懸浮安定劑與陰離子性界面活性劑、陽離子性界面活性劑、兩性離子性界面活性劑、非離子性界面活性劑等界面活性劑。In addition, the above-mentioned suspension stabilizer and surfactants such as anionic surfactants, cationic surfactants, zwitterionic surfactants, and nonionic surfactants may also be used in combination.
陰離子性界面活性劑可舉出例如油酸鈉、蓖麻油鉀等脂肪酸油、月桂基硫酸鈉、月桂基硫酸銨等烷基硫酸酯鹽、十二基苯磺酸鈉等烷基苯磺酸鹽、烷基磺酸鹽、烷基萘磺酸鹽、烷磺酸鹽、琥珀磺酸鹽、二烷基磺基琥珀酸鹽、烷基磷酸酯鹽、萘磺酸福馬林縮合物、聚氧乙烯烷基苯基醚硫酸酯鹽、聚氧乙烯烷基硫酸酯鹽等。Anionic surfactants include, for example, fatty acid oils such as sodium oleate and potassium castor oil, alkyl sulfate ester salts such as sodium lauryl sulfate and ammonium lauryl sulfate, and alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate. , Alkyl Sulfonate, Alkyl Naphthalene Sulfonate, Alkyl Sulfonate, Succinate, Dialkyl Sulfosuccinate, Alkyl Phosphate, Naphthalene Sulfonate Formalin Condensate, Polyoxyethylene Alkyl phenyl ether sulfate, polyoxyethylene alkyl sulfate, etc.
非離子性界面活性劑可舉出例如聚氧乙烯烷基醚、聚氧乙烯烷基苯基醚、聚氧乙烯脂肪酸酯、山梨醇酐脂肪酸酯、聚氧山梨醇酐脂肪酸酯、聚氧乙烯烷基胺、甘油脂肪酸酯、氧乙烯-氧丙烯嵌段聚合物等。Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxysorbitan fatty acid esters, and polyoxyethylene fatty acid esters. Oxyethylene alkylamine, glycerin fatty acid ester, oxyethylene-oxypropylene block polymer, etc.
陽離子性界面活性劑可舉出例如月桂基胺乙酸酯、十八基胺乙酸酯等烷基胺鹽、月桂基三甲基銨氯化物等四級銨鹽等。Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride.
兩性離子界面活性劑可舉出月桂基二甲基胺氧化物、磷酸酯系或亞磷酸酯系界面活性劑。Zwitterionic surfactants include lauryl dimethylamine oxide, phosphate ester-based or phosphite-based surfactants.
此等懸浮安定劑或界面活性劑可單獨或組合2種以上使用；而考量所得粒子的粒徑與聚合時的分散穩定性，係適宜調整懸浮安定劑的選擇或用量來使用。一般而言，懸浮安定劑的添加量，相對於單體混合物100質量份為0.5～15質量份；界面活性劑的添加量，相對於水性介質100質量份為0.001～10質量份。 對如此調製之水性介質添加單體混合物而進行聚合。These suspension stabilizers or surfactants can be used alone or in combination of two or more; and considering the particle size of the obtained particles and the dispersion stability during polymerization, the selection or amount of the suspension stabilizer is appropriately adjusted for use. Generally speaking, the addition amount of the suspension stabilizer is 0.5-15 parts by mass relative to 100 parts by mass of the monomer mixture; the addition amount of the surfactant is 0.001-10 parts by mass relative to 100 parts by mass of the aqueous medium. The monomer mixture is added to the aqueous medium prepared in this way to perform polymerization.
單體混合物之分散方法可舉出例如在水性介質中直接添加單體混合物，藉由槳葉等的攪拌力形成單體液滴而使其分散於水性介質中的方法、使用由轉子與定子所構成之利用高剪切力的分散機之均質混合機、或超音波分散機等而使其分散的方法等。 其次，藉由將單體混合物形成球狀滴而分散的水性懸浮液加熱而起始聚合。聚合反應中，較佳攪拌水性懸浮液，此攪拌只要以例如可防止球狀液滴上浮或聚合後的粒子沉降之程度緩緩地進行即可。The method of dispersing the monomer mixture can include, for example, the method of directly adding the monomer mixture to the aqueous medium, forming monomer droplets by the stirring force of a blade or the like, and dispersing the monomer mixture in the aqueous medium. It is composed of a homomixer using a high-shearing force dispersing machine, or an ultrasonic dispersing machine, etc. to disperse it. Next, the polymerization is initiated by heating the dispersed aqueous suspension of the monomer mixture into spherical droplets. In the polymerization reaction, it is preferable to stir the aqueous suspension, and this stirring may be carried out slowly, for example, to the extent that the floating of spherical liquid droplets or the sedimentation of the polymerized particles can be prevented.
聚合溫度宜設為30～100℃左右，再更佳為40～80℃左右。再者，保持於此聚合溫度之時間，較佳為0.1～20小時左右。The polymerization temperature is preferably about 30 to 100°C, and more preferably about 40 to 80°C. Furthermore, the time to maintain the polymerization temperature is preferably about 0.1 to 20 hours.
聚合後，可藉由抽吸過濾、離心脫水、離心分離、加壓脫水等方法使粒子形成含水濾餅而分離，並進一步將所得含水濾餅水洗、乾燥而得到目標粒子。於此，粒子的平均粒徑的調整，可調整單體混合物與水的混合條件、懸浮安定劑或界面活性劑等添加量及上述攪拌機的攪拌條件、分散條件。After polymerization, the particles can be separated into a water-containing filter cake by methods such as suction filtration, centrifugal dehydration, centrifugal separation, pressure dehydration, etc., and the obtained water-containing filter cake can be further washed and dried to obtain target particles. Here, the average particle diameter of the particles can be adjusted by adjusting the mixing conditions of the monomer mixture and water, the addition amount of suspension stabilizers or surfactants, and the stirring conditions and dispersion conditions of the aforementioned mixer.
[有機微粒子] 有機微粒子係具有對光學薄膜賦予貼附耐性之機能。構成有機微粒子之樹脂的實例包含：含有選自由(甲基)丙烯酸酯類、伊康酸二酯類、馬來酸二酯類、乙烯基酯類、烯烴類、苯乙烯類、(甲基)丙烯醯胺類、烯丙基化合物、乙烯基醚類、乙烯基酮類、乙烯基雜環化合物、不飽和腈類、不飽和單體類及不飽和羧酸類所成群組的1種以上所衍生之結構單元的聚合物、或聚矽氧系樹脂、氟系樹脂、聚苯硫醚等。此外，(甲基)丙烯酸係指丙烯酸或甲基丙烯酸。[Organic particles] The organic fine particles have the function of imparting adhesion resistance to the optical film. Examples of the resin constituting the organic fine particles include: containing selected from (meth)acrylates, itaconic acid diesters, maleic acid diesters, vinyl esters, olefins, styrenes, and (methyl) Acrylic amines, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, unsaturated nitriles, unsaturated monomers, and unsaturated carboxylic acids Derivative structural unit polymer, or silicone resin, fluorine resin, polyphenylene sulfide, etc. In addition, (meth)acrylic acid means acrylic acid or methacrylic acid.
構成聚合物之(甲基)丙烯酸酯類的實例包含(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、乙二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯等。伊康酸二酯類的實例包含伊康酸二甲酯、伊康酸二甲酯、伊康酸二丙酯等。馬來酸二酯類的實例包含馬來酸二甲酯、馬來酸二甲酯、馬來酸二丙酯等。乙烯基酯類的實例包含乙酸乙烯酯、丙酸乙烯酯、丁基乙烯酯、異丁酸乙烯酯、己酸乙烯酯、氯乙酸乙烯酯、甲氧基乙酸乙烯酯、乙酸乙烯基苯酯、苯甲酸乙烯酯、水楊酸乙烯酯等。烯烴類的實例包含二環戊二烯、乙烯、丙烯、1-丁烯、1-戊烯、氯乙烯、偏二氯乙烯、異戊二烯、氯丁二烯、丁二烯、2,3-二甲基丁二烯等。苯乙烯類的實例包含苯乙烯、甲基苯乙烯、二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、異丙基苯乙烯、氯甲基苯乙烯、甲氧基苯乙烯、乙醯氧基苯乙烯、氯苯乙烯、二氯苯乙烯、溴苯乙烯、三氟甲基苯乙烯、乙烯基苯甲酸甲基酯、二乙烯基苯等。(甲基)丙烯醯胺類的實例包含(甲基)丙烯醯胺、甲基(甲基)丙烯醯胺、乙基(甲基)丙烯醯胺、丙基(甲基)丙烯醯胺、丁基(甲基)丙烯醯胺、三級丁基(甲基)丙烯醯胺、苯基(甲基)丙烯醯胺、二甲基(甲基)丙烯醯胺、亞甲基雙丙烯醯胺等。烯丙基化合物的實例包含乙酸烯丙酯、己酸烯丙酯、月桂酸烯丙酯、苯甲酸烯丙酯等。乙烯基醚類的實例包含甲基乙烯基醚、丁基乙烯基醚、己基乙烯基醚、甲氧基乙基乙烯基醚、二甲胺基乙基乙烯基醚等。乙烯基酮類的實例包含甲基乙烯基酮、苯基乙烯基酮、甲氧基乙基乙烯基酮等。乙烯基雜環化合物的實例包含乙烯基吡啶、N-乙烯基咪唑、N-乙烯基噁唑啶酮、N-乙烯基***、N-乙烯基吡咯烷酮等。不飽和腈類的實例包含丙烯腈、甲基丙烯腈等。不飽和羧酸類的實例包含(甲基)丙烯酸、伊康酸、伊康酸單酯、馬來酸、馬來酸單酯等。Examples of (meth)acrylates constituting the polymer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, ethylene glycol two (Meth)acrylate, trimethylolpropane tri(meth)acrylate, etc. Examples of itaconic acid diesters include dimethyl itaconic acid, dimethyl itaconic acid, dipropyl itaconic acid, and the like. Examples of maleic acid diesters include dimethyl maleate, dimethyl maleate, dipropyl maleate, and the like. Examples of vinyl esters include vinyl acetate, vinyl propionate, butyl vinyl, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, methoxy vinyl acetate, vinyl phenyl acetate, Vinyl benzoate, vinyl salicylate, etc. Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3 -Dimethylbutadiene, etc. Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, ethylene Acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, trifluoromethylstyrene, methyl vinyl benzoate, divinylbenzene, etc. Examples of (meth)acrylamides include (meth)acrylamide, methyl(meth)acrylamide, ethyl(meth)acrylamide, propyl(meth)acrylamide, butyl Base (meth)acrylamide, tertiary butyl (meth)acrylamide, phenyl (meth)acrylamide, dimethyl (meth)acrylamide, methylene bisacrylamide, etc. . Examples of allyl compounds include allyl acetate, allyl hexanoate, allyl laurate, allyl benzoate, and the like. Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, and the like. Examples of vinyl ketones include methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, and the like. Examples of vinyl heterocyclic compounds include vinyl pyridine, N-vinylimidazole, N-vinyloxazolidinone, N-vinyltriazole, N-vinylpyrrolidone, and the like. Examples of unsaturated nitriles include acrylonitrile, methacrylonitrile, and the like. Examples of unsaturated carboxylic acids include (meth)acrylic acid, itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, and the like.
其中，較佳為含有選自由(甲基)丙烯酸酯類、乙烯基酯類、苯乙烯類、烯烴類所成群組的1種以上所衍生之結構單元的聚合物，更佳為含有(甲基)丙烯酸酯類所衍生之結構單元的聚合物、含有苯乙烯類所衍生之結構單元的聚合物、含有(甲基)丙烯酸酯類所衍生之結構單元與苯乙烯類所衍生之結構單元的共聚物，再更佳為含有(甲基)丙烯酸酯類所衍生之結構單元與苯乙烯類所衍生之結構單元的共聚物。Among them, it is preferably a polymer containing one or more structural units derived from the group consisting of (meth)acrylates, vinyl esters, styrenes, and olefins, and more preferably contains (former Yl)acrylic ester-derived structural unit polymer, styrene-derived structural unit polymer, (meth)acrylate-derived structural unit and styrene-derived structural unit The copolymer is more preferably a copolymer containing structural units derived from (meth)acrylates and structural units derived from styrenes.
由此種聚合物所構成的有機微粒子(聚合物粒子)可藉由任意方法，例如乳化聚合、懸浮聚合、分散聚合、種子聚合等方法來製造。其中，基於容易獲得粒徑一致的聚合物粒子之觀點等，較佳為在水性介質下的種子聚合或乳化聚合。Organic microparticles (polymer particles) composed of such polymers can be produced by any method, such as emulsion polymerization, suspension polymerization, dispersion polymerization, seed polymerization, and the like. Among them, from the viewpoint that it is easy to obtain polymer particles having uniform particle diameters, etc., seed polymerization or emulsion polymerization in an aqueous medium is preferred.
作為聚合物粒子之製造方法，可舉出例如： ・使單體混合物分散於水性介質中後進行聚合的1階段聚合法、 ・使單體在水性介質中聚合而得到種子粒後，使種子粒吸收單體混合物後進行聚合的2階段聚合法、 ・重複製造2階段聚合法之種子粒之步驟的多階段聚合法等。 此等聚合法可依據聚合物粒子所期望的平均粒徑適宜選擇。此外，供製造種子粒的單體不特別限定，聚合物粒子用之單體皆可使用。As a method of manufacturing polymer particles, for example: ・One-stage polymerization method in which the monomer mixture is dispersed in an aqueous medium and then polymerized, ・After the monomer is polymerized in an aqueous medium to obtain seed particles, the seed particles absorb the monomer mixture and then polymerize the two-stage polymerization method, ・Multi-stage polymerization method that repeats the steps of producing seed grains of the 2-stage polymerization method. These polymerization methods can be appropriately selected according to the desired average particle diameter of the polymer particles. In addition, the monomer for producing seed particles is not particularly limited, and any monomer for polymer particles can be used.
有機微粒子可為具有芯-殼構造之粒子。此種有機微粒子的實例包含：具有含有(甲基)丙烯酸酯之均聚物或共聚物之低Tg的芯層與高Tg的殼層的芯-殼粒子等。The organic microparticles may be particles having a core-shell structure. Examples of such organic microparticles include core-shell particles having a low Tg core layer and a high Tg shell layer containing a homopolymer or copolymer of (meth)acrylate.
有機微粒子與環烯烴系樹脂之折射率差的絕對值Δn，基於高度抑制光學薄膜的霧度上升之觀點，較佳為0.1以下，更佳為0.085以下，再更佳為0.065以下。The absolute value Δn of the refractive index difference between the organic fine particles and the cycloolefin resin is preferably 0.1 or less, more preferably 0.085 or less, and still more preferably 0.065 or less from the viewpoint of highly suppressing the increase in the haze of the optical film.
有機微粒子的平均一次粒徑較佳為50～300nm。有機微粒子的平均粒徑若為50nm以上，易對光學薄膜賦予充分的貼附耐性。有機微粒子的平均一次粒徑若為300nm以下，則容易抑制霧度的上升。The average primary particle diameter of the organic fine particles is preferably 50 to 300 nm. If the average particle diameter of the organic fine particles is 50 nm or more, it is easy to impart sufficient adhesion resistance to the optical film. If the average primary particle diameter of the organic fine particles is 300 nm or less, it is easy to suppress the increase in haze.
再者，藉由使有機微粒子成為小粒徑，可使有機微粒子之本發明之彈性模數增加。此理由尚不明確，但可如下推定。茲推測因粒子表面有表面張力作用，比起塊體會更堅硬地表現其作用；但推測因粒徑變小，粒子每單位體積的表面積的比例增大，其結果，本發明之彈性模數變高。惟，粒徑過小時，由於形成於薄膜表面之凹凸的高度會變小，推斷對貼附耐性的效果會變小。Furthermore, by making the organic microparticles have a small particle size, the elastic modulus of the organic microparticles of the present invention can be increased. The reason for this is not clear, but it can be presumed as follows. It is assumed that due to the surface tension of the particle surface, the effect will be harder than that of the block; however, it is assumed that due to the smaller particle size, the ratio of the surface area per unit volume of the particle increases. As a result, the elastic modulus of the present invention changes high. However, if the particle size is too small, the height of the unevenness formed on the film surface will decrease, and it is estimated that the effect on adhesion resistance will decrease.
平均一次粒徑能以由電子顯微鏡照片直接量測一次粒子的大小之方法求得。具體而言，能以穿透型電子顯微鏡照片(TEM)測定粒子影像，並將隨機地選出之100個一次粒子之等面積圓相當直徑的平均值作為平均一次粒徑。The average primary particle size can be obtained by directly measuring the size of the primary particles from electron micrographs. Specifically, the particle image can be measured with a transmission electron micrograph (TEM), and the average value of the equivalent area circle diameter of 100 randomly selected primary particles can be used as the average primary particle size.
有機微粒子的含量，相對於光學薄膜的總質量較佳為0.03～1.0質量%，更佳為0.05～0.6質量%，再更佳為0.08～0.4質量%。有機微粒子的含量若為0.03質量%以上，易對光學薄膜賦予充分的貼附耐性；若為1.0質量%以下，則容易抑制霧度的上升。The content of the organic fine particles is preferably 0.03 to 1.0% by mass relative to the total mass of the optical film, more preferably 0.05 to 0.6% by mass, and still more preferably 0.08 to 0.4% by mass. If the content of organic fine particles is 0.03% by mass or more, it is easy to impart sufficient adhesion resistance to the optical film; if it is 1.0% by mass or less, it is easy to suppress the increase in haze.
[交聯劑] 作為控制本發明之樹脂及有機微粒子的彈性模數之方法，可使上述之環烯烴系樹脂(甲基)丙烯酸系樹脂或有機微粒子含有交聯劑。交聯劑可使用能與上述樹脂交聯的周知之交聯劑。 可適宜使用例如EGDMA(乙二醇二甲基丙烯酸酯)、DVB(二乙烯基苯)、TMPTA(三羥甲基丙烷三丙烯酸酯)、PETA(季戊四醇三丙烯酸酯)、TAIC(三聚異氰酸三烯丙酯)、PETTA(季戊四醇四丙烯酸酯)、DPPA(二季戊四醇五丙烯酸酯)及DPHA(二季戊四醇六丙烯酸酯)等多官能單體等。[Crosslinking agent] As a method of controlling the elastic modulus of the resin and organic fine particles of the present invention, the above-mentioned cycloolefin resin (meth)acrylic resin or organic fine particles may contain a crosslinking agent. As the crosslinking agent, a well-known crosslinking agent capable of crosslinking with the above-mentioned resin can be used. For example, EGDMA (ethylene glycol dimethacrylate), DVB (divinylbenzene), TMPTA (trimethylolpropane triacrylate), PETA (pentaerythritol triacrylate), TAIC (trimeric isocyanate) can be suitably used. Triallyl acid), PETTA (pentaerythritol tetraacrylate), DPPA (dipentaerythritol pentaacrylate) and DPHA (dipentaerythritol hexaacrylate) and other multifunctional monomers.
[其他成分] 本發明之光學薄膜，在不損及本發明之效果的範圍內，亦可視需求進一步包含其他成分。其他成分的實例分別包含周知之高沸點溶劑、界面活性劑、紫外線吸收劑或抗氧化劑等。 光學薄膜能以1層(單層)構成或以多層構成。[Other ingredients] The optical film of the present invention may further contain other components as required within the range that does not impair the effects of the present invention. Examples of other components include well-known high-boiling solvents, surfactants, ultraviolet absorbers, or antioxidants. The optical film can be composed of one layer (single layer) or multiple layers.
[物性] 茲就本發明之彈性模數以外的其他物性加以敘述。 (內部霧度) 本發明之光學薄膜的內部霧度，依以下方法測定時，較佳為0.08%以下。 ＜內部霧度的測定方法＞ 在23℃・55%RH的環境下調濕5小時以上後，根據下述方法評定光學薄膜的內部霧度。圖2為顯示內部霧度之測定程序的圖。[Properties] The physical properties other than the modulus of elasticity of the present invention are described here. (Internal Haze) The internal haze of the optical film of the present invention is preferably 0.08% or less when measured by the following method. ＜Measuring method of internal haze＞ After adjusting the humidity for more than 5 hours in an environment of 23°C and 55%RH, the internal haze of the optical film was evaluated according to the following method. Figure 2 is a diagram showing the procedure for measuring internal haze.
1) 首先，依以下程序測定薄膜以外之測定器具的空白霧度1。在洗淨之載玻片11上滴下一滴(0.05mL)甘油12。此時，勿使氣泡進入液滴中。於其上載置蓋玻片。即使未按壓蓋玻片，甘油12仍會擴展。將其裝設於霧度計上，測定空白霧度1。
2) 其次，依以下程序測定包含試料的霧度2。首先，於載玻片11上滴下甘油12(0.05mL)(參照圖2(a))。於其上以勿使氣泡進入的方式載置待測試料薄膜13(參照圖2(b))。於試料薄膜13上滴下甘油12(0.05mL)(參照圖2(c))。於其上載置載玻片(參照圖2(d))。將所得層合體(自上方起為載玻片/甘油/試料薄膜/甘油/載玻片)裝設於霧度計上，測定霧度2。
3) 將上述1)中所得之霧度1與上述2)中所得之霧度2帶入下述式，算出內部霧度。
薄膜的內部霧度=霧度2-霧度11) First, use the following procedure to measure the
(相位差Ro及Rt) 當光學薄膜作為例如VA模式用之相位差薄膜使用時，在測定波長550nm、23℃、55%RH的環境下所測得之面內方向的相位差Ro較佳為20～120nm，更佳為30～100nm。光學薄膜的厚度方向的相位差Rt較佳為70～350nm，更佳為100～320nm。(Phase difference Ro and Rt) When the optical film is used as a retardation film for VA mode, for example, the retardation Ro in the in-plane direction measured in an environment with a measurement wavelength of 550nm, 23°C, and 55%RH is preferably 20-120nm, more preferably 30～100nm. The retardation Rt in the thickness direction of the optical film is preferably 70 to 350 nm, more preferably 100 to 320 nm.
光學薄膜的Ro及Rt係分別以下述式定義。 式(2a)：Ro=(nx -ny )×d 式(2b)：Rt=((nx +ny )/2-nz )×d (式中， nx 表示光學薄膜的面內慢軸方向(折射率達最大之方向)的折射率，ny 表示與光學薄膜的面內慢軸正交之方向的折射率， nz 表示光學薄膜的厚度方向的折射率， d表示光學薄膜的厚度(nm))。The Ro and Rt systems of the optical film are defined by the following formulas, respectively. Formula (2a): Ro=(n x -n y )×d Formula (2b): Rt=((n x +n y )/2-n z )×d (where n x represents the surface of the optical film The refractive index in the direction of the internal slow axis (the direction in which the refractive index reaches the maximum), n y represents the refractive index in the direction orthogonal to the in-plane slow axis of the optical film, n z represents the refractive index in the thickness direction of the optical film, and d represents the optical film. The thickness of the film (nm)).
光學薄膜的面內慢軸係指薄膜面上折射率最大的軸。光學薄膜的面內慢軸可藉由自動雙折射率計Axo Scan Mueller Matrix Polarimeter(Axo Matrix公司製)來確認。The in-plane slow axis of the optical film refers to the axis with the largest refractive index on the film surface. The in-plane slow axis of the optical film can be confirmed with the automatic birefringence meter Axo Scan Mueller Matrix Polarimeter (manufactured by Axo Matrix).
光學薄膜的Ro及Rt的測定可根據以下方法來進行。 1) 將光學薄膜在23℃、55%RH的環境下進行調濕24小時。此光學薄膜的平均折射率係以阿貝折射計測定，厚度d係使用市售測微計來測定。 2) 分別使用自動雙折射率計Axo Scan Mueller Matrix Polarimeter(Axo Matrix公司製)，在23℃、55%RH的環境下測定調濕後之光學薄膜在測定波長550nm下的遲滯值Ro及Rt。The measurement of Ro and Rt of the optical film can be performed according to the following method. 1) The optical film is humidified for 24 hours in an environment of 23°C and 55% RH. The average refractive index of this optical film was measured with an Abbe refractometer, and the thickness d was measured with a commercially available micrometer. 2) Using the automatic birefringence meter Axo Scan Mueller Matrix Polarimeter (manufactured by Axo Matrix), respectively, the hysteresis values Ro and Rt of the optical film after humidity control at a measurement wavelength of 550 nm were measured under an environment of 23°C and 55% RH.
光學薄膜的相位差Ro及Rt主要可根據拉伸倍率來調整。為提高光學薄膜的相位差Ro及Rt，較佳提高拉伸倍率。The phase difference Ro and Rt of the optical film can be adjusted mainly according to the stretching magnification. In order to increase the retardation Ro and Rt of the optical film, it is preferable to increase the stretching ratio.
(厚度) 光學薄膜的厚度可採例如5～100μm，較佳為5～40μm。(thickness) The thickness of the optical film can be, for example, 5-100 μm, preferably 5-40 μm.
《光學薄膜之製造方法》 本發明之光學薄膜較佳以溶液製膜法(澆鑄法)所製成。 亦即，本發明之光學薄膜可經由以下步驟來製造：1)製得至少包含前述之環烯烴系樹脂及(甲基)丙烯酸系樹脂的至少一者、有機微粒子與視需求而定之交聯劑、包含高沸點溶劑之溶劑的膠漿之步驟；2)將所得膠漿流延於金屬支持體上，予以乾燥及剝離而得到膜狀物之步驟；及3)將所得膜狀物朝彼此正交的2方向進行拉伸之步驟。"Manufacturing Method of Optical Film" The optical film of the present invention is preferably produced by a solution film method (casting method). That is, the optical film of the present invention can be manufactured through the following steps: 1) Prepare at least one of the aforementioned cycloolefin resin and (meth)acrylic resin, organic microparticles, and crosslinking agent as required , The step of the dope containing the solvent of the high boiling point solvent; 2) the step of casting the obtained dope on the metal support, drying and peeling to obtain the film; and 3) the step of making the obtained film facing each other The step of stretching in the two directions of the intersection.
關於1)之步驟 使環烯烴系樹脂及(甲基)丙烯酸系樹脂的至少一者、有機微粒子與視需求而定之交聯劑溶解於溶劑中來調製膠漿。膠漿所使用之溶劑係至少包含可溶解上述樹脂的有機溶劑(良溶劑)。About the steps of 1) At least one of cycloolefin resin and (meth)acrylic resin, organic fine particles, and optionally a crosslinking agent are dissolved in a solvent to prepare a dope. The solvent used in the dope contains at least an organic solvent (good solvent) that can dissolve the above-mentioned resin.
良溶劑的實例包含二氯甲烷等氯系有機溶劑；乙酸甲酯、乙酸乙酯、丙酮、四氫呋喃等非氯系有機溶劑。其中，較佳為二氯甲烷。Examples of good solvents include chlorine-based organic solvents such as dichloromethane; and non-chlorine-based organic solvents such as methyl acetate, ethyl acetate, acetone, and tetrahydrofuran. Among them, dichloromethane is preferred.
膠漿所使用之溶劑亦可進一步包含不良溶劑。不良溶劑的實例包含碳原子數1～4之直鏈或支鏈狀的脂肪族醇。若提高膠漿中之醇的比率，則膜狀物容易凝膠化而更容易由金屬支持體剝離。碳原子數1～4之直鏈或支鏈狀的脂肪族醇可舉出甲醇、乙醇、正丙醇、異丙醇、正丁醇、二級丁醇、三級丁醇。此等當中，由膠漿的穩定性、沸點亦較低且乾燥性佳等而言較佳為乙醇。The solvent used in the glue may further include a poor solvent. Examples of poor solvents include linear or branched aliphatic alcohols having 1 to 4 carbon atoms. If the ratio of alcohol in the dope is increased, the film will easily gel and be more easily peeled off from the metal support. The linear or branched aliphatic alcohols having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, isopropanol, n-butanol, secondary butanol, and tertiary butanol. Among these, ethanol is preferable in terms of the stability, boiling point, and dryness of the cement paste.
又，有機微粒子的添加方法不特別限制，可將有機微粒子直接添加於溶劑中，亦可調製有機微粒子之集合體後再添加於溶劑中。尤其是當有機微粒子為前述聚合物粒子時，可將聚合物粒子之集合體添加於溶劑中。聚合物粒子之集合體可藉由使包含聚合物粒子、界面活性劑、無機粉末與水性介質的漿液進行噴霧乾燥，而得到聚合物粒子之集合體。聚合物粒子之集合體的調製可根據日本特開2010-138365號公報所記載之方法來進行。聚合物粒子之集合體係由彼此之連結(熔合)經抑制的多個聚合物粒子所構成。因此，操作處理性優良，若使集合體分散於環烯烴系樹脂或溶劑中，則容易地分離成聚合物粒子，而能夠使聚合物粒子的分散性更良好。In addition, the method of adding the organic fine particles is not particularly limited. The organic fine particles may be directly added to the solvent, or an aggregate of organic fine particles may be prepared and then added to the solvent. Especially when the organic fine particles are the aforementioned polymer particles, an aggregate of polymer particles can be added to the solvent. The aggregate of polymer particles can be obtained by spray-drying a slurry containing polymer particles, a surfactant, an inorganic powder, and an aqueous medium. The assembly of polymer particles can be prepared according to the method described in JP 2010-138365 A. The aggregate system of polymer particles is composed of a plurality of polymer particles whose connection (fusion) with each other is inhibited. Therefore, handling properties are excellent, and if the aggregate is dispersed in a cycloolefin-based resin or a solvent, it is easily separated into polymer particles, and the dispersibility of the polymer particles can be made more favorable.
關於2)之步驟 將所得膠漿流延於金屬支持體上。膠漿的流延的可由流延模中排出來進行。About the steps of 2) The obtained glue is cast on a metal support. The casting of the dope can be carried out by discharging it from the casting die.
其次，使流延於金屬支持體上之膠漿中的溶劑蒸發而使其乾燥。將經乾燥之膠漿由金屬支持體剝離，而得到膜狀物。由金屬支持體剝離時之膠漿的殘留溶劑量(剝離時的殘留溶劑量)，基於更容易降低所得光學薄膜的相位差Ro或Rt之觀點，較佳為10～150質量%，更佳為20～40質量%。剝離時的殘留溶劑量若為10質量%以上，於乾燥或拉伸時環烯烴系樹脂容易流動而容易成為無配向，因此容易降低所得光學薄膜的Ro或Rt。剝離時的殘留溶劑量若為150質量%以下，則剝離膠漿時所需的力不易過大，而容易抑制膠漿的破裂。Secondly, the solvent in the glue cast on the metal support is evaporated to dry it. The dried glue is peeled from the metal support to obtain a film. The amount of residual solvent of the dope when peeling from the metal support (the amount of residual solvent during peeling) is preferably 10 to 150% by mass, more preferably from the viewpoint of making it easier to reduce the retardation Ro or Rt of the resulting optical film 20-40% by mass. If the amount of residual solvent during peeling is 10% by mass or more, the cycloolefin-based resin easily flows during drying or stretching, and is likely to become non-aligned, and therefore it is easy to reduce Ro or Rt of the resulting optical film. If the amount of residual solvent during peeling is 150% by mass or less, the force required for peeling the dope will not easily become too large, and it will be easy to suppress cracking of the dope.
膠漿的殘留溶劑量係依下述式定義。以下亦同。 膠漿的殘留溶劑量(質量%)=(膠漿的加熱處理前質量-膠漿的加熱處理後質量)/膠漿的加熱處理後質量×100 此外，測定殘留溶劑量時的加熱處理係指120℃、60分鐘的加熱處理。The amount of residual solvent in the dope is defined by the following formula. The same goes for the following. The amount of residual solvent of the glue (mass%) = (the mass of the glue before the heat treatment-the mass of the glue after the heat treatment) / the mass of the glue after the heat treatment × 100 In addition, the heat treatment at the time of measuring the amount of residual solvent refers to a heat treatment at 120°C for 60 minutes.
關於3)之步驟 將所得膜狀物朝至少彼此正交的二方向進行拉伸(雙軸拉伸)。拉伸方向較佳為膜狀物的寬度方向(TD方向)及與其正交的運送方向(MD方向)。About the steps of 3) The resulting film is stretched in at least two directions orthogonal to each other (biaxial stretching). The stretching direction is preferably the width direction (TD direction) of the film and the conveying direction (MD direction) orthogonal to it.
就拉伸倍率，較佳使TD方向的拉伸倍率/MD方向的拉伸倍率為例如1.0～3.0。TD方向與MD方向的拉伸倍率，基於例如使光學薄膜發揮作為VA用之相位差薄膜的機能之觀點，可各自定為1.01～3.5倍；基於例如發揮作為IPS用之相位差薄膜的機能之觀點，可各自定為1.01～1.3倍。拉伸倍率愈高，所得光學薄膜的殘留應力易愈大。拉伸倍率係定義為(拉伸後之薄膜的拉伸方向大小)/ (拉伸前之薄膜的拉伸方向大小)。Regarding the stretching ratio, the stretching ratio in the TD direction/the stretching ratio in the MD direction is preferably 1.0 to 3.0, for example. The stretching magnifications in the TD direction and the MD direction can be set to 1.01 to 3.5 times, respectively, based on, for example, the optical film functioning as a retardation film for VA; for example, it is based on the function of a retardation film for IPS. Viewpoints can be set at 1.01 to 1.3 times each. The higher the stretching ratio, the greater the residual stress of the obtained optical film. The stretch magnification is defined as (the size of the film in the stretch direction after stretching)/(the size of the film in the stretch direction before stretching).
此外，光學薄膜的面內慢軸方向(於面內折射率達最大之方向)通常為拉伸倍率達最大之方向，係與光學薄膜的收縮率達最大之第1方向一致。In addition, the in-plane slow axis direction of the optical film (the direction in which the in-plane refractive index reaches the maximum) is usually the direction in which the stretch magnification reaches the maximum, which coincides with the first direction in which the shrinkage rate of the optical film reaches the maximum.
將所用樹脂的玻璃轉移溫度設為Tg時，拉伸溫度較佳為(Tg-65)℃～(Tg+60)℃，更佳為(Tg-50)℃～(Tg+50)℃，再更佳為(Tg-30)℃～(Tg+50)℃。拉伸溫度若為(Tg-30)℃以上，不僅容易使膜狀物成為適於拉伸的柔軟度，且因拉伸時對膜狀物所施加的張力不會過大，過度的殘留應力不易殘留於所得之光學薄膜，且Ro或Rt亦不易過度增大。拉伸溫度若為(Tg+60)℃以下，則適度的殘留應力易殘留於拉伸後的光學薄膜，且容易高度抑制膜狀物中溶劑的氣化所致之氣泡的產生。具體而言，拉伸溫度可採100～220℃。When the glass transition temperature of the resin used is Tg, the stretching temperature is preferably (Tg-65)℃～(Tg+60)℃, more preferably (Tg-50)℃～(Tg+50)℃, and then More preferably, it is (Tg-30)°C to (Tg+50)°C. If the stretching temperature is (Tg-30)°C or higher, not only is it easy to make the film suitable for stretching, but also because the tension applied to the film during stretching will not be too large, excessive residual stress is not easy It remains in the obtained optical film, and Ro or Rt is not easy to increase excessively. If the stretching temperature is (Tg+60)°C or lower, moderate residual stress is likely to remain in the stretched optical film, and it is easy to highly suppress the generation of bubbles due to the vaporization of the solvent in the film. Specifically, the stretching temperature can be 100 to 220°C.
拉伸開始時之膜狀物中的殘留溶劑量較佳為2～50質量%。拉伸開始時之殘留溶劑量若為2質量%以上，因殘留溶劑所產生的塑化效果，使拉伸時之膜狀物的實質Tg降低，而使得光學薄膜的Ro或Rt不易增大。拉伸開始時之殘留溶劑量若為50質量%以下，則可高度抑制膜狀物中溶劑的氣化所致之氣泡的產生。The amount of residual solvent in the film at the start of stretching is preferably 2 to 50% by mass. If the amount of residual solvent at the beginning of stretching is 2% by mass or more, the plasticizing effect produced by the residual solvent will reduce the substantial Tg of the film during stretching, making it difficult for the Ro or Rt of the optical film to increase. If the amount of residual solvent at the start of stretching is 50% by mass or less, the generation of bubbles due to the vaporization of the solvent in the film can be highly suppressed.
膜狀物之MD方向的拉伸能以例如使多個輥產生周速差，並於此期間利用輥周速差的方法(輥法)來進行。膜狀物之TD方向的拉伸能以例如將膜狀物的兩端以夾具或針銷固定，並將夾具或針銷的間隔朝行進方向擴大的方法(拉幅機法)來進行。The stretching of the film in the MD direction can be performed by, for example, a method (roll method) in which a difference in circumferential speed is generated between a plurality of rolls, and the difference in the circumferential speed of the rolls is used in the meantime. Stretching in the TD direction of the film can be performed by, for example, fixing both ends of the film with clamps or pins, and expanding the interval between the clamps or pins in the traveling direction (tenter method).
[偏光板] 本發明之偏光板係包含偏光件與本發明之光學薄膜。本發明之光學薄膜較佳配置於偏光件的至少其中一面(至少與液晶胞相對向的面)。偏光件與光學薄膜係經由接著劑層接著而成。[Polarizer] The polarizing plate of the present invention includes a polarizer and the optical film of the present invention. The optical film of the present invention is preferably arranged on at least one surface of the polarizer (at least the surface opposite to the liquid crystal cell). The polarizer and the optical film are formed by bonding through an adhesive layer.
(偏光件) 偏光件係僅使一定方向之偏波面的光通過的元件，為聚乙烯醇系偏光薄膜。聚乙烯醇系偏光薄膜有使聚乙烯醇系薄膜經碘染色者與經雙色性染料染色者。(Polarized parts) The polarizer is an element that only passes light on the polarization plane in a certain direction, and is a polyvinyl alcohol-based polarizing film. Polyvinyl alcohol-based polarizing films include those dyed with iodine and those dyed with dichroic dyes.
聚乙烯醇系偏光薄膜可為對聚乙烯醇系薄膜實施單軸拉伸後，以碘或雙色性染料染色的薄膜(較佳為進一步以硼化合物實施耐久性處理之薄膜)；亦可為將聚乙烯醇系薄膜以碘或雙色性染料染色後，經單軸拉伸的薄膜(較佳為進一步以硼化合物實施耐久性處理之薄膜)。偏光件的吸收軸通常與最大拉伸方向平行。The polyvinyl alcohol-based polarizing film may be a polyvinyl alcohol-based film that is uniaxially stretched and then dyed with iodine or a two-color dye (preferably a film that is further treated with a boron compound for durability); The polyvinyl alcohol-based film is uniaxially stretched after being dyed with iodine or a dichroic dye (preferably a film further subjected to durability treatment with a boron compound). The absorption axis of the polarizer is generally parallel to the maximum stretching direction.
可使用例如日本特開2003-248123號公報、日本特開2003-342322號公報等所記載之乙烯單元的含量1～4莫耳%、聚合度2000～4000、皂化度99.0～99.99莫耳%的乙烯改性聚乙烯醇。 偏光件的厚度較佳為5～30μm，由為了將偏光板薄型化等而言，更佳為5～20μm。For example, ethylene unit content of 1-4 mol%, polymerization degree of 2000-4000, and saponification degree of 99.0-99.99 mol% described in JP 2003-248123 A and JP 2003-342322 A can be used. Ethylene modified polyvinyl alcohol. The thickness of the polarizer is preferably 5 to 30 μm, and more preferably 5 to 20 μm for the purpose of reducing the thickness of the polarizing plate or the like.
(其他光學薄膜) 當本發明之光學薄膜僅配置於偏光件的其中一面時，於偏光件的另一面可配置其他光學薄膜。其他光學薄膜的實例包含市售纖維素酯薄膜(例如Konica Minolta TAC KC8UX、KC5UX、KC4UX、KC8UCR3、KC4SR、KC4BR、KC4CR、KC4DR、KC4FR、KC4KR、KC8UY、KC6UY、KC4UY、KC4UE、KC8UE、KC8UY-HA、KC2UA、KC4UA、KC6UAKC、2UAH、KC4UAH、KC6UAH，以上為Konica Minolta (股)製；Fujitac T40UZ、Fujitac T60UZ、Fujitac T80UZ、Fujitac TD80UL、Fujitac TD60UL、Fujitac TD40UL、Fujitac R02、Fujitac R06，以上為FUJIFILM(股)製)等。(Other optical films) When the optical film of the present invention is only disposed on one side of the polarizer, other optical films can be disposed on the other side of the polarizer. Examples of other optical films include commercially available cellulose ester films (e.g. Konica Minolta TAC KC8UX, KC5UX, KC4UX, KC8UCR3, KC4SR, KC4BR, KC4CR, KC4DR, KC4FR, KC4KR, KC8UY, KC6UY, KC4C8UY, KC8UE, KC4UE, KC4 , KC2UA, KC4UA, KC6UAKC, 2UAH, KC4UAH, KC6UAH, the above are made by Konica Minolta (stock); Fujitac T40UZ, Fujitac T60UZ, Fujitac T80UZ, Fujitac TD80UL, Fujitac TD60UL, Fujitac FUt60UL40, Fuji FUtac R06 Stock) system) and so on.
其他保護薄膜的厚度不特別限定，較佳為10～100μm，更佳為10～60μm，特佳為20～60μm。The thickness of other protective films is not particularly limited, but is preferably 10 to 100 μm, more preferably 10 to 60 μm, and particularly preferably 20 to 60 μm.
(偏光板之製造方法) 本發明之偏光板可經由接著劑將偏光件與本發明之光學薄膜貼合而得。接著劑可為完全皂化型聚乙烯醇水溶液(水糊)或活性能量線硬化性接著劑。(Method of manufacturing polarizing plate) The polarizing plate of the present invention can be obtained by bonding the polarizer and the optical film of the present invention through an adhesive. The adhesive may be a fully saponified polyvinyl alcohol aqueous solution (water paste) or an active energy ray curable adhesive.
其中，由即使為薄膜強度亦高，而容易獲得平面性優良的偏光板而言，本發明之光學薄膜與偏光件較佳藉由活性能量線硬化性接著劑貼合而成。Among them, since it is easy to obtain a polarizing plate with high film strength and excellent flatness, the optical film of the present invention and the polarizer are preferably formed by bonding an active energy ray curable adhesive.
活性能量線硬化性接著劑可為利用光自由基聚合之光自由基聚合型組成物、利用光陽離子聚合之光陽離子聚合型組成物，以及併用光自由基聚合及光陽離子聚合之混合型組成物的任一種。The active energy ray curable adhesive can be a photo-radical polymerization type composition using photo-radical polymerization, a photo-cation polymerization type composition using photo-cation polymerization, and a mixed type composition using both photo-radical polymerization and photo-cation polymerization. Of any kind.
作為光自由基聚合型組成物，已知有以特定比例包含日本特開2008-009329號公報所記載之含有羥基或羧基等極性基之自由基聚合性化合物及不含極性基之自由基聚合性化合物的組成物等。尤其是，自由基聚合性化合物較佳為具有可進行自由基聚合之乙烯性不飽和鍵的化合物。具有可進行自由基聚合之乙烯性不飽和鍵的化合物的較佳實例包含具有(甲基)丙烯醯基之化合物。具有(甲基)丙烯醯基之化合物的實例包含N取代(甲基)丙烯醯胺系化合物、(甲基)丙烯酸酯系化合物等。(甲基)丙烯醯胺係指丙烯醯胺或甲基丙烯醯胺。As a photo-radical polymerizable composition, a radical polymerizable compound containing a polar group such as a hydroxyl group or a carboxyl group and a radical polymerizable compound containing no polar group described in JP 2008-009329 A, and a radical polymerizable compound containing no polar group are known in a specific ratio. The composition of the compound, etc. In particular, the radical polymerizable compound is preferably a compound having an ethylenically unsaturated bond capable of radical polymerization. Preferred examples of the compound having an ethylenically unsaturated bond capable of radical polymerization include a compound having a (meth)acryloyl group. Examples of the compound having a (meth)acryloyl group include N-substituted (meth)acrylamide-based compounds, (meth)acrylate-based compounds, and the like. (Meth)acrylamide refers to acrylamide or methacrylamide.
光陽離子聚合型組成物可舉出如日本特開2011-028234號公報所揭示之包含(α)陽離子聚合性化合物、(β)光陽離子聚合起始劑、(γ)於波長長於380nm的光顯示極大吸收的光敏化劑及(δ)萘系光敏化助劑之各成分的組成物。The photocationically polymerizable composition may include (α) a cationically polymerizable compound, (β) a photocationic polymerization initiator, and (γ) a light display with a wavelength longer than 380 nm as disclosed in Japanese Patent Application Publication No. 2011-028234 It is a composition of each component of a photosensitizer with great absorption and (δ) naphthalene-based photosensitizer auxiliary.
使用活性能量線硬化性接著劑的偏光板之製造方法係包含：1)對偏光件與光學薄膜的接著面中至少一者塗布活性能量線硬化性接著劑之步驟；2)經由所得接著劑層貼合偏光件與光學薄膜之步驟；3)在經由接著劑層貼合偏光件與光學薄膜的狀態下照射活性能量線，使接著劑層硬化而得到偏光板之步驟；及4)將所得偏光板衝切(切斷)成既定形狀之步驟。於步驟1)前，亦可視需求實施4)對光學薄膜之接著偏光件的面進行易接著處理(電暈處理或電漿處理等)之步驟。The manufacturing method of a polarizing plate using an active energy ray curable adhesive includes: 1) applying an active energy ray curable adhesive to at least one of the adhesive surfaces of the polarizer and the optical film; 2) through the resulting adhesive layer The step of bonding the polarizer and the optical film; 3) the step of irradiating active energy rays in the state where the polarizing member and the optical film are bonded via the adhesive layer to harden the adhesive layer to obtain a polarizing plate; and 4) the resulting polarized light The step of punching (cutting) the board into a predetermined shape. Before step 1), if necessary, 4) the step of easy bonding treatment (corona treatment or plasma treatment, etc.) is carried out on the surface of the polarizing member of the optical film.
於步驟1)中，活性能量線硬化性接著劑的塗布係以使硬化後之接著劑層的厚度成為例如0.01～10μm，較佳為0.5～5μm的方式進行為佳。In step 1), the application of the active energy ray curable adhesive is preferably performed so that the thickness of the adhesive layer after curing becomes, for example, 0.01 to 10 μm, preferably 0.5 to 5 μm.
於步驟3)中，照射之活性能量線可使用可見光、紫外線、X射線及電子束等。由容易操作處理且硬化速度亦充分而言，一般較佳使用紫外線。紫外線的照射條件只要是可將接著劑硬化的條件即可。例如，紫外線的照射量以累計光量計較佳為50～1500mJ/cm2 ，更佳為100～500mJ/cm2 。In step 3), visible light, ultraviolet rays, X-rays, electron beams, etc. can be used as the active energy rays to be irradiated. In terms of easy handling and sufficient curing speed, it is generally preferable to use ultraviolet rays. The irradiation conditions of ultraviolet rays should just be the conditions which can harden the adhesive agent. For example, the irradiation amount of ultraviolet rays is preferably 50 to 1500 mJ/cm 2 , and more preferably 100 to 500 mJ/cm 2 in terms of cumulative light amount.
[液晶顯示裝置] 本發明之液晶顯示裝置係包含液晶胞、配置於液晶胞的其中一面的第1偏光板與配置於液晶胞的另一面的第2偏光板。第1及第2偏光板中的一者或兩者為本發明之偏光板。[Liquid crystal display device] The liquid crystal display device of the present invention includes a liquid crystal cell, a first polarizing plate arranged on one side of the liquid crystal cell, and a second polarizing plate arranged on the other side of the liquid crystal cell. One or both of the first and second polarizing plates are the polarizing plates of the present invention.
圖3為顯示液晶顯示裝置之基本構成的一例的示意圖。如圖3所示，本發明之液晶顯示裝置10係包含液晶胞30、配置於液晶胞30的其中一面的第1偏光板50、配置於液晶胞30的另一面的第2偏光板70與背光90。FIG. 3 is a schematic diagram showing an example of the basic structure of a liquid crystal display device. As shown in FIG. 3, the liquid
液晶胞30的顯示模式可為例如STN、TN、OCB、HAN、VA(MVA、PVA)、IPS、OCB等。其中，較佳為VA(MVA、PVA)模式及IPS模式。The display mode of the
第1偏光板50係包含配置於液晶胞30的其中一面(目視側的面)的第1偏光件51、配置於第1偏光件51之與液晶胞30相反之一側的面(目視測的面)的保護薄膜53(F1)與配置於第1偏光件51之液晶胞30側的面的保護薄膜55(F2)。The first
第2偏光板70係包含配置於液晶胞30的另一面(背光90側的面)的第2偏光件71、配置於第2偏光件71之液晶胞30側的面的保護薄膜73(F3)與配置於第2偏光件71之與液晶胞30相反之一側的面(背光90側的面)的保護薄膜75(F4)。The second
第1偏光件51的吸收軸與第2偏光件71的吸收軸較佳成正交(成正交尼科耳)。The absorption axis of the
保護薄膜53(F1)、55(F2)、73(F3)及75(F4)之至少一者可採本發明之光學薄膜。其中，本發明之光學薄膜較佳使用於作為保護薄膜55(F2)或73(F3)。保護薄膜55(F2)或73(F3)包含本發明之光學薄膜的液晶顯示裝置具有良好的正面對比，且亦可減少顯示不均。 [實施例]At least one of the protective films 53 (F1), 55 (F2), 73 (F3) and 75 (F4) can be the optical film of the present invention. Among them, the optical film of the present invention is preferably used as a protective film 55 (F2) or 73 (F3). The liquid crystal display device containing the protective film 55 (F2) or 73 (F3) of the optical film of the present invention has good front contrast and can also reduce display unevenness. [Example]
以下舉出實施例具體地說明本發明，惟本發明非限定於此等。此外，實施例中係使用「份」或「%」之標示，除非特別敘明，否則表示「質量份」或「質量%」。Examples are given below to specifically illustrate the present invention, but the present invention is not limited to these. In addition, in the examples, the indication of "parts" or "%" is used, unless otherwise specified, it means "parts by mass" or "% by mass".
[實施例1]
《光學薄膜1的製作》
[有機微粒子1的製作]
對安裝有溫度計、回流冷卻器、氮氣導入管、攪拌器的玻璃製反應器加入去離子水200質量份及月桂基硫酸鈉(SLS)0.6質量份，邊通入氮氣邊加熱至80～85℃，且邊攪拌邊將過硫酸銨0.8質量份添加於所得水溶液中。[Example 1]
"Production of
對所得水溶液進一步以1小時滴加苯乙烯(St)10質量份、甲基丙烯酸甲酯(MMA)50質量份、二乙烯基苯(DVB)20質量份，接著將所得混合液攪拌1小時而得到乳膠。藉由噴霧乾燥將所得乳膠乾燥，而得到有機微粒子1。To the obtained aqueous solution, 10 parts by mass of styrene (St), 50 parts by mass of methyl methacrylate (MMA), and 20 parts by mass of divinylbenzene (DVB) were further added dropwise over 1 hour, and then the resulting mixed liquid was stirred for 1 hour. Get latex. The obtained latex was dried by spray drying to obtain organic
[微粒子分散液1的調製]
將3質量份的有機微粒子1與97質量份的二氯甲烷以直立式攪拌機攪拌混合50分鐘後，使用MILDER分散機(大平洋機工股份有限公司製)於1500rpm條件下予以分散，而得到微粒子分散液1。[Preparation of Fine Particle Dispersion Liquid 1]
3 parts by mass of organic
[膠漿1的調製]
其次，調製下述組成之膠漿1。首先，在加壓溶解槽中添加二氯甲烷及乙醇。接著，邊攪拌邊對加壓溶解槽投入環烯烴系樹脂I。接著投入上述調製之微粒子分散液1，將其加熱至60℃，邊攪拌邊使其完全溶解。加熱溫度係由室溫以5℃/min升溫，以30分鐘溶解後，以3℃/min降溫。[Preparation of glue 1]
Next, a
使用ROKI TECHNO(股)製SHP150將其以過濾流量300L/m2
・h、過濾壓力1.0×106
Pa過濾，而得到膠漿1。Using SHP150 manufactured by ROKI TECHNO (stock), it was filtered at a filtration flow rate of 300 L/m 2 ·h and a filtration pressure of 1.0×10 6 Pa to obtain a
(膠漿1的組成)
在不鏽鋼帶支持體上，使溶劑蒸發至流延(澆鑄)之薄膜中的殘留溶劑量成為30%。其次，以剝離張力128N/m由不鏽鋼帶支持體上剝離。一邊將剝離之薄膜以多個滾筒運送，一邊將所得膜狀物以拉幅機在150℃(Tg-15℃)之條件下朝寬度方向拉伸1.2倍。其後，一邊用輥運送一邊進一步使其乾燥，將以拉幅機夾具夾住的端部用雷射切割機縱切並予以捲繞，而得到厚度40μm的光學薄膜1。On the stainless steel belt support, the solvent evaporates to 30% of the residual solvent in the cast (cast) film. Next, it was peeled from the stainless steel belt support with a peeling tension of 128 N/m. While conveying the peeled film with a plurality of rollers, the obtained film was stretched 1.2 times in the width direction under the conditions of 150°C (Tg-15°C) with a tenter. After that, it was further dried while being transported by a roller, and the end portion clamped by the tenter clamp was slit with a laser cutter and wound to obtain an
《光學薄膜2～12的製作》
在光學薄膜1的製作時，如表I所示變更樹脂的種類、微粒子及層構成進行製作，以與光學薄膜1同樣的方式製成光學薄膜2～12。此外，有機微粒子的平均一次粒徑的大小，係使用在由MMA-St所構成之有機微粒子的調製時，藉由控制界面活性劑SLS的添加量，而調製成表中所示平均一次粒徑的大小的微粒子分散液。
在光學薄膜12的製作中，係使用替代微粒子分散液而添加等量之二氯甲烷的膠漿12。"Production of Optical Film 2-12"
In the production of the
進而，光學薄膜7係採用由含有有機微粒子的層與不含有機微粒子的層所構成的層合薄膜。於光學薄膜7的製造時，係使用不含有機微粒子的膠漿12、及以下述條件所調製之含有有機微粒子的膠漿12’。於製膜步驟中，自流延口流延膠漿12，及於其兩側流延膠漿12’，同時流延3層。至共流延後的剝離～拉伸～捲繞為止係採用與其他實施例相同的條件。由此，製成在薄膜的兩表面分別具有乾膜厚4μm之含有機微粒子層的光學薄膜7。
又，在光學薄膜10中，二氧化矽係使用與膠漿1所含微粒子固含量相同質量的二氧化矽。Furthermore, the optical film 7 is a laminated film composed of a layer containing organic fine particles and a layer not containing organic fine particles. In the production of the optical film 7, a
(膠漿12’的調製)
對350質量份的膠漿12添加50質量份之用於光學薄膜2的微粒子分散液所調製而成。
此外，表中，微粒子一欄之[]內的數值係表示用於微粒子的製作之材料的質量份。
又，表I所示縮寫如下。(Preparation of glue 12')
It is prepared by adding 50 parts by mass of the fine particle dispersion liquid for the
(樹脂) COP：環烯烴系樹脂I(ARTON-G7810(JSR公司製，重量平均分子量=140000))(通式(A-2)表示之單體與其他單體的共聚物(前述(5)之聚合物)) 丙烯酸樹脂：Dianal BR85(Mw=280000)(Mitsubishi Chemical股份有限公司製)(丙烯酸樹脂中分子之(甲基)丙烯酸系單體的比例：90質量%以上)(Resin) COP: Cycloolefin resin I (ARTON-G7810 (manufactured by JSR, weight average molecular weight = 140000)) (copolymer of monomer represented by general formula (A-2) and other monomers (polymer of (5) above) )) Acrylic resin: Dianal BR85 (Mw=280000) (manufactured by Mitsubishi Chemical Co., Ltd.) (the ratio of the (meth)acrylic monomer in the molecule of the acrylic resin: 90% by mass or more)
(微粒子) MMA：甲基丙烯酸甲酯(東京化成工業股份有限公司製，純度99.8%以上) St：苯乙烯(東京化成工業股份有限公司製，純度99%以上) DVB：二乙烯基苯(m-、p-混合物，FUJIFILM Wako Pure Chemical股份有限公司製，純度93%) EGDMA：乙二醇二甲基丙烯酸酯(東京化成工業股份有限公司製，純度97.0%%以上) 二氧化矽：AEROSIL R812(Japan Aerosil股份有限公司製)(Fine particles) MMA: Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., purity 99.8% or more) St: Styrene (manufactured by Tokyo Chemical Industry Co., Ltd., purity 99% or more) DVB: Divinylbenzene (m-, p-mixture, manufactured by FUJIFILM Wako Pure Chemical Co., Ltd., purity 93%) EGDMA: Ethylene glycol dimethacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., purity 97.0%% or more) Silicon dioxide: AEROSIL R812 (manufactured by Japan Aerosil Co., Ltd.)
《評定》 [平均一次粒徑的測定] 平均一次粒徑係以由電子顯微鏡照片直接量測一次粒子的大小的方法求得。具體而言，係以穿透型電子顯微鏡照片(TEM)(Hitachi High-Technologies公司製H-7650)測定粒子影像，並將隨機地選出之100個一次粒子之等面積圓相當直徑的平均值作為平均一次粒徑。"assessment" [Measurement of average primary particle size] The average primary particle size is obtained by directly measuring the size of primary particles from electron micrographs. Specifically, the particle image was measured with a transmission electron micrograph (TEM) (H-7650 manufactured by Hitachi High-Technologies), and the average diameter of the equal area circle of 100 randomly selected primary particles was taken as Average primary particle size.
[彈性模數的測定] 以前述方法進行測定，將不含有機微粒子之樹脂部分的平均彈性模數設為E1、將有機微粒子部分的平均彈性模數設為E2時，算出兩者的比值(E2/E1)。[Determination of Elastic Modulus] Measured by the aforementioned method, and when the average elastic modulus of the resin portion not containing organic fine particles is set to E1, and the average elastic modulus of the organic fine particle portion is set to E2, the ratio (E2/E1) of the two is calculated.
[內部霧度的測定] 將所得光學薄膜在23℃、55%RH的環境下進行調濕5小時以上後，以前述方法求出內部霧度。依以下評定基準來判定。以△以上為合格。 ◎：0.02%以下 ○：超過0.02%且為0.05%以下 △：超過0.05%且為0.08%以下 ×：超過0.08%[Determination of internal haze] After the obtained optical film was subjected to humidity control in an environment of 23° C. and 55% RH for 5 hours or more, the internal haze was determined by the aforementioned method. It is judged according to the following evaluation criteria. △ or above is considered qualified. ◎: 0.02% or less ○: More than 0.02% and less than 0.05% △: more than 0.05% and less than 0.08% ×: more than 0.08%
[貼附耐性的評定] 將光學薄膜切成既定的大小，得到2片薄膜。在溫度25℃、相對濕度55%的環境下，使其中一片薄膜的其中一面(A面)與另一片薄膜的另一面(B面)接觸，並以6MPa施加負載30分鐘。其後，除去負載，藉由影像解析軟體(WinROOF2018，三谷商事股份有限公司製)測定貼附部分的面積相對於施加負載部分之總面積的比率(貼附面積率)，依以下評定基準來判定。以△以上為合格。[Assessment of adhesion tolerance] Cut the optical film into a predetermined size to obtain 2 films. In an environment with a temperature of 25°C and a relative humidity of 55%, one side (side A) of one of the films was brought into contact with the other side (side B) of the other film, and a load of 6 MPa was applied for 30 minutes. After that, the load is removed, and the ratio of the area of the attached part to the total area of the load-applied part (attached area ratio) is measured by the image analysis software (WinROOF2018, manufactured by Mitani Corporation), and judged based on the following evaluation criteria . △ or above is considered qualified.
◎：貼附面積為10%以下 ○：貼附面積超過10%且為20%以下 △：貼附面積超過20%且為40%以下 ×：貼附面積超過40% 將以上結果示於表I。 此外，表中顯示為無法測定之處係薄膜製造時的運送性極差而無法捲繞、或於捲繞後因薄膜彼此顯著的黏住，無法採取適於評定的薄膜片而無法測定。◎: The attached area is less than 10% ○: The attached area exceeds 10% and is less than 20% △: The attached area exceeds 20% and is less than 40% ×: The attachment area exceeds 40% The above results are shown in Table 1. In addition, the points indicated in the table that the measurement cannot be performed are because the transportability of the film during production is extremely poor and cannot be wound, or the film cannot be measured due to the remarkable adhesion of the films after winding, and the film sheet suitable for evaluation cannot be taken.
由表I可知，本發明之光學薄膜其貼附耐性與透明性(內部霧度)優異。It can be seen from Table I that the optical film of the present invention has excellent adhesion resistance and transparency (internal haze).
[實施例2] 3. 偏光板的製造 ＜偏光件的製作＞ 使厚度70μm的聚乙烯醇薄膜以35℃的水膨潤。將所得薄膜浸漬於由碘0.075g、碘化鉀5g及水100g所構成的水溶液中60秒，並進一步浸漬於由碘化鉀3g、硼酸7.5g及水100g所構成的45℃之水溶液中。將所得薄膜以拉伸溫度55℃、拉伸倍率5倍之條件進行單軸拉伸。將此單軸拉伸薄膜進行水洗後加以乾燥，而得到厚度20μm的偏光件。[Example 2] 3. Manufacture of polarizing plate ＜Production of Polarizing Parts＞ The polyvinyl alcohol film having a thickness of 70 μm was swelled with water at 35°C. The obtained film was immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide, and 100 g of water for 60 seconds, and was further immersed in an aqueous solution composed of 3 g of potassium iodide, 7.5 g of boric acid, and 100 g of water at 45°C. The obtained film was uniaxially stretched under the conditions of a stretching temperature of 55°C and a stretching ratio of 5 times. This uniaxially stretched film was washed with water and then dried to obtain a polarizer having a thickness of 20 μm.
＜偏光板101的製作＞ (活性能量線硬化性接著劑的調製) 將下述各成分混合後，進行脫泡而調製成活性能量線硬化性接著劑。此外，三芳基鋶六氟磷酸鹽係以50%碳酸伸丙酯溶液摻混，下述表示三芳基鋶六氟磷酸鹽的固含量。＜Production of polarizing plate 101＞ (Preparation of active energy ray curable adhesive) After mixing the components described below, defoaming is performed to prepare an active energy ray curable adhesive. In addition, the triarylsulfonium hexafluorophosphate is blended with a 50% propylene carbonate solution, and the solid content of the triarylsulfonium hexafluorophosphate is shown below.
準備上述製作之光學薄膜1，對其表面實施電暈放電處理。此外，電暈放電處理之條件係採電暈輸出強度2.0kW、線速度18m/分。其次，對光學薄膜之電暈放電處理面，將上述活性能量線硬化性接著劑，以棒式塗布器塗布成硬化後的膜厚為約3μm。對所得接著劑層貼合上述製作之偏光件的其中一面。The
另一方面，其他光學薄膜係準備纖維素三乙酸酯薄膜(KC4UA，Konica Minolta(股)製、膜厚40μm)，以與前述同樣的方式對其表面實施電暈處理。其次，對KC4UA之電暈放電處理面，將上述活性能量線硬化性接著劑，以棒式塗布器塗布成硬化後的膜厚為約3μm。對所得接著層貼合上述製作之附光學薄膜1之偏光件的另一面，而得到層合物。On the other hand, for other optical film systems, a cellulose triacetate film (KC4UA, manufactured by Konica Minolta Co., Ltd.,
其次，自貼合之層合物的兩面側，利用附帶式輸送機之紫外線照射裝置(燈係使用Fusion UV Systems公司製D燈泡)，以累計光量成為750mJ/cm2 的方式照射紫外線，使接著劑層硬化而製成偏光板101。Secondly, from both sides of the laminated laminate, use the UV irradiation device with conveyor (the lamp is D bulb made by Fusion UV Systems) to irradiate the UV light so that the cumulative amount of light becomes 750mJ/cm 2 to make the adhesion The agent layer is cured to form the polarizing plate 101.
＜偏光板102～112的製作＞
除將光學薄膜1變更為光學薄膜2～12以外係以與偏光板101同樣的方式製作偏光板102～112。＜Production of polarizing plate 102～112＞
The polarizing plates 102 to 112 were produced in the same manner as the polarizing plate 101 except that the
液晶顯示裝置的製作
＜液晶顯示裝置201的製作＞
為評定上述製作之偏光板的特性，而分別剝除黏貼於VA模式之SONY製40型液晶顯示器(BRAVIA X1)之液晶胞之觀察者側的面(前面)與光源側的面(背面)的偏光板。然後，分別將上述製作之偏光板101，使用丙烯酸系透明黏著劑貼合於所得液晶胞之光源側的面(背面)與觀察側的面(前面)而製成液晶顯示裝置201。偏光板的貼合係以貼合後之偏光板的穿透軸與原本貼合之偏光板的穿透軸一致的方式來進行。偏光板的黏貼係以使本發明之光學薄膜與液晶胞相接的方式(成為F2或F3的方式)來進行。Manufacture of liquid crystal display device
<Production of liquid crystal display device 201>
In order to evaluate the characteristics of the polarizer produced above, the observer side (front) and the light source side (back) of the liquid crystal cell of
＜液晶顯示裝置202～212的製作＞ 除將偏光板101變更為偏光板102～112以外係以與液晶顯示裝置201同樣的方式製作液晶顯示裝置202～212。<Production of liquid crystal display devices 202-212> The liquid crystal display devices 202 to 212 were produced in the same manner as the liquid crystal display device 201 except that the polarizing plate 101 was changed to the polarizing plates 102 to 112.
依以下方法評定所得液晶顯示裝置201～212之顯示影像的對比。在23℃、55%RH的環境下，使用ELDIM公司製EZ-Contrast160D，以液晶顯示裝置中的白顯示與黑顯示進行顯示畫面，依目視評定正面對比。The contrast of the displayed images of the obtained liquid crystal display devices 201 to 212 was evaluated according to the following methods. In an environment of 23°C and 55% RH, EZ-Contrast160D manufactured by ELDIM was used to display the screen with white display and black display in the liquid crystal display device, and the front contrast was evaluated visually.
其結果確認，使用本發明之光學薄膜的液晶顯示裝置201～209，與比較之液晶顯示裝置210～211相比，可顯示良好對比的影像。As a result, it was confirmed that the liquid crystal display devices 201 to 209 using the optical film of the present invention can display images with good contrast compared with the comparative liquid crystal display devices 210 to 211.
1:彈性模數曲線 2:不含有機微粒子之樹脂部分的彈性模數曲線 3:有機微粒子部分的彈性模數曲線 4:有機微粒子部分的彈性模數曲線的最大值 11:載玻片 12:甘油 13:試料薄膜 10:液晶顯示裝置 30:液晶胞 50:第1偏光板 51:第1偏光件 53:保護薄膜(F1) 55:保護薄膜(F2) 70:第2偏光板 71:第2偏光件 73:保護薄膜(F3) 75:保護薄膜(F4) 90:背光1: Elastic modulus curve 2: The elastic modulus curve of the resin part without organic particles 3: The elastic modulus curve of the organic microparticle part 4: The maximum value of the elastic modulus curve of the organic fine particles 11: glass slide 12: Glycerin 13: Sample film 10: Liquid crystal display device 30: liquid crystal cell 50: The first polarizer 51: The first polarizer 53: Protective film (F1) 55: Protective film (F2) 70: 2nd polarizing plate 71: The second polarizer 73: Protective film (F3) 75: Protective film (F4) 90: Backlight
[圖1]為根據具備懸臂之原子力顯微鏡之彈性模數的測定例 [圖2]為顯示內部霧度之測定程序的圖 [圖3]為顯示液晶顯示裝置之基本構成的一例的示意圖[Figure 1] An example of the measurement of the elastic modulus based on an atomic force microscope with a cantilever [Figure 2] A diagram showing the measurement procedure of the internal haze [FIG. 3] A schematic diagram showing an example of the basic structure of a liquid crystal display device
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