TW202210881A - Optical film, polarizing plate and method for manufacturing optical film in which a phase difference variation in a humidification reliability test is suppressed and a hue variation in the weathering test in the ultraviolet region is suppressed - Google Patents

Abstract

An object of the present invention is to provide an optical film and a polarizing plate including the optical film. The optical film has suppressed a phase difference variation in a humidification reliability test and a hue variation in the weathering test in the ultraviolet region, and has excellent adhesive property. The solution of the present invention is to use an optical film composed of a resin having a birefringence in a predetermined range and an orientation degree of 5% or more.

Description

光學薄膜、偏光板及光學薄膜之製造方法Optical film, polarizing plate and manufacturing method of optical film

本發明涉及光學薄膜、偏光板即光學薄膜之製造方法。The present invention relates to a manufacturing method of an optical film and a polarizing plate, that is, an optical film.

近年之顯示器市場中，為了延長電池之耐久時間、進而抑制發熱，而存在降低顯示器亮度之需求。因此，對於顯示器所用之偏光板，尋求光透射率高之偏光板。但是，將所述光透射率高之偏光板用於顯示器時，有在加濕條件下外觀變差之問題。In the display market in recent years, in order to prolong the battery life and suppress heat generation, there is a need to reduce the brightness of the display. Therefore, for polarizing plates used in displays, polarizing plates with high light transmittance are sought. However, when the above-mentioned polarizing plate with high light transmittance is used for a display, there is a problem that the appearance is deteriorated under humidified conditions.

並且，近年來顯示器在暴露於紫外線之環境中使用之情況增多(例如PID(公共資訊顯示器)、行動電話)，尤其對於光學薄膜配置於面板側之偏光板而言，有紫外光造成光學薄膜之色相變化，損害顯示器品質之問題。 先前技術文獻 專利文獻In addition, in recent years, the use of displays in environments exposed to ultraviolet rays has increased (such as PID (Public Information Display), mobile phones), especially for polarizers with optical films disposed on the panel side, ultraviolet light may cause the optical film to deteriorate. Hue changes, damage to the quality of the display. prior art literature Patent Literature

專利文獻1：日本專利第3325560號公報Patent Document 1: Japanese Patent No. 3325560

本發明係為了解決上述以往課題而做成者，其目的在於提供光學薄膜及包含該光學薄膜之偏光板，該光學薄膜已抑制住在加濕條件下之相位差變化，且已抑制住在紫外區之耐候性試驗中之色相變化，並且接著性優異。The present invention has been made in order to solve the above-mentioned conventional problems, and an object thereof is to provide an optical film and a polarizing plate including the optical film which suppress the retardation change under humidified conditions and suppress the ultraviolet Hue change in zone weather resistance test, and excellent adhesion.

用以解決課題之手段 本發明實施形態之光學薄膜係由雙折射Δnxy為0.015以上之樹脂構成，其定向度為5%以上，面內相位差Re(550)為20nm以下，在65℃及90%RH下保持500小時後之相位差變化率為10%以下，在紫外區之耐候性試驗中之b值的變化率為1%以下。 在一實施形態中，上述樹脂包含聚碳酸酯系樹脂。 在一實施形態中，上述聚碳酸酯系樹脂包含源自下述式(4)所示二羥基化合物之結構單元。 [化學式1]

在一實施形態中，上述聚碳酸酯系樹脂更包含源自脂環式二羥基化合物之結構單元，該脂環式二羥基化合物係以下述通式(II)表示，R¹ 為下述(IIb)所示結構，n=0。 HOCH₂ -R¹ -CH₂ OH   (II) [化學式2]

在一實施形態中，上述光學薄膜之厚度為10μm~50μm。 本發明另一實施形態係提供一種偏光板。該偏光板包含偏光件與透過接著劑層貼合於該偏光件之至少單面的上述光學薄膜。 根據本發明另一面向，提供上述光學薄膜之製造方法。該製造方法包含產線速度為7m/分鐘~15m/分鐘之製膜步驟。MEANS TO SOLVE THE PROBLEM The optical film of the embodiment of the present invention is composed of a resin having a birefringence Δnxy of 0.015 or more, an orientation degree of 5% or more, and an in-plane retardation Re(550) of 20 nm or less. The retardation change rate after holding at %RH for 500 hours is 10% or less, and the change rate of b value in the weather resistance test in the ultraviolet region is 1% or less. In one Embodiment, the said resin contains a polycarbonate-type resin. In one Embodiment, the said polycarbonate-type resin contains the structural unit derived from the dihydroxy compound represented by following formula (4). [Chemical formula 1]

In one embodiment, the above-mentioned polycarbonate resin further includes a structural unit derived from an alicyclic dihydroxy compound, and the alicyclic dihydroxy compound is represented by the following general formula (II), and R ¹ is the following (IIb ) shown in the structure, n=0. HOCH ₂ -R ¹ -CH ₂ OH (II) [Chemical formula 2]

In one embodiment, the thickness of the optical film is 10 μm to 50 μm. Another embodiment of the present invention provides a polarizing plate. The polarizer includes a polarizer and the above-mentioned optical film attached to at least one side of the polarizer through the adhesive layer. According to another aspect of the present invention, there is provided a method for manufacturing the above-mentioned optical film. The manufacturing method includes a film forming step with a production line speed of 7m/min to 15m/min.

發明效果 根據本發明實施形態，藉由將由特定樹脂構成且雙折射Δnxy為0.015以上之樹脂薄膜在特定條件下製膜，定向度會達一定值以上，結果可實現一種光學薄膜，其已抑制住加濕可靠性試驗中之相位差變化，已抑制住紫外區之耐候性試驗中之色相變化，並且接著性優異。Invention effect According to the embodiment of the present invention, by forming a resin film composed of a specific resin and having a birefringence Δnxy of 0.015 or more under specific conditions, the degree of orientation can reach a certain value or more, and as a result, an optical film that has suppressed humidification can be realized. The phase difference change in the reliability test has been suppressed from the hue change in the weather resistance test in the ultraviolet region, and the adhesion is excellent.

以下，針對本發明實施形態進行說明，但本發明不限定於該等實施形態。Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

(用語及符號之定義) 本說明書中之用語及符號之定義如下。 (1)折射率(nx、ny、nz) 「nx」係面內折射率達最大時之方向(即慢軸方向)之折射率，「ny」係在面內與慢軸正交之方向(即快軸方向)之折射率，「nz」係厚度方向之折射率。 (2)面內相位差(Re) 「Re(λ)」係在23℃下利用波長λnm之光測定之面內相位差。例如，「Re(550)」係在23℃下利用波長550nm之光測定之面內相位差。將層(薄膜)之厚度設為d(nm)時，Re(λ)可藉由式：Re(λ)=(nx-ny)×d求算。 (3)雙折射(Δnxy) 雙折射Δnxy可藉由式：Δnxy=nx-ny求算。(Definition of Terms and Symbols) Definitions of terms and symbols in this specification are as follows. (1) Refractive index (nx, ny, nz) "nx" is the refractive index in the direction of the maximum in-plane refractive index (ie, the slow axis direction), "ny" is the refractive index in the in-plane direction orthogonal to the slow axis (ie, the fast axis direction), "nz" is the refractive index in the thickness direction. (2) In-plane phase difference (Re) "Re(λ)" is the in-plane retardation measured at 23°C with light having a wavelength of λnm. For example, "Re(550)" is an in-plane retardation measured at 23°C with light having a wavelength of 550 nm. When the thickness of the layer (thin film) is set as d (nm), Re(λ) can be calculated by the formula: Re(λ)=(nx-ny)×d. (3) Birefringence (Δnxy) The birefringence Δnxy can be calculated by the formula: Δnxy=nx-ny.

A.光學薄膜 本發明實施形態之光學薄膜係由樹脂形成。為該樹脂代表上可舉聚碳酸酯樹脂。因此，本發明實施形態之光學薄膜代表上為聚碳酸酯樹脂薄膜。並且，本發明實施形態之光學薄膜宜不含紫外線吸收劑。藉由光學薄膜不含紫外線吸收劑，可在應用於影像顯示裝置時維持中性色相。A. Optical film The optical film of the embodiment of the present invention is formed of resin. A polycarbonate resin is exemplified as the resin. Therefore, the optical film of the embodiment of the present invention is typically a polycarbonate resin film. Furthermore, the optical film of the embodiment of the present invention preferably does not contain an ultraviolet absorber. Since the optical film does not contain UV absorbers, it can maintain a neutral hue when applied to image display devices.

構成上述光學薄膜之樹脂之雙折射Δnxy代表性上為0.015以上，宜為0.018以上。上述樹脂之雙折射Δnxy之上限例如可為0.040。藉由將由具有所述雙折射Δnxy之樹脂構成的樹脂薄膜以預定速度以上之產線速度進行製膜，定向度會達一定值以上，結果能在加濕條件下顯著抑制相位差變化。The birefringence Δnxy of the resin constituting the above-mentioned optical film is typically 0.015 or more, preferably 0.018 or more. The upper limit of the birefringence Δnxy of the resin may be, for example, 0.040. By forming a resin film composed of a resin having the birefringence Δnxy at a line speed equal to or higher than a predetermined speed, the degree of orientation reaches a certain value or more, and as a result, the change in retardation can be significantly suppressed under humidified conditions.

上述光學薄膜之定向度為5%以上，宜為5.5%以上，較宜為6%以上。定向度之上限例如為70%。光學薄膜之定向度若在所述範圍內，光學薄膜之接著性會變良好。所述範圍之定向度可藉由將上述樹脂薄膜以預定範圍之產線速度進行製膜而實現。上述定向度係藉由例如X射線繞射法(XRD)測定。The degree of orientation of the above-mentioned optical film is 5% or more, preferably 5.5% or more, and more preferably 6% or more. The upper limit of the degree of orientation is, for example, 70%. When the degree of orientation of the optical film is within the above-mentioned range, the adhesiveness of the optical film becomes favorable. The degree of orientation in the above range can be achieved by forming the above-mentioned resin film at a line speed in a predetermined range. The above-mentioned degree of orientation is measured by, for example, X-ray diffraction (XRD).

上述光學薄膜之面內相位差Re(550)為20nm以下，宜為15nm以下，較宜為10nm以下。面內相位差之下限例如可為0nm。即，上述光學薄膜宜實質上具有光學各向同性。光學薄膜之所述面內相位差Re(550)可藉由將上述樹脂薄膜以預定範圍之產線速度進行製膜而得。The in-plane retardation Re(550) of the optical film is 20 nm or less, preferably 15 nm or less, more preferably 10 nm or less. The lower limit of the in-plane retardation may be, for example, 0 nm. That is, the above-mentioned optical film preferably has substantially optical isotropy. The in-plane retardation Re(550) of the optical film can be obtained by film-forming the above-mentioned resin film at a line speed within a predetermined range.

上述光學薄膜在溫度65℃且濕度90%之條件下保存500小時(加濕試驗)後之相位差變化宜為10%以下，較宜為8%以下。下限例如可為0.01%。上述相位差變化(%)係以｜(Re₅₀₀ -Re₀ )/Re₀ ｜×100(%)表示。Re₀ 為試驗開始前之光學薄膜之面內相位差(nm)，Re₅₀₀ 為試驗後之光學薄膜之面內相位差(nm)。光學薄膜之相位差變化若在所述範圍內，在將光學薄膜應用於影像顯示裝置時可獲得如下優點：影像顯示裝置上各處之相位差造成之色相變化變小，從而抑制顯示上之顏色不均發生。The change in retardation of the optical film after being stored at a temperature of 65°C and a humidity of 90% for 500 hours (humidification test) is preferably 10% or less, more preferably 8% or less. The lower limit may be, for example, 0.01%. The above phase difference change (%) is represented by |(Re ₅₀₀ -Re ₀ )/Re ₀ |×100 (%). Re ₀ is the in-plane retardation (nm) of the optical film before the test starts, and Re ₅₀₀ is the in-plane retardation (nm) of the optical film after the test. If the phase difference change of the optical film is within the above range, the following advantages can be obtained when the optical film is applied to an image display device: the hue change caused by the phase difference in various places on the image display device becomes smaller, thereby suppressing the color on the display Uneven occurs.

上述光學薄膜在紫外區之耐候性試驗中已抑制b值之變化。b值之變化率為1%以下，宜為0.95%以下。b值之變化率之下限例如為0%。即，光學薄膜亦可良好地用於要求耐候性之用途上。光學薄膜藉由包含後述特定聚碳酸酯樹脂，可獲得所述優點。The above-mentioned optical film has suppressed the change of b value in the weather resistance test in the ultraviolet region. The rate of change of the b value is less than 1%, preferably less than 0.95%. The lower limit of the rate of change of the b value is, for example, 0%. That is, the optical film can also be favorably used for applications requiring weather resistance. The advantage can be obtained by including the specific polycarbonate resin described later in the optical film.

上述光學薄膜之厚度宜為10μm~50μm，較宜為20μm~40μm。The thickness of the above-mentioned optical film is preferably 10 μm to 50 μm, more preferably 20 μm to 40 μm.

上述光學薄膜之透濕度宜為250g/m² ・24h以下，較宜為150g/m² ・24h以下。下限例如可為1g/m² ・24h。光學薄膜之透濕度若在所述範圍內，便可獲得可抑制在加濕環境下之相位差變化之優點。The moisture permeability of the above-mentioned optical film is preferably 250g/m ² ·24h or less, more preferably 150g/m ² ·24h or less. The lower limit may be, for example, 1 g/m ² ·24h. When the water vapor transmission rate of the optical film is within the above-mentioned range, the advantage of suppressing the phase difference change in a humidified environment can be obtained.

上述光學薄膜之光彈性係數之絕對值宜為2×10^-11 m² /N以下，較宜為2.0×10^-13 m² /N~1.5×10^-11 m² /N，更宜為1.0×10-¹² m² /N~1.2×10^-11 m² /N。光彈性係數之絕對值若在所述範圍內，於加熱時產生了收縮應力時便不易發生相位差變化。結果，將光學薄膜用於影像顯示裝置時，可良好地防止影像顯示裝置之熱不均。The absolute value of the photoelastic coefficient of the above-mentioned optical film is preferably 2×10 ^-11 m ² /N or less, preferably 2.0×10 ^-13 m ² /N~1.5×10 ^-11 m ² /N, more preferably 1.0 × ^10-12 m ² /N~1.2×10 ^-11 m ² /N. If the absolute value of the photoelastic coefficient is within the above-mentioned range, the phase difference is unlikely to change when shrinkage stress is generated during heating. As a result, when the optical film is used for an image display device, thermal unevenness of the image display device can be well prevented.

根據本發明實施形態，如上述藉由使用具有特定範圍之雙折射Δnxy之樹脂，以預定範圍內之產線速度進行製膜，可獲得具有特定範圍之定向度之光學薄膜。該光學薄膜滿足所期望之面內相位差(實質上為光學各向同性)，並且兼顧抑制在加濕可靠性試驗中之相位差變化、抑制在紫外區之耐候性試驗中之色相變化及良好之接著性。According to an embodiment of the present invention, as described above, by using a resin having a birefringence Δnxy in a specific range and forming a film at a line speed within a predetermined range, an optical film having an orientation degree in a specific range can be obtained. The optical film satisfies the desired in-plane retardation (substantially optically isotropic), suppresses the retardation change in the humidification reliability test, suppresses the hue change in the ultraviolet region weather resistance test, and is good the continuity.

藉由將上述樹脂薄膜以預定速度以下之產線速度進行製膜，可獲得實質上具有光學各向同性之光學薄膜。但產線速度若在一定速度以下，所得光學薄膜之定向度會下降，導致在加濕可靠性試驗中之相位差變化及接著性降低。因此，藉由將上述產線速度設為一定速度以上，光學薄膜之定向度會提高，從而可抑制在加濕可靠性試驗中之相位差變化，進而接著性會提高。即，藉由將上述產線速度之範圍最佳化，可兼顧所期望之面內相位差、抑制在加濕可靠性試驗中之相位差變化及優異接著性。所述光學薄膜可適宜用於例如PID(公眾資訊顯示器)、行動電話。An optical film having substantially optical isotropy can be obtained by film-forming the above-mentioned resin film at a line speed below a predetermined speed. However, if the production line speed is below a certain speed, the orientation of the resulting optical film will decrease, resulting in a change in retardation and a decrease in adhesion in the humidification reliability test. Therefore, by setting the above-mentioned production line speed to be equal to or higher than a certain speed, the orientation degree of the optical film can be improved, the retardation change in the humidification reliability test can be suppressed, and the adhesiveness can be improved. That is, by optimizing the range of the above-mentioned line speed, the desired in-plane retardation, the suppression of the retardation change in the humidification reliability test, and the excellent adhesiveness can be achieved at the same time. The optical film can be suitably used, for example, for PID (Public Information Display), mobile phones.

B.構成材料 上述光學薄膜如上述代表上為包含聚碳酸酯樹脂之樹脂薄膜。B. Constituent materials The above-mentioned optical film is a resin film containing a polycarbonate resin as above-mentioned representatively.

(聚碳酸酯樹脂) 本發明聚碳酸酯樹脂係至少包含源自具有下述結構式(1)所示鍵結結構之二羥基化合物之結構單元者，其係藉由使二羥基化合物與碳酸二酯在聚合觸媒之存在下進行反應來製造，前述二羥基化合物係至少包含分子內具有至少一個鍵結結構-CH₂ -O-之二羥基化合物。 [化學式3]

(Polycarbonate resin) The polycarbonate resin of the present invention contains at least a structural unit derived from a dihydroxy compound having a bonding structure represented by the following structural formula (1), which is obtained by combining the dihydroxy compound with carbonic acid. The ester is produced by reacting in the presence of a polymerization catalyst, and the dihydroxy compound at least contains a dihydroxy compound having at least one bonding structure -CH ₂ -O- in the molecule. [Chemical formula 3]

此處，具有結構式(1)所示鍵結結構之二羥基化合物若為具有2個醇性羥基、且包含分子內具有連結基-CH₂ -O-之結構、並且可在聚合觸媒之存在下與碳酸二酯進行反應而生成之化合物，則可使用任意結構之化合物，亦可併用複數種。又，本發明聚碳酸酯樹脂中使用之二羥基化合物，亦可併用不具有結構式(1)所示鍵結結構之二羥基化合物。以下，有時將具有結構式(1)所示鍵結結構之二羥基化合物簡稱為二羥基化合物(A)，將不具有結構式(1)所示鍵結結構之二羥基化合物簡稱為二羥基化合物(B)。Here, if the dihydroxy compound having the bonding structure represented by the structural formula (1) has two alcoholic hydroxyl groups, and includes a structure having a linking group -CH ₂ -O- in the molecule, and can be used in the polymerization catalyst As the compound produced by reacting with the carbonic acid diester in the presence of a compound having an arbitrary structure, a plurality of compounds may be used in combination. Moreover, the dihydroxy compound used for the polycarbonate resin of this invention may use together the dihydroxy compound which does not have the bonding structure represented by structural formula (1). Hereinafter, the dihydroxy compound having the bonding structure represented by the structural formula (1) may be abbreviated as dihydroxy compound (A), and the dihydroxy compound not having the bonding structure represented by the structural formula (1) may be abbreviated as dihydroxy compound. Compound (B).

(二羥基化合物(A)) 二羥基化合物(A)中之「連結基-CH₂ -O-」係指與氫原子以外之原子相互鍵結而構成分子之結構。在該連結基中，至少可與氧原子鍵結之原子或可同時與碳原子與氧原子鍵結之原子以碳原子最佳。二羥基化合物(A)中之「連結基-CH₂ -O-」之數量宜為1個以上，較宜為2~4個。(Dihydroxy compound (A)) The "linking group -CH ₂ -O-" in the dihydroxy compound (A) means a structure in which an atom other than a hydrogen atom is bonded to each other to constitute a molecule. Among the linking groups, at least an atom that can be bonded to an oxygen atom or an atom that can be bonded to both a carbon atom and an oxygen atom is preferably a carbon atom. The number of "linking groups -CH ₂ -O-" in the dihydroxy compound (A) is preferably 1 or more, more preferably 2 to 4.

更具體言之，二羥基化合物(A)可列舉例如：9,9-雙(4-(2-羥基乙氧基)苯基)茀、9,9-雙(4-(2-羥基乙氧基)-3-甲基苯基)茀、9,9-雙(4-(2-羥基乙氧基)-3-異丙基苯基)茀、9,9-雙(4-(2-羥基乙氧基)-3-異丁基苯基)茀、9,9-雙(4-(2-羥基乙氧基)-3-三級丁基苯基)茀、9,9-雙(4-(2-羥基乙氧基)-3-環己基苯基)茀、9,9-雙(4-(2-羥基乙氧基)-3-苯基苯基)茀、9,9-雙(4-(2-羥基乙氧基)-3,5-二甲基苯基)茀、9,9-雙(4-(2-羥基乙氧基)-3-三級丁基-6-甲基苯基)茀、9,9-雙(4-(3-羥基-2,2-二甲基丙氧基)苯基)茀所例示之側鏈具有芳香族基且於主鏈具有鍵結於芳香族基之醚基之化合物；雙[4-(2-羥基乙氧基)苯基]甲烷、雙[4-(2-羥基乙氧基)苯基]二苯甲烷、1,1-雙[4-(2-羥基乙氧基)苯基]乙烷、1,1-雙[4-(2-羥基乙氧基)苯基]-1-苯基乙烷、2,2-雙[4-(2-羥基乙氧基)苯基]丙烷、2,2-雙[4-(2-羥基乙氧基)-3-甲基苯基]丙烷、2,2-雙[3,5-二甲基-4-(2-羥基乙氧基)苯基]丙烷、1,1-雙[4-(2-羥基乙氧基)苯基]-3,3,5-三甲基環己烷、1,1-雙[4-(2-羥基乙氧基)苯基]環己烷、1,4-雙[4-(2-羥基乙氧基)苯基]環己烷、1,3-雙[4-(2-羥基乙氧基)苯基]環己烷、2,2-雙[4-(2-羥基乙氧基)-3-苯基苯基]丙烷、2,2-雙[(2-羥基乙氧基)-3-異丙基苯基]丙烷、2,2-雙[3-三級丁基-4-(2-羥基乙氧基)苯基]丙烷、2,2-雙[4-(2-羥基乙氧基)苯基]丁烷、2,2-雙[4-(2-羥基乙氧基)苯基]-4-甲基戊烷、2,2-雙[4-(2-羥基乙氧基)苯基]辛烷、1,1-雙[4-(2-羥基乙氧基)苯基]癸烷、2,2-雙[3-溴-4-(2-羥基乙氧基)苯基]丙烷、2,2-雙[3-環己基-4-(2-羥基乙氧基)苯基]丙烷所例示之雙(羥基烷氧基芳基)烷烴類；1,1-雙[4-(2-羥基乙氧基)苯基]環己烷、1,1-雙[3-環己基-4-(2-羥基乙氧基)苯基]環己烷、1,1-雙[4-(2-羥基乙氧基)苯基]環戊烷所例示之雙(羥基烷氧基芳基)環烷烴類；4,4’-雙(2-羥基乙氧基)二苯基醚、4,4’-雙(2-羥基乙氧基)-3,3’-二甲基二苯基醚所例示之二羥基烷氧基二芳基醚類；4,4’-雙(2-羥基乙氧基苯基)硫醚、4,4’-雙[4-(2-二羥基乙氧基)-3-甲基苯基]硫醚所例示之雙羥基烷氧基芳基硫醚類；4,4’-雙(2-羥基乙氧基苯基)亞碸、4,4’-雙[4-(2-二羥基乙氧基)-3-甲基苯基]亞碸所例示之雙羥基烷氧基芳基亞碸類；4,4’-雙(2-羥基乙氧基苯基)碸、4,4’-雙[4-(2-二羥基乙氧基)-3-甲基苯基]碸所例示之雙羥基烷氧基芳基碸類；1,4-雙羥基乙氧基苯、1,3-雙羥基乙氧基苯、1,2-雙羥基乙氧基苯、1,3-雙[2-[4-(2-羥基乙氧基)苯基]丙基]苯、1,4-雙[2-[4-(2-羥基乙氧基)苯基]丙基]苯、4,4’-雙(2-羥基乙氧基)聯苯、1,3-雙[4-(2-羥基乙氧基)苯基]-5,7-二甲基金剛烷、下述式(4)所示二羥基化合物所代表之糖醇酐；及下述通式(6)所示具有螺甘油等環狀醚結構之化合物，該等可單獨使用，亦可組合2種以上來使用。More specifically, the dihydroxy compound (A) includes, for example, 9,9-bis(4-(2-hydroxyethoxy)phenyl)perylene, 9,9-bis(4-(2-hydroxyethoxy) yl)-3-methylphenyl) fluoride, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl) fluoride, 9,9-bis(4-(2- Hydroxyethoxy)-3-isobutylphenyl) fluoride, 9,9-bis(4-(2-hydroxyethoxy)-3-tertiary butylphenyl) fluoride, 9,9-bis( 4-(2-Hydroxyethoxy)-3-cyclohexylphenyl) fluoride, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl) fluoride, 9,9- Bis(4-(2-hydroxyethoxy)-3,5-dimethylphenyl) stilbene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butyl-6 The side chains exemplified by -methylphenyl) fluoride and 9,9-bis(4-(3-hydroxy-2,2-dimethylpropoxy) phenyl) fluoride have an aromatic group and have an aromatic group on the main chain. Compounds bonded to ether groups of aromatic groups; bis[4-(2-hydroxyethoxy)phenyl]methane, bis[4-(2-hydroxyethoxy)phenyl]diphenylmethane, 1, 1-Bis[4-(2-hydroxyethoxy)phenyl]ethane, 1,1-bis[4-(2-hydroxyethoxy)phenyl]-1-phenylethane, 2,2 -Bis[4-(2-hydroxyethoxy)phenyl]propane, 2,2-bis[4-(2-hydroxyethoxy)-3-methylphenyl]propane, 2,2-bis[ 3,5-Dimethyl-4-(2-hydroxyethoxy)phenyl]propane, 1,1-bis[4-(2-hydroxyethoxy)phenyl]-3,3,5-tris Methylcyclohexane, 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane, 1,4-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane Alkane, 1,3-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane, 2,2-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]propane , 2,2-bis[(2-hydroxyethoxy)-3-isopropylphenyl]propane, 2,2-bis[3-tert-butyl-4-(2-hydroxyethoxy)benzene yl]propane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]butane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]-4-methyl Pentane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]octane, 1,1-bis[4-(2-hydroxyethoxy)phenyl]decane, 2,2 -Bis[3-bromo-4-(2-hydroxyethoxy)phenyl]propane, 2,2-bis[3-cyclohexyl-4-(2-hydroxyethoxy)phenyl]propane exemplified Bis(hydroxyalkoxyaryl)alkanes; 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane, 1,1-bis[3-cyclohexyl-4-(2 Bis(hydroxyalkoxyaryl)cycloalkanes exemplified by -hydroxyethoxy)phenyl]cyclohexane and 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclopentane ; 4,4'-bis(2-hydroxyethoxy)diphenyl ether, 4,4'-bis(2-hydroxyethoxy) )-3,3'-dimethyldiphenyl ether exemplified by dihydroxyalkoxydiaryl ethers; 4,4'-bis(2-hydroxyethoxyphenyl)sulfide, 4,4 '-bis[4-(2-dihydroxyethoxy)-3-methylphenyl]sulfide exemplified by bishydroxyalkoxyaryl sulfides; 4,4'-bis(2-hydroxyethyl) oxyphenyl) arylene, bishydroxyalkoxyaryl arylene exemplified by 4,4'-bis[4-(2-dihydroxyethoxy)-3-methylphenyl]arylene; Dihydroxyl group exemplified by 4,4'-bis(2-hydroxyethoxyphenyl)sine and 4,4'-bis[4-(2-dihydroxyethoxy)-3-methylphenyl]sine Alkoxyaryl benzenes; 1,4-bishydroxyethoxybenzene, 1,3-bishydroxyethoxybenzene, 1,2-bishydroxyethoxybenzene, 1,3-bis[2-[ 4-(2-Hydroxyethoxy)phenyl]propyl]benzene, 1,4-bis[2-[4-(2-hydroxyethoxy)phenyl]propyl]benzene, 4,4'- Bis(2-hydroxyethoxy)biphenyl, 1,3-bis[4-(2-hydroxyethoxy)phenyl]-5,7-dimethyladamantane, represented by the following formula (4) Anhydrous sugar represented by a dihydroxy compound; and a compound having a cyclic ether structure such as spiroglycerol represented by the following general formula (6) can be used alone or in combination of two or more.

[化學式4]

[Chemical formula 4]

該等二羥基化合物(A)可單獨使用，亦可組合2種以上來使用。本發明中，前述式(4)所示二羥基化合物可列舉處於立體異構物關係之異山梨醇、異甘露糖醇、異艾杜糖醇，該等可單獨使用1種，亦可組合2種以上來使用。These dihydroxy compounds (A) may be used alone or in combination of two or more. In the present invention, examples of the dihydroxy compound represented by the aforementioned formula (4) include isosorbide, isomannitol, and isoiditol, which are in a stereoisomeric relationship, and these may be used alone or in combination of two. Use more than one species.

此外，二羥基化合物(A)中，由取得及製造容易度、光學特性、成形性之方面來看，以將由資源豐富存在、可容易取得之各種澱粉製造之山梨糖醇進行脫水縮合而得之異山梨醇最佳。本案發明中，二羥基化合物(A)可適宜使用異山梨醇。In addition, the dihydroxy compound (A) is obtained by dehydrating and condensing sorbitol produced from various starches that are abundant in resources and can be easily obtained from the viewpoints of availability and production ease, optical properties, and moldability. Isosorbide is the best. In the present invention, isosorbide can be suitably used as the dihydroxy compound (A).

(二羥基化合物(B)) 本發明中，二羥基化合物可使用二羥基化合物(A)以外之二羥基化合物的二羥基化合物(B)。作為二羥基化合物(B)，可將例如脂環式二羥基化合物、脂肪族二羥基化合物、氧伸烷基二醇類、芳香族二羥基化合物、具有環狀醚結構之二醇類作為成為聚碳酸酯之結構單元的二羥基化合物，並與二羥基化合物(A)、例如式(4)所示二羥基化合物一同使用。(Dihydroxy compound (B)) In this invention, the dihydroxy compound (B) of a dihydroxy compound other than a dihydroxy compound (A) can be used as a dihydroxy compound. As the dihydroxy compound (B), for example, alicyclic dihydroxy compounds, aliphatic dihydroxy compounds, oxyalkylene glycols, aromatic dihydroxy compounds, and glycols having a cyclic ether structure can be used as a polymer The dihydroxy compound of the structural unit of carbonate is used together with the dihydroxy compound (A), for example, the dihydroxy compound represented by the formula (4).

本發明中可使用之脂環式二羥基化合物無特別限定，宜使用通常包含五員環結構或六員環結構之化合物。又，六員環結構可藉由共價鍵固定成椅形或船形。藉由脂環式二羥基化合物為五員環或六員環結構，可提高所得聚碳酸酯之耐熱性。脂環式二羥基化合物中所含碳原子數通常為70以下，宜為50以下，較宜為30以下。該值越大，耐熱性便越高，但難以合成、難以精製或成本昂貴。碳原子數越小，則越容易精製、越容易取得。The alicyclic dihydroxy compound that can be used in the present invention is not particularly limited, and a compound usually containing a five-membered ring structure or a six-membered ring structure is preferably used. Also, the six-membered ring structure can be fixed in a chair shape or a boat shape by covalent bonds. Since the alicyclic dihydroxy compound has a five-membered or six-membered ring structure, the heat resistance of the obtained polycarbonate can be improved. The number of carbon atoms contained in the alicyclic dihydroxy compound is usually 70 or less, preferably 50 or less, and more preferably 30 or less. The larger the value, the higher the heat resistance, but it is difficult to synthesize, difficult to purify or expensive. The smaller the number of carbon atoms, the easier it is to purify and obtain.

本發明中可使用之包含五員環結構或六員環結構之脂環式二羥基化合物，具體上可舉下述通式(II)或(III)所示脂環式二羥基化合物。 HOCH₂ -R¹ -CH₂ OH     (II) HO-R² -OH            (III) (式(II)、(III)中，R¹ 、R² 分別表示碳原子數4~20之環伸烷基) 關於屬上述通式(II)所示脂環式二羥基化合物之環己烷二甲醇，包含通式(II)中之R¹ 以下述通式(IIa)(式中，R³ 表示碳原子數1~12之烷基或氫原子)表示之各種異構物。所述異構物具體上可列舉1,2-環己烷二甲醇、1,3-環己烷二甲醇、1,4-環己烷二甲醇等。The alicyclic dihydroxy compound containing a five-membered ring structure or a six-membered ring structure that can be used in the present invention specifically includes the alicyclic dihydroxy compound represented by the following general formula (II) or (III). HOCH ₂ -R ¹ -CH ₂ OH (II) HO-R ² -OH (III) (In formulas (II) and (III), R ¹ and R ² respectively represent a cycloalkylene group having 4 to 20 carbon atoms ) With regard to cyclohexanedimethanol, which is an alicyclic dihydroxy compound represented by the above general formula (II), R ¹ in the general formula (II) is represented by the following general formula (IIa) (in the formula, R ³ represents a carbon atom) Various isomers represented by 1 to 12 alkyl groups or hydrogen atoms). Specific examples of the isomers include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and the like.

[化學式5]

[Chemical formula 5]

關於屬上述通式(II)所示脂環式二羥基化合物之三環癸烷二甲醇、五環十五烷二甲醇，包含通式(II)中之R¹ 以下述通式(IIb)(式中，n表示0或1)表示之各種異構物。Regarding tricyclodecanedimethanol and pentacyclopentadecandimethanol, which are alicyclic dihydroxy compounds represented by the above general formula (II), R ¹ in the general formula (II) is represented by the following general formula (IIb) ( In the formula, n represents various isomers represented by 0 or 1).

[化學式6]

[Chemical formula 6]

關於屬上述通式(II)所示脂環式二羥基化合物之十氫萘二甲醇或三環十四烷二甲醇，包含通式(II)中之R¹ 以下述通式(IIc)(式中，m表示0或1)表示之各種異構物。所述異構物具體上可列舉2,6-十氫萘二甲醇、1,5-十氫萘二甲醇、2,3-十氫萘二甲醇等。Regarding decahydronaphthalene dimethanol or tricyclotetradecane dimethanol, which is an alicyclic dihydroxy compound represented by the general formula (II), R ¹ in the general formula (II) is represented by the following general formula (IIc) (formula Among them, m represents various isomers represented by 0 or 1). Specific examples of the isomers include 2,6-decalin, 1,5-decalin, 2,3-decalin, and the like.

[化學式7]

[Chemical formula 7]

此外，關於屬上述通式(II)所示脂環式二羥基化合物之降莰烷二甲醇，包括通式(II)中之R¹ 以下述通式(IId)表示之各種異構物。所述異構物具體上可列舉2,3-降莰烷二甲醇、2,5-降莰烷二甲醇等。In addition, the norbornane dimethanol which is an alicyclic dihydroxy compound represented by the above-mentioned general formula (II) includes various isomers in which R ¹ in the general formula (II) is represented by the following general formula (IId). Specific examples of the isomers include 2,3-norbornanedimethanol, 2,5-norbornanedimethanol, and the like.

[化學式8]

[Chemical formula 8]

關於屬通式(II)所示脂環式二羥基化合物之金剛烷二甲醇，包含通式(II)中之R¹ 以下述通式(IIe)表示之各種異構物。所述異構物具體上可列舉1,3-金剛烷二甲醇等。The adamantane dimethanol, which is an alicyclic dihydroxy compound represented by the general formula (II), includes various isomers in which R ¹ in the general formula (II) is represented by the following general formula (IIe). Specific examples of the isomers include 1,3-adamantane dimethanol and the like.

[化學式9]

[Chemical formula 9]

又，屬上述通式(III)所示脂環式二羥基化合物之環己二醇包含通式(III)中之R² 以下述通式(IIIa)(式中，R³ 表示碳原子數1~12之烷基或氫原子)表示之各種異構物。所述異構物具體上可列舉1,2-環己二醇、1,3-環己二醇、1,4-環己二醇、2-甲-1,4-環己二醇等。In addition, the cyclohexanediol, which is an alicyclic dihydroxy compound represented by the above general formula (III), contains R2 in the general ^formula (III) and is represented by the following general formula (IIIa) (in the formula, ^R3 represents a carbon number of 1 Various isomers represented by alkyl or hydrogen atoms of ~12. Specific examples of the isomers include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, and the like.

[化學式10]

[Chemical formula 10]

關於屬上述通式(III)所示脂環式二羥基化合物之三環癸烷二醇、五環十五烷二醇，包含通式(III)中之R² 以下述通式(IIIb)(式中，n表示0或1)表示之各種異構物。Regarding tricyclodecanediol and pentacyclopentadecanediol, which are alicyclic dihydroxy compounds represented by the above general formula (III), R ² in the general formula (III) is represented by the following general formula (IIIb) ( In the formula, n represents various isomers represented by 0 or 1).

[化學式11]

[Chemical formula 11]

關於屬上述通式(III)所示脂環式二羥基化合物之十氫萘二醇或三環十四烷二醇，包含通式(III)中之R² 以下述通式(IIIc)(式中，m表示0或1)表示之各種異構物。所述異構物具體上可使用2,6-十氫萘二醇、1,5-十氫萘二醇、2,3-十氫萘二醇等。Regarding decalin or tricyclotetradecanediol, which are alicyclic dihydroxy compounds represented by the above general formula (III), R ² in the general formula (III) is represented by the following general formula (IIIc) (formula Among them, m represents various isomers represented by 0 or 1). Specifically, 2,6-decalin, 1,5-decalin, 2,3-decalin, and the like can be used as the isomer.

[化學式12]

[Chemical formula 12]

關於屬上述通式(III)所示脂環式二羥基化合物之降莰烷二醇，包含通式(III)中之R² 以下述通式(IIId)表示之各種異構物。所述異構物具體上可使用2,3-降莰烷二醇、2,5-降莰烷二醇等。The norbornanediol which is an alicyclic dihydroxy compound represented by the above-mentioned general formula (III) includes various isomers represented by the following general formula (IIId) in which R ² in the general formula (III) is represented. Specifically, 2,3-norbornanediol, 2,5-norbornanediol and the like can be used as the isomer.

[化學式13]

[Chemical formula 13]

關於上述通式(III)所示脂環式二羥基化合物之金剛烷二醇，包含通式(III)中之R² 以下述通式(IIIe)表示之各種異構物。所述異構物具體上可使用1,3-金剛烷二醇等。The adamantane diol of the alicyclic dihydroxy compound represented by the general formula (III) includes various isomers in which R ² in the general formula (III) is represented by the following general formula (IIIe). Specifically, 1,3-adamantanediol or the like can be used as the isomer.

[化學式14]

[Chemical formula 14]

上述脂環式二羥基化合物之具體例中，尤宜為環己烷二甲醇類、三環癸烷二甲醇類、金剛烷二醇類、五環十五烷二甲醇類，由取得容易度、處理容易度之觀點來看，宜為1,4-環己烷二甲醇、1,3-環己烷二甲醇、1,2-環己烷二甲醇、三環癸烷二甲醇。本案發明中，二羥基化合物(B)可適宜使用三環癸烷二甲醇。Among the specific examples of the above-mentioned alicyclic dihydroxy compounds, cyclohexanedimethanols, tricyclodecanedimethanols, adamantanediols, and pentacyclopentadecandimethanols are particularly preferred, due to the ease of obtaining, From the viewpoint of ease of handling, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and tricyclodecanedimethanol are preferable. In the present invention, tricyclodecane dimethanol can be suitably used as the dihydroxy compound (B).

本發明中可使用之脂肪族二羥基化合物，可列舉例如乙二醇、1,3-丙二醇、1,2-丙二醇、1,4-丁二醇、1,3-丁二醇、1,2-丁二醇、1,5-庚二醇、1,6-己二醇。本發明中可使用之氧伸烷基二醇類，可列舉例如二乙二醇、三乙二醇、四乙二醇、聚乙二醇。The aliphatic dihydroxy compound that can be used in the present invention includes, for example, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, and 1,2-propanediol. -Butanediol, 1,5-heptanediol, 1,6-hexanediol. Examples of the oxyalkylene glycols usable in the present invention include diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol.

本發明中可使用之芳香族二羥基化合物，可列舉例如2,2-雙(4-羥基苯基)丙烷[=雙酚A]、2,2-雙(4-羥基-3,5-二甲基苯基)丙烷、2,2-雙(4-羥基-3,5-二乙基苯基)丙烷、2,2-雙(4-羥基-(3,5-二苯基)苯基)丙烷、2,2-雙(4-羥基-3,5-二溴苯基)丙烷、2,2-雙(4-羥基苯基)戊烷、2,4’-二羥基-二苯甲烷、雙(4-羥基苯基)甲烷、雙(4-羥基-5-硝基苯基)甲烷、1,1-雙(4-羥基苯基)乙烷、3,3-雙(4-羥基苯基)戊烷、1,1-雙(4-羥基苯基)環己烷、雙(4-羥基苯基)碸、2,4’-二羥基二苯基碸、雙(4-羥基苯基)硫醚、4,4’-二羥基二苯基醚、4,4’-二羥基-3,3’-二氯二苯基醚、4,4’-二羥基-2,5-二乙氧基二苯基醚、9,9-雙[4-(2-羥基乙氧基)苯基]茀、9,9-雙[4-(2-羥基乙氧基-2-甲基)苯基]茀、9,9-雙(4-羥基苯基)茀、9,9-雙(4-羥基-2-甲基苯基)茀。The aromatic dihydroxy compound that can be used in the present invention includes, for example, 2,2-bis(4-hydroxyphenyl)propane [=bisphenol A], 2,2-bis(4-hydroxy-3,5-di Methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl) ) propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxyphenyl)pentane, 2,4'-dihydroxy-diphenylmethane , bis(4-hydroxyphenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyl) Phenyl)pentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) bismuth, 2,4'-dihydroxydiphenyl bismuth, bis (4-hydroxybenzene) base) thioether, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 4,4'-dihydroxy-2,5-diphenyl ether Ethoxydiphenyl ether, 9,9-bis[4-(2-hydroxyethoxy)phenyl]pyridine, 9,9-bis[4-(2-hydroxyethoxy-2-methyl) Phenyl] fluoride, 9,9-bis(4-hydroxyphenyl) fluoride, 9,9-bis(4-hydroxy-2-methylphenyl) fluoride.

本發明中可使用之具有環狀醚結構之二醇類，可列舉例如螺甘油類、二㗁烷二醇類。此外，上述例示化合物係本發明中可使用之脂環式二羥基化合物、脂肪族二羥基化合物、氧伸烷基二醇類、芳香族二羥基化合物、具有環狀醚結構之二醇類之一例，但完全不受該等所限。可以與式(4)所示二羥基化合物一同使用該等化合物中之1種或2種以上。The diols having a cyclic ether structure that can be used in the present invention include, for example, spiroglycerols and diethylene glycols. In addition, the above-mentioned exemplified compounds are examples of alicyclic dihydroxy compounds, aliphatic dihydroxy compounds, oxyalkylene glycols, aromatic dihydroxy compounds, and glycols having a cyclic ether structure that can be used in the present invention , but not so limited at all. One or more of these compounds may be used together with the dihydroxy compound represented by the formula (4).

藉由使用該等二羥基化合物(B)，可獲得改善符合用途之柔軟性、提高耐熱性、改善成形性等效果。二羥基化合物(A)、例如式(4)所示二羥基化合物相對於構成本發明聚碳酸酯樹脂之全部二羥基化合物之比率無特別限定，宜為10莫耳%以上，較宜為40莫耳%以上，更宜為60莫耳%以上，且宜為90莫耳%以下，較宜為80莫耳%以下，更宜為70莫耳%以下。若源自其它二羥基化合物之結構單元之含有比率過多，則有會使光學特性等性能降低之情形。By using these dihydroxy compounds (B), effects such as improving flexibility according to the application, improving heat resistance, and improving moldability can be obtained. The ratio of the dihydroxy compound (A), such as the dihydroxy compound represented by the formula (4), to all the dihydroxy compounds constituting the polycarbonate resin of the present invention is not particularly limited, but is preferably 10 mol % or more, more preferably 40 mol % % or more, more preferably 60 mol% or more, and preferably 90 mol% or less, more preferably 80 mol% or less, more preferably 70 mol% or less. When the content ratio of the structural unit derived from another dihydroxy compound is too large, performance, such as an optical characteristic, may fall.

上述其它二羥基化合物之中，使用脂環式二羥基化合物時，二羥基化合物(A)、例如式(4)所示二羥基化合物與脂環式二羥基化合物之合計相對於構成聚碳酸酯之全部二羥基化合物之比率無特別限定，宜為80莫耳%以上，較宜為90莫耳%以上，更宜為95莫耳%以上。Among the above-mentioned other dihydroxy compounds, when an alicyclic dihydroxy compound is used, the sum of the dihydroxy compound (A), for example, the dihydroxy compound represented by the formula (4) and the alicyclic dihydroxy compound, is relative to the amount of the polycarbonate constituting the The ratio of all the dihydroxy compounds is not particularly limited, but is preferably 80 mol % or more, more preferably 90 mol % or more, and more preferably 95 mol % or more.

又，關於本發明聚碳酸酯樹脂中源自二羥基化合物(A)、例如式(4)所示二羥基化合物之結構單元與源自脂環式二羥基化合物之結構單元之含有比率，可以任意比率進行選擇，宜為源自式(4)所示二羥基化合物之結構單元:源自脂環式二羥基化合物之結構單元=1:99~99:1(莫耳%)，尤宜為源自式(4)所示二羥基化合物之結構單元:源自脂環式二羥基化合物之結構單元=10:90~90:10(莫耳%)。若與上述範圍相比，源自式(4)所示二羥基化合物之結構單元多且源自脂環式二羥基化合物之結構單元少，則有容易著色之傾向，反之，若源自式(4)所示二羥基化合物之結構單元少且源自脂環式二羥基化合物之結構單元多，則有分子量難以上升之傾向。Moreover, the content ratio of the structural unit derived from the dihydroxy compound (A), for example, the dihydroxy compound represented by the formula (4), and the structural unit derived from the alicyclic dihydroxy compound in the polycarbonate resin of the present invention can be arbitrarily determined. The ratio is selected, preferably the structural unit derived from the dihydroxy compound represented by the formula (4): the structural unit derived from the alicyclic dihydroxy compound=1:99~99:1 (mol%), especially the source From the structural unit of the dihydroxy compound represented by the formula (4): from the structural unit of the alicyclic dihydroxy compound=10:90~90:10 (mol%). If the structural unit derived from the dihydroxy compound represented by the formula (4) is large and the structural unit derived from the alicyclic dihydroxy compound is small compared with the above range, the coloring tends to be easy. On the contrary, if the structural unit derived from the formula ( 4) When the structural unit of the dihydroxy compound shown is small and the structural unit derived from the alicyclic dihydroxy compound is many, the molecular weight tends to be difficult to increase.

並且，使用脂肪族二羥基化合物、氧伸烷基二醇類、芳香族二羥基化合物、具有環狀醚結構之二醇類時，二羥基化合物(A)、例如式(4)所示二羥基化合物與該等各二羥基化合物之合計相對於構成聚碳酸酯之全部二羥基化合物之比率無特別限定，可以任意比率進行選擇。又，源自二羥基化合物(A)、例如式(4)所示二羥基化合物之結構單元與源自該等各二羥基化合物之結構單元之含有比率亦無特別限定，可以任意之比率進行選擇。In addition, when using aliphatic dihydroxy compounds, oxyalkylene glycols, aromatic dihydroxy compounds, and diols having a cyclic ether structure, dihydroxy compounds (A), such as dihydroxy compounds represented by formula (4) The ratio of the compound and the total of these dihydroxy compounds to all the dihydroxy compounds constituting the polycarbonate is not particularly limited, and can be selected at any ratio. In addition, the content ratio of the structural unit derived from the dihydroxy compound (A), for example, the dihydroxy compound represented by the formula (4), and the structural unit derived from each of these dihydroxy compounds is not particularly limited, and an arbitrary ratio can be selected. .

聚碳酸酯系樹脂之詳細內容記載於例如日本專利特開2012-31370號公報(日本專利第5448264號)。本說明書中係援用該專利文獻之記載作為參考。Details of the polycarbonate-based resin are described in, for example, Japanese Patent Laid-Open No. 2012-31370 (Japanese Patent No. 5448264). The description of this patent document is used as a reference in this specification.

C.光學薄膜之製造方法 光學薄膜例如可藉由將B項中記載之聚碳酸酯系樹脂等樹脂進行薄膜成形來獲得。作為形成薄膜之方法，可採用任意且適當之成形加工法。作為具體例，可列舉擠製成形法、吹塑成形法、澆鑄塗敷法(例如流鑄法)、壓延成形法等。其中，可宜採用可提高所得薄膜之平滑性、可獲得良好光學均勻性之擠製成形法或澆鑄塗敷法，較宜採用澆鑄塗敷法。澆鑄塗敷法之產線速度宜為7m/分鐘~15m/分鐘，較宜為7m/分鐘~12m/分鐘。藉由將B項中記載之樹脂薄膜以預定速度以下之產線速度進行製膜，可獲得實質上具有光學各向同性之光學薄膜。但是，產線速度為一定速度以下時，所得光學薄膜之定向度會下降，導致在加濕可靠性試驗中之相位差變化及接著性降低。於是，藉由將上述產線速度設為一定速度以上，光學薄膜之定向度會上升，從而可抑制在加濕可靠性試驗中之相位差變化，進而接著性會提高。即，藉由以上述範圍之產線速度進行澆鑄製膜，可兼顧所期望之面內相位差、抑制在加濕可靠性試驗中之相位差變化及優異之接著性。進而，藉由以上述範圍之產線速度進行澆鑄製膜，可抑制MD方向(長邊方向)之膜厚不均及膜厚不均所引起之相位差不均。C. Manufacturing method of optical film The optical film can be obtained, for example, by film-forming resins such as polycarbonate-based resins described in the section B. As a method of forming a thin film, any and appropriate molding processing method can be adopted. As a specific example, an extrusion molding method, a blow molding method, a casting coating method (for example, a casting method), a calendering method, etc. are mentioned. Among them, the extrusion forming method or the casting coating method, which can improve the smoothness of the obtained film and obtain good optical uniformity, can be suitably used, and the casting coating method is more suitable. The production line speed of the casting coating method should be 7m/min~15m/min, more preferably 7m/min~12m/min. An optical film having substantially optical isotropy can be obtained by film-forming the resin film described in the item B at a line speed below a predetermined speed. However, when the production line speed is below a certain speed, the degree of orientation of the optical film obtained decreases, resulting in a change in retardation and a decrease in adhesiveness in the humidification reliability test. Therefore, by setting the above-mentioned line speed to be equal to or higher than a certain speed, the orientation degree of the optical film is increased, the retardation change in the humidification reliability test can be suppressed, and the adhesiveness is improved. That is, by performing film formation by casting at the production line speed in the above-mentioned range, desired in-plane retardation, suppression of retardation change in the humidification reliability test, and excellent adhesiveness can be achieved at the same time. Furthermore, by performing film-forming by casting at the production line speed in the above-mentioned range, the film thickness unevenness in the MD direction (long-side direction) and the retardation unevenness caused by the film thickness unevenness can be suppressed.

D.偏光板 偏光板代表上具有偏光件與上述光學薄膜，上述光學薄膜係藉由接著劑層而貼合於該偏光件之至少單面。如上所述，光學薄膜與偏光件之接著性優異。該偏光件中，亦可在偏光件之至少單面具有保護層。進而，亦可在該偏光板之與視辨側相反之側的面具有黏著劑層及分離件。對於偏光件、保護層、黏著劑層即分離件，可援用本領域周知之構成，因此省略詳細說明。D. Polarizing plate The polarizing plate typically has a polarizer and the above-mentioned optical film, and the above-mentioned optical film is attached to at least one side of the polarizer through an adhesive layer. As described above, the adhesion between the optical film and the polarizer is excellent. In the polarizer, a protective layer may also be provided on at least one side of the polarizer. Furthermore, an adhesive layer and a separator may be provided in the surface on the opposite side to the viewing side of this polarizing plate. As for the polarizer, the protective layer, and the separator, that is, the adhesive layer, the structures known in the art can be used, and therefore detailed descriptions are omitted.

作為構成上述接著劑層之接著劑組成物，代表上可舉出活性能量線硬化型接著劑組成物。該活性能量線硬化型接著劑組成物包含活性能量線硬化型化合物。Typical examples of the adhesive composition constituting the above-mentioned adhesive layer include active energy ray-curable adhesive compositions. This active energy ray hardening adhesive composition contains an active energy ray hardening compound.

本發明活性能量線硬化型接著劑組成物例如為含有活性能量線硬化型化合物(A)、(B)及(C)作為硬化性成分之活性能量線硬化型接著劑組成物；當將組成物總量設為100重量%時，含有0.0~4.0重量%之SP值為29.0(MJ/m³ )^1/2 以上且32.0(MJ/m³ )^1/2 以下之活性能量線硬化型化合物(A)、5.0~98.0重量%之SP值為18.0(MJ/m³ )^1/2 以上且小於21.0(MJ/m³ )^1/2 之活性能量線硬化型化合物(B)、及5.0~98.0重量%之SP值為21.0(MJ/m³ )^1/2 以上且26.0(MJ/m³ )^1/2 以下之活性能量線硬化型化合物(C)。此外，本發明中「組成物總量」係指除了活性能量線硬化型化合物外還包含各種引發劑或添加劑之總量。The active energy ray curable adhesive composition of the present invention is, for example, an active energy ray curable adhesive composition containing active energy ray curable compounds (A), (B) and (C) as curable components; When the total amount is 100% by weight, 0.0 to 4.0% by weight ^of the active energy ray ^{- curable compound} ( A), 5.0-98.0 wt% SP value of 18.0 (MJ/m ³ ) ^1/2 or more and less than 21.0 (MJ/m ³ ) ^1/2 active energy ray hardening compound (B), and 5.0-98.0 The active energy ray-curable compound (C) whose SP value in % by weight is 21.0 (MJ/m ³ ) ^1/2 or more and 26.0 (MJ/m ³ ) ^1/2 or less. In addition, the "total amount of the composition" in the present invention refers to the total amount of various initiators or additives in addition to the active energy ray-curable compound.

活性能量線硬化型化合物(A)若為具有(甲基)丙烯酸酯基等自由基聚合性基、且SP值為29.0(MJ/m³ )^1/2 以上且32.0(MJ/m³ )^1/2 以下之化合物，便可無限定地使用。作為活性能量線硬化型化合物(A)之具體例，例如可列舉羥基乙基丙烯醯胺(SP值29.5)、N-羥甲基丙烯醯胺(SP值31.5)等。此外，本發明中(甲基)丙烯酸酯基係指丙烯酸酯基及/或甲基丙烯酸酯基。If the active energy ray-curable compound (A) has a radically polymerizable group such as a (meth)acrylate group, and has an SP value of 29.0 (MJ/m ³ ) ^1/2 or more and 32.0 (MJ/m ³ ) ¹ Compounds with ^/2 or less can be used without limitation. As a specific example of an active energy ray hardening-type compound (A), a hydroxyethyl acrylamide (SP value 29.5), N-methylol acrylamide (SP value 31.5), etc. are mentioned, for example. Moreover, in this invention, a (meth)acrylate group means an acrylate group and/or a methacrylate group.

活性能量線硬化型化合物(B)若為具有(甲基)丙烯酸酯基等自由基聚合性基、且SP值為18.0(MJ/m³ )^1/2 以上且小於21.0(MJ/m³ )^1/2 之化合物，便可無限定地使用。作為活性能量線硬化型化合物(B)之具體例，例如可列舉三丙二醇二丙烯酸酯(SP值19.0)、1,9-壬二醇二丙烯酸酯(SP值19.2)、三環癸烷二甲醇二丙烯酸酯(SP值20.3)、環狀三羥甲丙烷縮甲醛丙烯酸酯(SP值19.1)、二㗁烷二醇二丙烯酸酯(SP值19.4)、EO改質二甘油四丙烯酸酯(SP值20.9)等。此外，作為活性能量線硬化型化合物(B)亦可適宜使用市售品，例如可列舉ARONIX M-220(東亞合成公司製，SP值19.0)、Light Acrylate 1,9ND-A(共榮社化學公司製，SP值19.2)、Light Acrylate DGE-4A(共榮社化學公司製，SP值20.9)、Light Acrylate DCP-A(共榮社化學公司製，SP值20.3)、SR-531(SARTOMER公司製，SP值19.1)、CD-536(SARTOMER公司製，SP值19.4)等。If the active energy ray-curable compound (B) has a radically polymerizable group such as a (meth)acrylate group, and has an SP value of 18.0 (MJ/m ³ ) ^1/2 or more and less than 21.0 (MJ/m ³ ) ^1/2 of the compound can be used without limitation. Specific examples of the active energy ray-curable compound (B) include tripropylene glycol diacrylate (SP value: 19.0), 1,9-nonanediol diacrylate (SP value: 19.2), and tricyclodecane dimethanol. Diacrylate (SP value 20.3), cyclic trimethylolpropane formal acrylate (SP value 19.1), diethylene glycol diacrylate (SP value 19.4), EO modified diglycerol tetraacrylate (SP value 20.9) etc. Moreover, a commercial item can also be used suitably as an active energy ray hardening-type compound (B), for example, ARONIX M-220 (made by Toagosei Co., Ltd., SP value 19.0), Light Acrylate 1,9ND-A (Kyoeisha Chemical Co., Ltd.) can be mentioned. Co., Ltd., SP value 19.2), Light Acrylate DGE-4A (Kyoeisha Chemical Co., Ltd., SP value 20.9), Light Acrylate DCP-A (Kyoeisha Chemical Co., Ltd., SP value 20.3), SR-531 (Sartomer Co., Ltd. manufactured by SARTOMER, SP value 19.1), CD-536 (manufactured by SARTOMER, SP value 19.4), etc.

活性能量線硬化型化合物(C)若為具有(甲基)丙烯酸酯基等自由基聚合性基、且SP值為21.0(MJ/m³ )^1/2 以上且26.0(MJ/m³ )^1/2 以下之化合物，便可無限定地使用。作為活性能量線硬化型化合物(C)之具體例，例如可列舉丙烯醯嗎福林(SP值22.9)、N-甲氧基甲基丙烯醯胺(SP值22.9)、N-乙氧基甲基丙烯醯胺(SP值22.3)等。此外，作為活性能量線硬化型化合物(C)亦可適宜使用市售品，例如可列舉ACMO(KOHJIN公司製，SP值22.9)、Wasmer 2MA(笠野興產公司製，SP值22.9)、Wasmer EMA(笠野興產公司製，SP值22.3)、Wasmer 3MA(笠野興產公司製，SP值22.4)等。If the active energy ray-curable compound (C) has a radically polymerizable group such as a (meth)acrylate group, and has an SP value of 21.0 (MJ/m ³ ) ^1/2 or more and 26.0 (MJ/m ³ ) ¹ Compounds with ^/2 or less can be used without limitation. Specific examples of the active energy ray-curable compound (C) include acryl molybdenum (SP value: 22.9), N-methoxymethacrylamide (SP value: 22.9), N-ethoxymethyl base acrylamide (SP value 22.3) and so on. Moreover, a commercial item can also be used suitably as an active energy ray hardening-type compound (C), for example, ACMO (manufactured by Kohjin Co., Ltd., SP value 22.9), Wasmer 2MA (manufactured by Kasano Kosan Co., Ltd., SP value 22.9), Wasmer EMA (manufactured by Kasano Kosan Co., Ltd., SP value 22.3), Wasmer 3MA (manufactured by Kasano Kosan Co., Ltd., SP value 22.4), etc.

上述接著劑組成物之詳細內容例如記載於日本專利特開2019-147865號公報。本說明書中係援用該特許文獻之記載作為參考。藉由將上述光學薄膜與由上述接著劑組成物構成之接著劑層貼合，光學薄膜之接著性會變得更優異。The details of the above-mentioned adhesive composition are described in, for example, Japanese Patent Laid-Open No. 2019-147865. The description of this patent document is used in this specification as a reference. The adhesiveness of an optical film becomes more excellent by bonding the said optical film and the adhesive agent layer which consists of the said adhesive agent composition.

實施例 以下，藉由實施例來具體說明本發明，但本發明不受該等實施例所限。此外，各特性之測定方法及評估方法如下所示。 (1)面內相位差 將實施例及比較例中所得光學薄膜切成4cm長及4cm寬，作為測定試料。針對該測定試料，使用Axometrics公司製之製品名「Axoscan」，測定面內相位差Re(550)。 (2)折射率及雙折射Δnxy 用阿貝折射率計(DR-M2，ATAGO公司製)測定。測定係在23℃環境下進行。 (3)厚度 10μm以下之厚度係使用干涉膜厚計(大塚電子公司製，製品名「MCPD-9800」)進行測定。大於10μm之厚度係使用數位測微計(ANRITSU公司製，製品名「KC-351C」)進行測定。 (4)定向度 使用實施例及比較例中所得光學薄膜，藉由X射線繞射法(XRD)求出定向度。 (5)加濕相位差變化 將實施例及比較例中所得光學薄膜切成5cm×5cm，用手墨輥在單面貼附黏著劑，將黏著劑面貼附於鹼玻璃之單面而獲得試驗片。將試驗片在溫度65℃且濕度90%之烘箱中保存500小時(加濕試驗)，算出試驗開始前及試驗後之相位差變化(%)。將相位差變化為10%以下者評估為佳，大於10%者評估為不佳。 (6)平行色相a值及b值 求出實施例及比較例中所得光學薄膜之平行色相a值及平行色相b值。測定係使用分光光度計(日本分光公司製，商品名「V-7100」)來進行。將投入至紫外線褪色試驗機(裝置名；紫外線褪色計試驗機U48，Suga Test Instruments Co.,Ltd.製)之前之b值與投入100h後之b值之變化率為1%以下者評估為佳，大於1%者評估為不佳。 (7)接著性 將實施例及比較例中所得光學薄膜與偏光件進行貼合，而獲得積層體。將所得積層體切成與偏光件之延伸方向平行之方向為200mm、正交方向為15mm之大小，將該積層體貼合於玻璃板。並且，用切刀在光學薄膜與偏光件之間製造切口，利用TENSILON萬能試驗機RTC(股份公司A&D公司製)，沿著90度方向將光學薄膜與偏光件以1000mm/分鐘之剝離速度進行剝離，測定其剝離強度(N/15mm)。將剝離強度為1N/15mm以上之情況評估為佳，將小於1N/15mm之情況評估為不佳。Example Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In addition, the measurement method and evaluation method of each characteristic are as follows. (1) In-plane phase difference The optical films obtained in the Examples and Comparative Examples were cut into pieces of 4 cm in length and 4 cm in width, and used as measurement samples. For this measurement sample, the in-plane retardation Re (550) was measured using the product name "Axoscan" manufactured by Axometrics. (2) Refractive index and birefringence Δnxy Measured with an Abbe refractometer (DR-M2, manufactured by ATAGO). The measurement is carried out in a 23°C environment. (3) Thickness The thickness of 10 μm or less was measured using an interference film thickness meter (manufactured by Otsuka Electronics Co., Ltd., product name “MCPD-9800”). Thickness factors larger than 10 μm were measured using a digital micrometer (manufactured by ANRITSU, product name “KC-351C”). (4) Orientation The degree of orientation was determined by X-ray diffraction (XRD) using the optical films obtained in Examples and Comparative Examples. (5) Humidification phase difference change The optical films obtained in the Examples and Comparative Examples were cut into 5 cm×5 cm, and the adhesive was attached to one side with a hand ink roller, and the adhesive surface was attached to one side of the alkali glass to obtain a test piece. The test piece was stored in an oven with a temperature of 65° C. and a humidity of 90% for 500 hours (humidification test), and the phase difference change (%) before the start of the test and after the test was calculated. Those with a phase difference change of less than 10% were evaluated as good, and those greater than 10% were evaluated as poor. (6) Parallel hue a value and b value The parallel hue a value and the parallel hue b value of the optical films obtained in Examples and Comparative Examples were determined. The measurement was performed using a spectrophotometer (manufactured by JASCO Corporation, trade name "V-7100"). It is best to evaluate the difference between the b value before being put into an ultraviolet fading tester (device name; UV light fading tester U48, manufactured by Suga Test Instruments Co., Ltd.) and the b value after 100 hours of input. , more than 1% were assessed as poor. (7) Adhesion The optical films and polarizers obtained in Examples and Comparative Examples were bonded together to obtain a laminate. The obtained laminate was cut into a size of 200 mm in the direction parallel to the extending direction of the polarizer and 15 mm in the orthogonal direction, and the laminate was attached to a glass plate. In addition, a slit was made between the optical film and the polarizer with a cutter, and the optical film and the polarizer were peeled off at a peeling speed of 1000 mm/min along a 90-degree direction using a Tensilon universal testing machine RTC (manufactured by A&D Co., Ltd.). , and measure its peel strength (N/15mm). The case where the peel strength was 1 N/15 mm or more was evaluated as good, and the case where the peel strength was less than 1 N/15 mm was evaluated as unfavorable.

[實施例1] 在反應容器中，相對於異山梨醇(以下有時簡寫為「ISB」)81.98質量份，投入三環癸烷二甲醇(以下有時簡寫為「TCDDM」)47.19質量份、碳酸二苯酯(以下有時簡寫為「DPC」)175.1質量份及作為觸媒之碳酸銫0.2質量%水溶液0.979質量份，在氮氣環境下，作為反應之第一階段之步驟，將加熱槽溫度加熱至150℃，根據需要邊攪拌邊使原料溶解(約15分鐘)。接著，使壓力自常壓成為13.3kPa，邊耗費1小時使加熱槽溫度上升至190℃，邊將產生之苯酚取出至反應容器外。將反應容器整體以190℃保持15分鐘後，作為第二階段之步驟，使反應容器內之壓力成為6.67kPa，耗費15分鐘使加熱槽溫度上升至230℃，將產生之苯酚取出至反應容器外。由於攪拌機之攪拌轉矩逐漸上升，故耗費8分鐘升溫至250℃，進而為了去除所產生之苯酚而使反應容器內之壓力達到0.200kPa以下。在達到預定之攪拌轉矩後，結束反應，將生成之反應物擠出至水中，而獲得聚碳酸酯樹脂之丸粒。所得聚碳酸酯樹脂之雙折射Δnxy為0.015。將所得聚碳酸酯樹脂在100℃下真空乾燥12小時後，使用具備單軸擠製機(東芝機械公司製，料筒設定溫度：250℃)、T模具(寬度1700mm，設定溫度：250℃)、澆鑄輥(設定溫度：60℃)及捲取機之薄膜製膜裝置，將製膜產線速度設為7m/分鐘，製作由聚碳酸酯樹脂構成之光學薄膜。所得光學薄膜之定向度為7.4%，面內相位差Re(550)為6nm，厚度為40μm。將所得學薄膜供於上述(5)~(7)之評估。將結果示於表1。[Example 1] In the reaction container, 47.19 parts by mass of tricyclodecane dimethanol (hereinafter abbreviated as "TCDDM"), diphenyl carbonate ( Hereinafter, it is sometimes abbreviated as "DPC") 175.1 parts by mass and 0.979 parts by mass of a 0.2 mass % aqueous solution of cesium carbonate as a catalyst, in a nitrogen atmosphere, as the first step of the reaction, the temperature of the heating tank was heated to 150 ℃, The raw materials are dissolved while stirring as necessary (about 15 minutes). Next, the pressure was set to 13.3 kPa from normal pressure, and the generated phenol was taken out of the reaction vessel while raising the temperature of the heating tank to 190° C. over 1 hour. After the entire reaction vessel was kept at 190°C for 15 minutes, as a second step, the pressure in the reaction vessel was adjusted to 6.67 kPa, the temperature of the heating tank was raised to 230°C for 15 minutes, and the generated phenol was taken out of the reaction vessel . Since the stirring torque of the stirrer gradually increased, the temperature was raised to 250° C. in 8 minutes, and the pressure in the reaction vessel was made 0.200 kPa or less in order to remove the generated phenol. After reaching a predetermined stirring torque, the reaction was terminated, and the resulting reactant was extruded into water to obtain pellets of polycarbonate resin. The birefringence Δnxy of the obtained polycarbonate resin was 0.015. After vacuum-drying the obtained polycarbonate resin at 100°C for 12 hours, a uniaxial extruder (manufactured by Toshiba Machine Co., Ltd., barrel setting temperature: 250°C) and a T die (width 1700 mm, setting temperature: 250°C) were used. , a casting roll (set temperature: 60° C.) and a film film forming device of a winder, the film production line speed was set to 7 m/min, and an optical film composed of polycarbonate resin was produced. The degree of orientation of the obtained optical film was 7.4%, the in-plane retardation Re(550) was 6 nm, and the thickness was 40 μm. The obtained thin films were used for the evaluations of (5) to (7) above. The results are shown in Table 1.

[實施例2] 將製膜產線速度設為8m/分鐘、將厚度設為30μm，除此之外與實施例1相同操作而獲得光學薄膜。所得光學薄膜之定向度為5.7%，面內相位差Re(550)為3nm。將所得光學薄膜供於與實施例1相同之評估。將結果示於表1。[Example 2] An optical film was obtained in the same manner as in Example 1, except that the film-forming line speed was 8 m/min and the thickness was 30 μm. The degree of orientation of the obtained optical film was 5.7%, and the in-plane retardation Re(550) was 3 nm. The resulting optical film was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[實施例3] 將聚碳酸酯樹脂之雙折射Δnxy設為0.018、將製膜產線速度設為10m/分鐘及將厚度設為20μm，除此之外與實施例1相同操作而獲得光學薄膜。所得光學薄膜之定向度為6.1%，面內相位差Re(550)為2nm。將所得光學薄膜供於與實施例1相同之評估。將結果示於表1。[Example 3] An optical film was obtained in the same manner as in Example 1, except that the birefringence Δnxy of the polycarbonate resin was set to 0.018, the film-forming line speed was set to 10 m/min, and the thickness was set to 20 μm. The degree of orientation of the obtained optical film was 6.1%, and the in-plane retardation Re(550) was 2 nm. The resulting optical film was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[實施例4] 將聚碳酸酯樹脂之雙折射Δnxy設為0.024、將製膜產線速度設為12m/分鐘及將厚度設為20μm，除此之外與實施例1相同操作而獲得光學薄膜。所得光學薄膜之定向度為8.1%，面內相位差Re(550)為2nm。將所得光學薄膜供於與實施例1相同之評估。將結果示於表1。[Example 4] An optical film was obtained in the same manner as in Example 1, except that the birefringence Δnxy of the polycarbonate resin was set to 0.024, the film-forming line speed was set to 12 m/min, and the thickness was set to 20 μm. The orientation degree of the obtained optical film was 8.1%, and the in-plane retardation Re(550) was 2 nm. The resulting optical film was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[比較例1] 將聚碳酸酯樹脂之雙折射Δnxy設為0.016、將製膜產線速度設為5m/分鐘，除此之外與實施例1相同操作而獲得光學薄膜。所得光學薄膜之定向度為4.8%，面內相位差Re(550)為5nm。將所得光學薄膜供於與實施例1相同之評估。將結果示於表1。[Comparative Example 1] An optical film was obtained in the same manner as in Example 1, except that the birefringence Δnxy of the polycarbonate resin was set to 0.016 and the film-forming line speed was set to 5 m/min. The degree of orientation of the obtained optical film was 4.8%, and the in-plane retardation Re(550) was 5 nm. The resulting optical film was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[比較例2] 使用雙折射Δnxy為0.018之三醋酸纖維素(TAC)薄膜(柯尼卡美能達公司製，商品名「KC4UA」)及將產線速度設為15m/分鐘，除此之外與實施例1相同操作而獲得光學薄膜。所得光學薄膜之定向度為5.1%，面內相位差Re(550)為2nm。將所得光學薄膜供於與實施例1相同之評估。將結果示於表1。[Comparative Example 2] It is the same as Example 1 except that a triacetate cellulose (TAC) film with a birefringence Δnxy of 0.018 (manufactured by Konica Minolta Co., Ltd., trade name "KC4UA") is used and the line speed is set to 15 m/min. operation to obtain an optical film. The degree of orientation of the obtained optical film was 5.1%, and the in-plane retardation Re(550) was 2 nm. The resulting optical film was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[比較例3] (聚酯碳酸酯系樹脂之聚合) 使用由2個具備攪拌葉片及控制在100℃之回流冷卻器之立式反應器構成之批式聚合裝置來進行聚合。投入雙[9-(2-苯氧羰基乙基)茀-9-基]甲烷29.60質量份(0.046mol)、異山梨醇(ISB)29.21質量份(0.200mol)、螺甘油(SPG)42.28質量份(0.139mol)、碳酸二苯酯(DPC)63.77質量份(0.298mol)及作為觸媒之醋酸鈣一水合物1.19×10^-2 質量份(6.78×10^-5 mol)。將反應器內進行減壓氮氣置換後，用熱介質進行加溫，在內溫達到100℃之時間點開始攪拌。在升溫開始40分鐘後使內溫到達220℃，以保持該溫度之方式進行控制，同時開始減壓，在到達220℃後耗用90分鐘使成為13.3kPa。將與聚合反應一同副生成之苯酚蒸氣導入至100℃之回流冷卻器，將苯酚蒸氣中所含若干量單體成分返回至反應器，將未凝聚之苯酚蒸氣導入至45℃之冷凝器並回收。往第1反應器中導入氮氣，暫時恢復至大氣壓後，將第1反應器內之經寡聚物化之反應液移至第2反應器。接著，開始第2反應器內之升溫及減壓，耗用50分鐘使成為內溫240℃、壓力0.2kPa。然後，使聚合進行，直至達到預定之攪拌功率。在到達預定功率之時間點往反應器中導入氮氣來恢復壓力，將生成之聚酯碳酸酯系樹脂擠出至水中，對束料進行切割而獲得丸粒。所得聚碳酸酯樹脂之雙折射Δnxy為0.012。[Comparative Example 3] (Polymerization of polyester carbonate-based resin) Polymerization was performed using a batch polymerization apparatus composed of two vertical reactors equipped with stirring blades and a reflux cooler controlled at 100°C. 29.60 parts by mass (0.046 mol) of bis[9-(2-phenoxycarbonylethyl)perpen-9-yl]methane, 29.21 parts by mass (0.200 mol) of isosorbide (ISB), and 42.28 parts by mass of spiroglycerol (SPG) were added parts (0.139 mol), 63.77 parts by mass (0.298 mol) of diphenyl carbonate (DPC), and 1.19×10 ^-2 parts by mass (6.78×10 ^-5 mol) of calcium acetate monohydrate as a catalyst. After the inside of the reactor was replaced with nitrogen under reduced pressure, it was heated with a heat medium, and stirring was started when the internal temperature reached 100°C. 40 minutes after the start of temperature increase, the internal temperature was controlled to reach 220°C, and the pressure reduction was started while maintaining the temperature. After reaching 220°C, it took 90 minutes to reach 13.3 kPa. Introduce the phenol vapor by-produced with the polymerization reaction to a reflux cooler at 100°C, return a certain amount of monomer components contained in the phenol vapor to the reactor, and introduce the uncondensed phenol vapor into a condenser at 45°C and recover . Nitrogen gas was introduced into the first reactor and the pressure was temporarily returned to atmospheric pressure, and then the oligomerized reaction liquid in the first reactor was transferred to the second reactor. Next, the temperature increase and pressure reduction in the second reactor were started, and it took 50 minutes to achieve an internal temperature of 240° C. and a pressure of 0.2 kPa. Then, the polymerization is allowed to proceed until a predetermined stirring power is reached. When the predetermined power is reached, nitrogen gas is introduced into the reactor to restore the pressure, the resulting polyester carbonate-based resin is extruded into water, and the strands are cut to obtain pellets. The birefringence Δnxy of the obtained polycarbonate resin was 0.012.

(光學薄膜之製作) 將所得聚酯碳酸酯系樹脂(丸粒)在80℃下真空乾燥5小時後，使用具備單軸擠製機(東芝機械公司製，料筒設定溫度：270℃)、T模具(寬度1700mm，設定溫度：270℃)、澆鑄輥(設定溫度：75℃)及捲取機之薄膜製膜裝置，將製膜產線速度設為8m/分鐘，製作厚度40μm之長條狀光學薄膜。所得光學薄膜之定向度為4.3%，面內相位差Re(550)為7nm。將所得光學薄膜供於與實施例1相同之評估。將結果示於表1。(Fabrication of Optical Film) After vacuum-drying the obtained polyester carbonate-based resin (pellet) at 80°C for 5 hours, a uniaxial extruder (manufactured by Toshiba Machine Co., Ltd., barrel setting temperature: 270°C) and a T die (width 1700 mm, Set temperature: 270°C), casting roll (set temperature: 75°C), and film forming device of a winder, and set the film forming line speed to 8 m/min to produce a long optical film with a thickness of 40 μm. The degree of orientation of the obtained optical film was 4.3%, and the in-plane retardation Re(550) was 7 nm. The resulting optical film was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[比較例4] 對厚度40μm之三醋酸纖維素薄膜進行研光處理，進行塗佈。所得光學薄膜之面內相位差Re(550)為3nm，厚度為2μm。將所得光學薄膜供於與實施例1相同之評估。將結果示於表1。[Comparative Example 4] The triacetate cellulose film with a thickness of 40 μm was polished and coated. The in-plane retardation Re(550) of the obtained optical film was 3 nm, and the thickness was 2 μm. The resulting optical film was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[表1]

[Table 1]

由表1明顯可知，本發明實施例之光學薄膜在加濕相位差變化、耐候性及接著性之各方面均優異。推測這是藉由將包含具有特定雙折射Δnxy之特定聚碳酸酯樹脂的樹脂薄膜以特定產線速度進行製膜而實現之。進而，由實施例1~4與比較例4之比較可知，藉由使用不含紫外線吸收劑之光學薄膜，可抑制在耐候性試驗中之色相變化。As is apparent from Table 1, the optical films of the examples of the present invention are excellent in all aspects of humidification retardation change, weather resistance, and adhesiveness. It is presumed that this is achieved by forming a resin film containing a specific polycarbonate resin having a specific birefringence Δnxy at a specific line speed. Furthermore, from the comparison of Examples 1-4 and the comparative example 4, it turns out that the hue change in a weather resistance test can be suppressed by using the optical film which does not contain an ultraviolet absorber.

產業上之可利用性 本發明實施形態之光學薄膜及偏光板可適宜用於影像顯示裝置。industrial availability The optical film and polarizing plate of the embodiment of the present invention can be suitably used for an image display device.

(無)(none)

Claims (7)

一種光學薄膜，係由雙折射Δnxy為0.015以上之樹脂構成者；其定向度為5%以上，面內相位差Re(550)為20nm以下，在65℃及90%RH下保持500小時後之相位差變化率為10%以下，在紫外區之耐候性試驗中之b值的變化率為1%以下。An optical film composed of a resin with a birefringence Δnxy of 0.015 or more; the degree of orientation is 5% or more, the in-plane retardation Re(550) is 20 nm or less, and the film is kept at 65°C and 90% RH for 500 hours. The retardation change rate is 10% or less, and the b value change rate in the weather resistance test in the ultraviolet region is 1% or less. 如請求項1之光學薄膜，其中前述樹脂包含聚碳酸酯系樹脂。The optical film according to claim 1, wherein the aforementioned resin comprises a polycarbonate-based resin. 如請求項2之光學薄膜，其中前述聚碳酸酯系樹脂包含源自下述式(4)所示二羥基化合物之結構單元， [化學式1]

。The optical film according to claim 2, wherein the polycarbonate-based resin comprises a structural unit derived from a dihydroxy compound represented by the following formula (4), [Chemical formula 1]

. 如請求項3之光學薄膜，其中前述聚碳酸酯系樹脂更包含源自脂環式二羥基化合物之結構單元，該脂環式二羥基化合物係以下述通式(II)表示，R¹ 為下述(IIb)所示結構，n=0， HOCH₂ -R¹ -CH₂ OH   (II) [化學式2]

。The optical film according to claim 3, wherein the polycarbonate resin further comprises a structural unit derived from an alicyclic dihydroxy compound, the alicyclic dihydroxy compound is represented by the following general formula (II), and R ¹ is the following The structure shown in (IIb), n=0, HOCH ₂ -R ¹ -CH ₂ OH (II) [Chemical formula 2]

. 如請求項1之光學薄膜，其厚度為10μm~50μm。As claimed in claim 1, the optical film has a thickness of 10 μm to 50 μm. 一種偏光板，其包含偏光件與透過接著劑層貼合於該偏光件之至少單面的如請求項1至5中任一項之光學薄膜。A polarizing plate, comprising a polarizer and an optical film according to any one of claims 1 to 5, which are adhered to at least one side of the polarizer through an adhesive layer. 一種光學薄膜之製造方法，係製造如請求項1至5中任一項之光學薄膜之方法，且包含產線速度為7m/分鐘~15m/分鐘之製膜步驟。A method for manufacturing an optical film, which is a method for manufacturing the optical film as claimed in any one of claims 1 to 5, and includes a film-forming step with a production line speed of 7 m/min to 15 m/min.