TW202210564A - Retardation film, polarizing plate with retardation layer, and method for manufacturing retardation film suppressing the change in retardation in the humidification reliability test and the change in hue in the weather resistance test in the ultraviolet region - Google Patents

Abstract

This invention aims to provide a retardation film and a polarizing plate with a retardation layer containing the retardation film. The retardation film suppresses the change in retardation in the humidification reliability test and the change in hue in the weather resistance test in the ultraviolet region. It also has excellent adhesion. The solution is a retardation film having an orientation degree of 30% or more and is made of a resin having birefringence in a predetermined range.

Description

相位差薄膜、附相位差層之偏光板及相位差薄膜之製造方法Retardation film, polarizing plate with retardation layer, and manufacturing method of retardation film

本發明涉及相位差薄膜、附相位差層之偏光板及相位差薄膜之製造方法。The present invention relates to a retardation film, a polarizing plate with a retardation layer, and a method for manufacturing the retardation 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)，尤其對於相位差薄膜配置於面板側之偏光板而言，有紫外光造成相位差薄膜之色相變化，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 retardation films disposed on the panel side, ultraviolet light causes retardation. The color change of the film will damage 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，其目的在於提供相位差薄膜及包含該相位差薄膜之附相位差層之偏光板，該相位差薄膜已抑制住在加濕可靠性試驗中之相位差變化，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 of the present invention is to provide a retardation film and a polarizing plate with a retardation layer including the retardation film, the retardation film being suppressed from being subjected to a humidification reliability test. The retardation changes, and the hue change in the weather resistance test in the ultraviolet region has been suppressed, and the adhesion is excellent.

用以解決課題之手段 本發明實施形態中之相位差薄膜係由雙折射Δnxy為0.015以上之樹脂構成，且其定向度為30%以上，正面相位差Re(550)為100nm~180nm或220nm~340nm，在65℃及90%RH下保持500小時後之相位差變化率為1.5%以下，在紫外區之耐候性試驗中之b值之變化率為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 係下述(IIb)所示結構，n=0。 HOCH₂ -R¹ -CH₂ OH　(II) [化學式2]

在一實施形態中，上述相位差薄膜之厚度為10μm~50μm。 本發明另一實施形態係提供一種附相位差層之偏光板。該附相位差層之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相位差薄膜。在一實施形態中，上述相位差薄膜係透過上述接著劑層直接貼合於上述偏光件之至少單面。在一實施形態中，上述接著劑層係由活性能量線硬化型接著劑組成物構成。 根據本發明另一面向，提供上述相位差薄膜之製造方法。該製造方法包含延伸由上述樹脂形成之樹脂薄膜之步驟。MEANS TO SOLVE THE PROBLEM The retardation film in the embodiment of the present invention is composed of a resin having a birefringence Δnxy of 0.015 or more, the degree of orientation is 30% or more, and the front retardation Re(550) is 100nm~180nm or 220nm~ 340nm, the retardation change rate after 500 hours at 65°C and 90% RH is less than 1.5%, and the change rate of b value in the weather resistance test in the ultraviolet region is less than 1%. 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 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 retardation film has a thickness of 10 μm to 50 μm. Another embodiment of the present invention provides a polarizing plate with a retardation layer. The polarizing plate with retardation layer includes a polarizer and the above-mentioned retardation film attached to at least one side of the polarizer through the adhesive layer. In one embodiment, the retardation film is directly bonded to at least one side of the polarizer through the adhesive layer. In one embodiment, the adhesive layer is composed of an active energy ray-curable adhesive composition. According to another aspect of the present invention, a method for manufacturing the above retardation film is provided. The manufacturing method includes the step of extending a resin film formed of the above-mentioned resin.

發明效果 根據本發明實施形態，藉由延伸由雙折射Δnxy為0.015以上之預定樹脂構成之樹脂薄膜，定向度會達一定值以上，結果可實現一種相位差薄膜，其已抑制住在加濕可靠性試驗中之相位差變化，且已抑制住在紫外區之耐候性試驗中之色相變化。Invention effect According to the embodiment of the present invention, by extending a resin film composed of a predetermined resin having a birefringence Δnxy of 0.015 or more, the degree of orientation becomes a certain value or more, and as a result, a retardation film can be realized, which has been suppressed in the humidification reliability test. The retardation change in the UV region has been suppressed, and the hue change in the weather resistance test in the ultraviolet region has been suppressed.

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.相位差薄膜 本發明實施形態之相位差薄膜包含聚碳酸酯樹脂。因此，本發明實施形態之相位差薄膜代表上為聚碳酸酯樹脂薄膜之延伸薄膜。並且，本發明實施形態之相位差薄膜宜不含紫外線吸收劑。藉由相位差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. retardation film The retardation film of the embodiment of the present invention contains a polycarbonate resin. Therefore, the retardation film of the embodiment of the present invention is typically a stretched film of a polycarbonate resin film. In addition, the retardation film of the embodiment of the present invention preferably does not contain an ultraviolet absorber. Since the retardation film does not contain ultraviolet absorbers, it can maintain a neutral hue when applied to an image display device.

構成上述相位差薄膜之樹脂之雙折射Δnxy代表上為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。藉由延伸具有所述雙折射Δnxy之樹脂，可獲得已抑制住在加濕條件下之相位差變化的相位差薄膜。The birefringence Δnxy of the resin constituting the above retardation film is representatively 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 extending the resin having the birefringence Δnxy, it is possible to obtain a retardation film in which the retardation change under humidified conditions has been suppressed.

上述相位差薄膜之定向度為30%以上，宜為31%以上，較宜為32%以上。定向度之上限例如為70%。相位差薄膜之定向度若在所述範圍內，相位差薄膜之接著性會變良好。所述範圍之定向度可藉由延伸上述樹脂薄膜而實現。上述定向度例如係藉由X射線繞射法(XRD)測定。The degree of orientation of the above retardation film is 30% or more, preferably 31% or more, and more preferably 32% or more. The upper limit of the degree of orientation is, for example, 70%. When the degree of orientation of the retardation film is within the above-mentioned range, the adhesiveness of the retardation film becomes favorable. The degree of orientation in the range can be achieved by extending the above-mentioned resin film. The above-mentioned degree of orientation is measured by, for example, X-ray diffraction (XRD).

上述相位差薄膜之面內相位差Re(550)為100nm~180nm或220nm~340nm，宜為120nm~160nm或240nm~320nm。即，相位差薄膜可作為λ/2相位差板或λ/4相位差板發揮功能。The in-plane retardation Re(550) of the above retardation film is 100nm~180nm or 220nm~340nm, preferably 120nm~160nm or 240nm~320nm. That is, the retardation film can function as a λ/2 retardation plate or a λ/4 retardation plate.

上述相位差薄膜在溫度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1.5%以下，較宜為1.4%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 為試驗開始前之相位差薄膜之面內相位差(nm)，Re₅₀₀ 為試驗後之相位差薄膜之面內相位差(nm)。相位差薄膜之相位差變化若在所述範圍內，在將相位差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 phase difference change of the above retardation film after being stored for 500 hours (humidification test) at a temperature of 65°C and a humidity of 90% is preferably 1.5% or less, more preferably 1.4% 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 retardation film before the start of the test, and Re ₅₀₀ is the in-plane retardation (nm) of the retardation film after the test. If the phase difference change of the retardation film is within the range, the following advantages can be obtained when the retardation film is applied to the image display device: the hue change caused by the phase difference in various places on the image display device is reduced, thereby suppressing the display on the display device. color unevenness occurs.

上述相位差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，相位差薄膜亦可良好地用於要求耐候性之用途上。相位差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 retardation film has suppressed the change in 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 retardation film can also be favorably used for applications requiring weather resistance. The above-mentioned advantage can be obtained by containing the specific polycarbonate resin mentioned later in the retardation film.

上述相位差薄膜之厚度宜為10μm~50μm，較宜為20μm~40μm。The thickness of the above retardation film is preferably 10 μm to 50 μm, more preferably 20 μm to 40 μm.

上述相位差薄膜之透濕度宜為250g/m² ・24h以下，較宜為150g/m² ・24h以下。下限例如可為1g/m² ・24h。相位差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 retardation 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. If the water vapor transmission rate of the retardation film is within the above-mentioned range, the advantage of suppressing the retardation change in a humidified environment can be obtained.

上述相位差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，可良好地防止所得影像顯示裝置之熱不均。The absolute value of the photoelastic coefficient of the above retardation film is preferably 2 × 10 ^-11 m ² /N or less, more 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, thermal unevenness of the resulting image display device can be well prevented.

根據本發明實施形態，如上述藉由延伸由具有特定範圍之雙折射Δnxy之樹脂構成的樹脂薄膜，可獲得具有特定範圍之定向度之相位差薄膜。該相位差薄膜滿足所期望之面內相位差，並且已抑制住在加濕可靠性試驗中之相位差變化，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。所述相位差薄膜可適宜用於例如PID(公眾資訊顯示器)、行動電話。According to the embodiment of the present invention, as described above, by extending a resin film composed of a resin having a birefringence Δnxy in a specific range, a retardation film having an orientation degree in a specific range can be obtained. The retardation film satisfies the desired in-plane retardation, has suppressed the retardation change in the humidification reliability test, has suppressed the hue change in the weather resistance test in the ultraviolet region, and is excellent in adhesiveness. The retardation film can be suitably used for, for example, a PID (Public Information Display) and a mobile phone.

B.構成材料 上述相位差薄膜如上述代表上為聚碳酸酯樹脂之延伸樹脂薄膜。B. Constituent materials The above-mentioned retardation film is represented by the above-mentioned stretched resin film of polycarbonate resin.

(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 dicarbonic 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 sugars represented by dihydroxy compounds; and compounds 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.相位差薄膜之製造方法 本發明實施形態之相位差薄膜之製造方法包含將樹脂薄膜進行延伸處理。樹脂薄膜係由上述B項中說明之聚碳酸酯樹脂形成之薄膜。C. Manufacturing method of retardation film The manufacturing method of the retardation film which concerns on embodiment of this invention includes extending|stretching a resin film. The resin film is a film formed of the polycarbonate resin described in the item B above.

在一實施形態中，相位差薄膜係藉由將樹脂薄膜進行單軸延伸或固定端單軸延伸而製作。作為固定端單軸延伸之具體例，可列舉使樹脂薄膜一邊沿長邊方向行進一邊沿寬度方向(橫向)延伸之方法。延伸倍率宜為1.1倍~3.5倍，較宜為1.5倍~3.0倍，更宜為2.0倍~2.5倍。藉由將由B項中記載之聚碳酸酯樹脂形成之樹脂薄膜以所述延伸倍率延伸，溶劑對相位差薄膜之滲透性會發生變化，形成與接著劑層之相溶層，從而接著力會提高。該現象在相位差薄膜之相位差值越高時越明顯。即，藉由將特定聚碳酸酯樹脂以如上述之延伸倍率延伸，可顯著抑制相位差薄膜在加濕條件下之相位差變化。In one embodiment, the retardation film is produced by uniaxially stretching a resin film or by uniaxially stretching a fixed end. As a specific example of the uniaxial extension of the fixed end, a method of extending the resin film in the width direction (horizontal direction) while advancing in the longitudinal direction can be mentioned. The extension ratio is preferably 1.1 times to 3.5 times, more preferably 1.5 times to 3.0 times, and more preferably 2.0 times to 2.5 times. By extending the resin film formed of the polycarbonate resin described in the item B at the stretching ratio, the permeability of the solvent to the retardation film is changed, and a compatible layer with the adhesive layer is formed, thereby improving the adhesive force. . This phenomenon is more obvious when the retardation value of the retardation film is higher. That is, by extending the specific polycarbonate resin at the above-mentioned stretching ratio, the retardation change of the retardation film under humidification conditions can be significantly suppressed.

上述樹脂薄膜之延伸溫度宜為Tg-30℃~Tg+30℃，較宜為Tg-15℃~Tg+15℃，更宜為Tg-10℃~Tg+10℃。藉由在所述溫度下延伸，在本發明中可獲得具有適當特性之相位差薄膜。此外，Tg係薄膜之構成材料的玻璃轉移溫度。The stretching temperature of the resin film is preferably Tg-30°C~Tg+30°C, more preferably Tg-15°C~Tg+15°C, more preferably Tg-10°C~Tg+10°C. By extending at the temperature, a retardation film having appropriate characteristics can be obtained in the present invention. In addition, Tg is the glass transition temperature of the constituent material of the thin film.

D.附相位差層之偏光板 上述A項~C項中記載之相位差薄膜可以與其它光學薄膜及/或光學構件之積層體之形式提供。在一實施形態中，相位差薄膜可以與偏光板之積層體(附相位差層之偏光板)之形式提供。因此，本發明包含具有上述相位差薄膜之附相位差層的偏光板。本發明實施形態之附相位差層之偏光板具備偏光板與由上述相位差薄膜構成之相位差層。相位差薄膜中，偏光板之偏光件的吸收軸與相位差薄膜的慢軸形成之角度可根據用途及目的來適當設定。在一實施形態中，上述角度宜為40°~50°，較宜為42°~48°，更宜為約45°。D. Polarizing plate with retardation layer The retardation film described in the above items A to C can be provided in the form of a laminate with other optical films and/or optical members. In one embodiment, the retardation film can be provided in the form of a laminate with a polarizing plate (polarizing plate with retardation layer). Therefore, the present invention includes a polarizing plate with a retardation layer having the above retardation film. The polarizing plate with retardation layer according to the embodiment of the present invention includes a polarizing plate and a retardation layer composed of the above-mentioned retardation film. In the retardation film, the angle formed by the absorption axis of the polarizer of the polarizing plate and the slow axis of the retardation film can be appropriately set according to the application and purpose. In one embodiment, the above-mentioned angle is preferably 40°~50°, more preferably 42°~48°, and more preferably about 45°.

附相位差層之偏光板代表上具有偏光件與透過接著劑層貼合於偏光件之至少單面的上述相位差薄膜。如上述，相位差薄膜與偏光件之接著性優異。The polarizing plate with retardation layer represents the above-mentioned retardation film having a polarizer and a transparent adhesive layer attached to at least one side of the polarizer. As described above, the adhesion between the retardation film and the polarizer is excellent.

作為構成上述接著劑層之接著劑組成物，代表上可舉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。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.

該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。藉由組合上述接著劑層與上述相位差薄膜，會在相位差薄膜與接著劑層之間形成相溶層，從而相位差薄膜之接著性會變良好。因此，在附相位差層之偏光板之製作中，便沒有必要在相位差薄膜與接著劑層之間設置易接著層。因此，上述附相位差層之偏光板中，宜為相位差薄膜藉由接著劑層直接貼合於偏光件之至少單面。所述不具有易接著劑層之該附相位差層之偏光板可良好地抑制在加濕條件下之相位差變化。Details of the 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. By combining the above-mentioned adhesive layer and the above-mentioned retardation film, a compatible layer is formed between the retardation film and the adhesive layer, and the adhesiveness of the retardation film becomes good. Therefore, in the production of the polarizing plate with the retardation layer, it is not necessary to provide an easy-adhesion layer between the retardation film and the adhesive layer. Therefore, in the above-mentioned polarizing plate with retardation layer, it is preferable that the retardation film is directly attached to at least one side of the polarizer through the adhesive layer. The polarizing plate with the retardation layer without the easy-adhesion agent layer can well suppress the retardation change under humidification conditions.

亦可在上述偏光件之至少單面具有保護層。並且，亦可在該附相位差層之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、黏著劑層及分離件可援用本領域周知之構成，因此省略詳細說明。A protective layer may also be provided on at least one side of the above-mentioned polarizer. In addition, an adhesive layer and a separator may be provided on the surface of the polarizing plate with retardation layer on the opposite side to the viewing side. For the polarizer, the protective layer, the adhesive layer, and the separator, structures known in the art can be used, and thus detailed descriptions are omitted.

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相位差薄膜切成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相位差薄膜，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附相位差層之偏光板切成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1.5%以下者評估為佳，大於1.5%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相位差薄膜之平行色相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相位差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，用切刀在相位差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度方向將相位差薄膜與偏光件以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 retardation films obtained in the Examples and Comparative Examples were cut out to 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 retardation films obtained in Examples and Comparative Examples. (5) Humidification phase difference change The polarizing plate with retardation layer obtained in Examples and Comparative Examples was cut into 5 cm×5 cm, the adhesive was attached to one side with a hand ink roller, and the adhesive surface was attached to one side of 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 1.5% were evaluated as good, and those greater than 1.5% 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 retardation 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 being put into it. , more than 1% were assessed as poor. (7) Adhesion The retardation films obtained in Examples and Comparative Examples were bonded to a polarizer 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 retardation film and the polarizer with a cutter, and the retardation 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.). The peeling was performed, and the peeling strength (N/15mm) was measured. 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] 1.樹脂薄膜之製作 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，製作厚度90μm之聚碳酸酯樹脂薄膜。[Example 1] 1. Production of resin film 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 forming device of a winder to produce a polycarbonate resin film with a thickness of 90 μm.

2.相位差薄膜之製作 使用同步雙軸延伸機，將未延伸之上述聚碳酸酯樹脂薄膜供於預熱處理及同步雙軸延伸而獲得相位差薄膜。預熱溫度設為140℃，延伸溫度設為138℃，長邊方向之延伸倍率設為2.4倍。所得相位差薄膜之定向度為31.1%，面內相位差Re(550)為140nm，加濕相位差變化率為1.21%，厚度為40μm。將所得相位差薄膜供於上述(6)及(7)之評估。將結果示於表1。2. Production of retardation film Using a simultaneous biaxial stretching machine, the unstretched polycarbonate resin film was subjected to preheating and simultaneous biaxial stretching to obtain a retardation film. The preheating temperature was 140° C., the stretching temperature was 138° C., and the stretching ratio in the longitudinal direction was 2.4 times. The obtained retardation film had an orientation degree of 31.1%, an in-plane retardation Re(550) of 140 nm, a humidification retardation change rate of 1.21%, and a thickness of 40 μm. The obtained retardation film was used for the evaluation of the above (6) and (7). The results are shown in Table 1.

3.偏光板之製作 作為樹脂基材，使用長條狀、Tg約75℃之非晶質間苯二甲酸共聚聚對苯二甲酸乙二酯薄膜(厚度：100μm)，在樹脂基材之單面實施了電暈處理。 於由聚乙烯醇(聚合度4200，皂化度99.2莫耳%)及乙醯乙醯基改質PVA(日本合成化學工業公司製，商品名「GOSEFIMER」)以9：1混合而成之PVA系樹脂100重量份中添加碘化鉀13重量份，將所得物質溶於水，而製備出PVA水溶液(塗佈液)。 在樹脂基材之電暈處理面上塗佈上述PVA水溶液，在60℃下乾燥，從而形成厚度13μm之PVA系樹脂層，製作出積層體。 將所得積層體在130℃之烘箱內沿縱向(長邊方向)單向延伸成2.4倍(空中輔助延伸處理)。 接著，將積層體在液溫40℃之不溶解浴(相對於水100重量份摻混硼酸4重量份而得之硼酸水溶液)中浸漬30秒鐘(不溶解處理)。 接著，在液溫30℃之染色浴(相對於水100重量份以1：7之重量比摻混碘與碘化鉀而得之碘水溶液)中，邊調整濃度邊浸漬60秒鐘，使最終獲得之偏光件的單體透射率(Ts)成為所期望之值(染色處理)。 接著，在液溫40℃之交聯浴(相對於水100重量份摻混3重量份碘化鉀、摻混5重量份硼酸而得之硼酸水溶液)中浸漬30秒鐘(交聯處理)。 然後，將積層體邊浸漬在液溫70℃之硼酸水溶液(硼酸濃度4重量%、碘化鉀濃度5重量%)中邊在周速不同之輥間沿縱向(長邊方向)進行單軸延伸，使總延伸倍率成為5.5倍(水中延伸處理)。 然後，將積層體在液溫20℃之洗淨浴(相對於水100重量份摻混4重量份碘化鉀而得之水溶液)中浸漬(洗淨處理)。 然後，邊在保持約90℃之烘箱中乾燥，邊使其與表面溫度保持約75℃之SUS製之加熱輥接觸(乾燥收縮處理)。 由此，在樹脂基材上形成厚度約5μm之偏光件，而獲得具有樹脂基材/偏光件之構成的偏光板。 進而，在所得偏光件之與樹脂基材相反之側的面，透過紫外線硬化型接著劑貼合環烯烴系薄膜(日本ZEON公司製，商品名「ZEONOR」)作為保護層。具體而言，係以硬化型接著劑之總厚度成為約1.0μm之方式進行塗敷，併使用滾軋機進行貼合。然後，從環烯烴系薄膜側照射UV光線，使接著劑硬化。接著，將樹脂基材剝離，而獲得具有環烯烴系薄膜(保護層)/偏光件之構成的偏光板。該保護層之面內相位差為135nm。關於保護層的慢軸與偏光件的吸收軸形成之角度，設為實質上平行。3. Production of polarizing plate As the resin substrate, a long, amorphous poly(ethylene terephthalate) film (thickness: 100 μm) with a Tg of about 75°C was used, and corona treatment was performed on one side of the resin substrate . It is a PVA system that is mixed with polyvinyl alcohol (degree of polymerization 4200, degree of saponification 99.2 mol%) and acetyl acetyl group modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "GOSEFIMER") in a ratio of 9:1 13 parts by weight of potassium iodide was added to 100 parts by weight of the resin, and the obtained substance was dissolved in water to prepare an aqueous PVA solution (coating liquid). The above-mentioned PVA aqueous solution was coated on the corona-treated surface of the resin substrate, and dried at 60° C. to form a PVA-based resin layer with a thickness of 13 μm, thereby producing a laminate. The obtained layered body was unidirectionally stretched 2.4 times in the longitudinal direction (longitudinal direction) in an oven at 130° C. (in-air assisted stretching treatment). Next, the layered body was immersed for 30 seconds in an insolubilization bath (a boric acid aqueous solution obtained by blending 4 parts by weight of boric acid with respect to 100 parts by weight of water) at a liquid temperature of 40°C (insolubility treatment). Next, in a dyeing bath at a liquid temperature of 30° C. (an iodine aqueous solution obtained by mixing iodine and potassium iodide at a weight ratio of 1:7 with respect to 100 parts by weight of water), immersion was carried out for 60 seconds while adjusting the concentration, so that the final obtained The single transmittance (Ts) of the polarizer becomes a desired value (dyeing treatment). Next, it was immersed for 30 seconds in a cross-linking bath (a boric acid aqueous solution obtained by mixing 3 parts by weight of potassium iodide and 5 parts by weight of boric acid with respect to 100 parts by weight of water) for 30 seconds (cross-linking treatment). Then, the laminate was dipped in a boric acid aqueous solution (boric acid concentration of 4 wt %, potassium iodide concentration of 5 wt %) at a liquid temperature of 70° C., and uniaxially stretched in the longitudinal direction (longitudinal direction) between rolls with different peripheral speeds to make The total stretching ratio was 5.5 times (in-water stretching treatment). Then, the layered body was immersed in a cleaning bath (aqueous solution obtained by mixing 4 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 20°C (cleaning treatment). Then, while drying in an oven maintained at about 90°C, it was brought into contact with a heating roll made of SUS whose surface temperature was maintained at about 75°C (drying shrinkage treatment). Thus, a polarizer having a thickness of about 5 μm was formed on the resin substrate, and a polarizing plate having a resin substrate/polarizer configuration was obtained. Further, a cycloolefin-based film (manufactured by ZEON Corporation, trade name "ZEONOR") as a protective layer was bonded to the surface of the obtained polarizer on the opposite side to the resin substrate through an ultraviolet curable adhesive. Specifically, it is applied so that the total thickness of the hardening type adhesive may be about 1.0 μm, and it is bonded using a rolling mill. Then, UV light is irradiated from the cycloolefin-based film side to harden the adhesive. Next, the resin substrate was peeled off to obtain a polarizing plate having a configuration of a cycloolefin-based film (protective layer)/polarizer. The in-plane retardation of the protective layer was 135 nm. The angle formed by the slow axis of the protective layer and the absorption axis of the polarizer is set to be substantially parallel.

4.附相位差層之偏光板之製作 在上述相位差薄膜之單面，使用MCD塗佈機(富士機械公司製)，以厚度成為0.7μm之方式塗敷活性能量線硬化型接著劑組成物，並用滾軋機貼合於上述偏光板之偏光件表面。活性能量線硬化型接著劑組成物係藉由將共榮社化學公司製「Light Acrylate 1.9ND-A」40份、東亞合成公司製「Aronix M-5700」20份、東亞合成公司製商品名「ARUFON UP1190」10份之各成分混合並在50℃下攪拌1小時而得。然後，從貼合後之相位差薄膜側，用活性能量線照射裝置照射可見光線使活性能量線硬化型接著劑硬化後，在70℃下進行3分鐘熱風乾燥，而獲得附相位差層之偏光板。偏光件的吸收軸與相位差薄膜的慢軸形成之角度設為45°。將所得附相位差層之偏光板供於上述(5)之評估。將結果示於表1。4. Production of polarizing plate with retardation layer On one side of the retardation film, an active-energy ray-curable adhesive composition was applied to a thickness of 0.7 μm using an MCD coater (manufactured by Fuji Machine Co., Ltd.), and then attached to the polarizing plate by a rolling mill. Polarizer surface. The active energy ray hardening type adhesive composition was prepared by combining 40 parts of "Light Acrylate 1.9ND-A" manufactured by Kyoeisha Chemical Co., Ltd., 20 parts of "Aronix M-5700" manufactured by Toagosei Corporation, and trade name "Toagosei Corporation." 10 parts of each component of ARUFON UP1190" was mixed and stirred at 50°C for 1 hour. Then, from the side of the phase difference film after lamination, visible light was irradiated with an active energy ray irradiation device to harden the active energy ray curable adhesive, and then hot air drying was performed at 70° C. for 3 minutes to obtain a polarized light with a retardation layer. plate. The angle formed by the absorption axis of the polarizer and the slow axis of the retardation film was set to 45°. The obtained polarizing plate with retardation layer was used for the evaluation of the above (5). The results are shown in Table 1.

[實施例2] 將厚度設為30μm，除此之外與實施例1相同操作而獲得相位差薄膜。所得相位差薄膜之定向度為31.9%，面內相位差Re(550)為140nm，加濕相位差變化率為1.15%。進而，與實施例1相同方式使用所得相位差薄膜，而獲得附相位差層之偏光板。將所得相位差薄膜及附相位差層之偏光板供於與實施例1相同之評估。將結果示於表1。[Example 2] A retardation film was obtained in the same manner as in Example 1 except that the thickness was 30 μm. The orientation degree of the obtained retardation film was 31.9%, the in-plane retardation Re(550) was 140 nm, and the humidification retardation change rate was 1.15%. Furthermore, using the obtained retardation film in the same manner as in Example 1, a polarizing plate with a retardation layer was obtained. The obtained retardation film and the polarizing plate with retardation layer were used for 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，預熱溫度設為138℃，延伸溫度設為135℃，除此之外與實施例1相同操作而獲得相位差薄膜。所得相位差薄膜之定向度為35.7%，面內相位差Re(550)為270nm，加濕相位差變化率為1.29%。進而，與實施例1相同方式使用所得相位差薄膜，而獲得附相位差層之偏光板。將所得相位差薄膜及附相位差層之偏光板供於與實施例1相同之評估。將結果示於表1。[Example 3] A retardation 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 preheating temperature was set to 138°C, and the stretching temperature was set to 135°C. The orientation degree of the obtained retardation film was 35.7%, the in-plane retardation Re(550) was 270 nm, and the humidification retardation change rate was 1.29%. Furthermore, using the obtained retardation film in the same manner as in Example 1, a polarizing plate with a retardation layer was obtained. The obtained retardation film and the polarizing plate with retardation layer were used for 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，將厚度設為30μm，將延伸倍率設為2.5倍，並且預熱溫度設為138℃，延伸溫度設為135℃，除此之外與實施例1相同操作而獲得相位差薄膜。所得相位差薄膜之定向度為34.6%，面內相位差Re(550)為260nm，加濕相位差變化率為1.31%。進而，與實施例1相同方式使用所得相位差薄膜，而獲得附相位差層之偏光板。將所得相位差薄膜及附相位差層之偏光板供於與實施例1相同之評估。將結果示於表1。[Example 4] The birefringence Δnxy of the polycarbonate resin was set to 0.024, the thickness was set to 30 μm, the stretching ratio was set to 2.5 times, the preheating temperature was set to 138° C., and the stretching temperature was set to 135° C. Other than that, the same as the examples 1 The same operation was performed to obtain a retardation film. The orientation degree of the obtained retardation film was 34.6%, the in-plane retardation Re(550) was 260 nm, and the humidification retardation change rate was 1.31%. Furthermore, using the obtained retardation film in the same manner as in Example 1, a polarizing plate with a retardation layer was obtained. The obtained retardation film and the polarizing plate with retardation layer were used for 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，將長邊方向之延伸倍率設為2.12倍，除此之外與實施例1相同操作而獲得相位差薄膜。所得相位差薄膜之定向度為29.4%，面內相位差Re(550)為140nm，加濕相位差變化率為2.81%。進而，設置了易接著層，除此之外與實施例1相同操作，使用所得相位差薄膜製作出附相位差層之偏光板。將所得相位差薄膜及附相位差層之偏光板供於與實施例1相同之評估。將結果示於表1。[Comparative Example 1] A retardation 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 extension ratio in the longitudinal direction was set to 2.12 times. The orientation degree of the obtained retardation film was 29.4%, the in-plane retardation Re(550) was 140 nm, and the humidification retardation change rate was 2.81%. Furthermore, except having provided the easily bonding layer, it carried out similarly to Example 1, and produced the polarizing plate with retardation layer using the obtained retardation film. The obtained retardation film and the polarizing plate with retardation layer were used for 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0.021之環烯烴系樹脂薄膜(日本ZEON公司製，商品名「ZEONOR」)，並且預熱溫度設為150℃，延伸溫度設為148℃，除此之外與實施例1相同操作而獲得相位差薄膜。所得相位差薄膜之定向度為30.1%，面內相位差Re(550)為140nm，加濕相位差變化率為1.2%。進而，設置了易接著層，除此之外與實施例1相同操作，使用所得相位差薄膜製作出附相位差層之偏光板。將所得相位差薄膜及附相位差層之偏光板供於與實施例1相同之評估。將結果示於表1。[Comparative Example 2] The same procedure as in Example 1 was used, except that a cycloolefin-based resin film with a birefringence Δnxy of 0.021 (manufactured by ZEON Co., Ltd., trade name "ZEONOR") was used, the preheating temperature was set to 150°C, and the stretching temperature was set to 148°C operation to obtain a retardation film. The orientation degree of the obtained retardation film was 30.1%, the in-plane retardation Re(550) was 140 nm, and the humidification retardation change rate was 1.2%. Furthermore, except having provided the easily bonding layer, it carried out similarly to Example 1, and produced the polarizing plate with retardation layer using the obtained retardation film. The obtained retardation film and the polarizing plate with retardation layer were used for 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.

(相位差薄膜之製作) 將所得聚酯碳酸酯系樹脂(丸粒)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：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，製作出厚度130μm之長條狀樹脂薄膜。將所得長條狀樹脂薄膜邊調整邊延伸，使得其獲得預定之相位差，從而獲得厚度40μm之相位差薄膜。關於延伸條件，沿長邊方向，延伸倍率為2.12倍。所得相位差薄膜之定向度為28.8%，面內相位差Re(550)為140nm，加濕相位差變化率為3.1%。進而，設置了易接著層，除此之外與實施例1相同操作，使用所得相位差薄膜製作出附相位差層之偏光板。將所得相位差薄膜及附相位差層之偏光板供於與實施例1相同之評估。將結果示於表1。(Production of retardation film) The obtained polyester carbonate-based resin (pellet) was vacuum-dried at 100° C. for 12 hours, and then used a uniaxial extruder (manufactured by Toshiba Machine Co., Ltd., barrel setting temperature: 270° C.), a T die (width 1700 mm, A set temperature: 270°C), a casting roll (set temperature: 75°C), and a film forming device of a winder were used to produce a long resin film with a thickness of 130 μm. The obtained long resin film was stretched while being adjusted so as to obtain a predetermined retardation, thereby obtaining a retardation film with a thickness of 40 μm. Regarding the stretching conditions, in the longitudinal direction, the stretching ratio was 2.12 times. The orientation degree of the obtained retardation film was 28.8%, the in-plane retardation Re(550) was 140 nm, and the humidification retardation change rate was 3.1%. Furthermore, except having provided the easily bonding layer, it carried out similarly to Example 1, and produced the polarizing plate with retardation layer using the obtained retardation film. The obtained retardation film and the polarizing plate with retardation layer were used for the same evaluation as in Example 1. The results are shown in Table 1.

[比較例4] 將表現向列液晶相之聚合性液晶(BASF公司製：商品名「Paliocolor LC242」，以下述式表示)10g、與針對該聚合性液晶化合物之光聚合引發劑(BASF公司制製：商品名「Irgacure 907」)3g溶解於甲苯40g，製備出液晶組成物(塗敷液)。液晶組成物之雙折射Δnxy為0.004。 [化學式15]

在聚對苯二甲酸乙二醇酯(PET)薄膜表面上用棒塗機塗敷上述液晶塗敷液，在90℃下加熱乾燥2分鐘，形成液晶層。在形成之液晶層上，使用金屬鹵素燈照射1mJ/cm² 之光，使該液晶層硬化，從而在PET薄膜上形成液晶硬化層。將液晶硬化層從PET薄膜剝離，而獲得相位差薄膜。所得相位差薄膜之面內相位差Re(550)為140nm，加濕相位差變化率為2%，厚度為2μm。進而，與實施例1相同方式使用所得相位差薄膜，而獲得附相位差層之偏光板。將所得相位差薄膜及附相位差層之偏光板供於與實施例1相同之評估。將結果示於表1。[Comparative Example 4] 10 g of a polymerizable liquid crystal (manufactured by BASF: trade name "Paliocolor LC242", represented by the following formula) exhibiting a nematic liquid crystal phase, and a photopolymerization initiator (manufactured by BASF) for the polymerizable liquid crystal compound Production: 3 g of trade name "Irgacure 907") was dissolved in 40 g of toluene to prepare a liquid crystal composition (coating liquid). The birefringence Δnxy of the liquid crystal composition was 0.004. [Chemical formula 15]

The above-mentioned liquid crystal coating liquid was applied on the surface of a polyethylene terephthalate (PET) film by a bar coater, and heated and dried at 90° C. for 2 minutes to form a liquid crystal layer. On the formed liquid crystal layer, a metal halide lamp was used to irradiate light of 1 mJ/cm ² to harden the liquid crystal layer, thereby forming a liquid crystal hardened layer on the PET film. The liquid crystal cured layer was peeled off from the PET film to obtain a retardation film. The in-plane retardation Re(550) of the obtained retardation film was 140 nm, the humidification retardation change rate was 2%, and the thickness was 2 μm. Furthermore, using the obtained retardation film in the same manner as in Example 1, a polarizing plate with a retardation layer was obtained. The obtained retardation film and the polarizing plate with retardation layer were used for 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，本發明實施例之相位差薄膜在加濕相位差變化率、耐候性及接著性之各方面均優異。推測這是藉由以特定延伸條件延伸包含特定聚碳酸酯樹脂之樹脂薄膜而實現的。進而可知，在加濕相位差變化之評估中，相較於具有易接著層之相位差薄膜，不具有易接著層之相位差薄膜抑制了加濕相位差變化(實施例1與比較例1之比較)。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相位差薄膜，能抑制在耐候性試驗中之色相變化。As is apparent from Table 1, the retardation films of the examples of the present invention are excellent in all aspects of the humidification retardation change rate, weather resistance, and adhesiveness. It is presumed that this is achieved by stretching a resin film containing a specific polycarbonate resin under specific stretching conditions. Furthermore, it can be seen that in the evaluation of the humidification retardation change, the retardation film without the easily bonding layer suppressed the humidification retardation change compared to the retardation film with the easily bonding layer (the difference between Example 1 and Comparative Example 1). Compare). 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 retardation film which does not contain an ultraviolet absorber.

產業上之可利用性 本發明實施形態之相位差薄膜及附相位差層之偏光板可適宜用於影像顯示裝置。industrial availability The retardation film and the polarizing plate with the retardation layer according to the embodiment of the present invention can be suitably used in an image display device.

(無)(none)

Claims (9)

一種相位差薄膜，係由雙折射Δnxy為0.015以上之樹脂構成者；其定向度為30%以上，正面相位差Re(550)為100nm~180nm或220nm~340nm，在65℃及90%RH下保持500小時後之相位差變化率為1.5%以下，於紫外區之耐候性試驗中之b值之變化率為1%以下。A retardation film, which is composed of a resin whose birefringence Δnxy is 0.015 or more; the degree of orientation is 30% or more, the frontal retardation Re(550) is 100nm~180nm or 220nm~340nm, at 65 ℃ and 90% RH The retardation change rate after holding for 500 hours is 1.5% or less, and the change rate of b value in the weather resistance test in the ultraviolet region is 1% or less. 如請求項1之相位差薄膜，其中前述樹脂包含聚碳酸酯系樹脂。The retardation film according to claim 1, wherein the resin includes a polycarbonate-based resin. 如請求項2之相位差薄膜，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 retardation 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之相位差薄膜，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 retardation 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 structure shown in the following (IIb), n=0, HOCH ₂ -R ¹ -CH ₂ OH (II) [Chemical formula 2]

. 如請求項1之相位差薄膜，其厚度為10μm~50μm。As claimed in claim 1, the retardation film has a thickness of 10 μm to 50 μm. 一種附相位差層之偏光板，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中任一項之相位差薄膜。A polarizing plate with a retardation layer, comprising a polarizer and a retardation film according to any one of claims 1 to 5, which is adhered to at least one side of the polarizer through an adhesive layer. 如請求項6之附相位差層之偏光板，其中於前述偏光件之至少單面透過前述接著劑層直接貼合有前述相位差薄膜。The polarizing plate with retardation layer according to claim 6, wherein the retardation film is directly attached to at least one side of the polarizer through the adhesive layer. 如請求項6之附相位差層之偏光板，其中前述接著劑層係由活性能量線硬化型接著劑組成物構成。The polarizing plate with retardation layer according to claim 6, wherein the adhesive layer is composed of an active energy ray-curable adhesive composition. 一種相位差薄膜之製造方法，係製造如請求項1至5中任一項之相位差薄膜之方法，且包含延伸由前述樹脂形成之樹脂薄膜之步驟。A method for producing a retardation film, which is a method for producing the retardation film as claimed in any one of claims 1 to 5, and includes a step of extending a resin film formed of the aforementioned resin.