TW201437265A - Production method of support with coating film - Google Patents
Production method of support with coating film Download PDFInfo
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- TW201437265A TW201437265A TW103111580A TW103111580A TW201437265A TW 201437265 A TW201437265 A TW 201437265A TW 103111580 A TW103111580 A TW 103111580A TW 103111580 A TW103111580 A TW 103111580A TW 201437265 A TW201437265 A TW 201437265A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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Abstract
Description
本發明關於一種帶塗佈膜的支撐物的製造方法，特別是涉及一種對使溶劑乾燥後的塗佈液照射活性能量線，使其硬化而形成塗佈膜的帶塗佈膜的支撐物的製造方法。 The present invention relates to a method for producing a support having a coating film, and more particularly to a support for a coated film which is formed by irradiating a coating liquid obtained by drying a solvent onto an active energy ray to form a coating film. Production method.
帶硬塗層(hard coat)的薄膜或帶防眩層的薄膜等是將塗佈液塗佈於薄膜上，對使溶劑乾燥後的塗佈液照射活性能量線而使其硬化來形成塗佈膜。 A hard coat film or a film with an antiglare layer is applied onto a film by applying a coating liquid, and the coating liquid obtained by drying the solvent is irradiated with an active energy ray to be cured to form a coating. membrane.
作為帶硬塗層的光學薄膜的用途，存在用作液晶監視器、電視機的偏光板等的保護層的情況。這時，在用於偏光板時，為了確保與黏接劑的密接性而進行皂化處理，然後利用黏接劑黏合於偏振器上。 As a use of an optical film with a hard coat layer, there exists a case where it is used as a protective layer of the polarizing plate of a liquid crystal monitor, and a television. At this time, when used for a polarizing plate, saponification treatment is performed in order to ensure adhesiveness with an adhesive, and it adheres to a polarizer with an adhesive.
如上所述用作液晶電視機或監視器的偏光板的保護層的帶硬塗層的光學薄膜中，由於因活性射線照射所引起的硬塗層的硬化收縮，會產生以塗佈面側為內側的捲曲，從而引起由偏光板加工的搬送時的曲折前進或貼合位置偏移、夾帶氣泡(bubble entrainment)所導致的產品良率下降。 In the hard-coated optical film used as the protective layer of the polarizing plate of the liquid crystal television or the monitor as described above, the hard coat shrinkage due to the irradiation of the active rays causes the coated side to be The curl on the inside causes a zigzag advancement during transfer by the polarizing plate, a misalignment of the bonding position, and a decrease in product yield due to bubble entrainment.
經照射活性能量線而硬化的塗佈膜雖然表面硬度高，但是存在塗佈膜的硬化收縮率大，從而捲曲增大的問題。再者，如果為了將捲曲縮小至實用程度以內而減小塗佈膜的膜厚，則無法獲得充分的表面硬度。 The coating film which is cured by irradiation with an active energy ray has a high surface hardness, but has a problem that the curing shrinkage rate of the coating film is large and curling is increased. Further, if the film thickness of the coating film is reduced in order to reduce the curl to a practical degree, sufficient surface hardness cannot be obtained.
因此，在專利文獻1中揭示了如下技術：藉由使用硬化後的體積收縮率為2%~10%的具有小體積收縮率的活性能量硬化性樹脂來作為硬塗層，可獲得捲曲少且具有優異的表面硬度的硬塗薄膜。 Therefore, Patent Document 1 discloses a technique in which, by using an active energy-curable resin having a small volume shrinkage ratio of 2% to 10% after shrinkage as a hard coat layer, a small amount of curl can be obtained. A hard coat film with excellent surface hardness.
然而，帶硬塗層的薄膜或帶防眩層的薄膜等的製造裝置是以盡可能小的尺寸加以構建。因此，設置照射活性能量線的裝置的空間受限，由此可設置的照射活性能量線的裝置的照射燈的數量也受限。 However, a manufacturing apparatus of a hard-coated film or an anti-glare film or the like is constructed in a size as small as possible. Therefore, the space in which the device for illuminating the active energy ray is limited is limited, and thus the number of illuminating lamps of the device that can illuminate the active energy ray can be limited.
但是，為了獲得所需的耐擦傷性，對塗佈膜的活性能量線的照射量需要達到某種程度(必要照射量)以上。然而，照射活性能量線的裝置的照射面積通常為固定，因此如果提高塗佈速度(搬送速度)，那麼活性能量線的照射時間縮短。 However, in order to obtain the desired scratch resistance, it is necessary to irradiate the active energy ray of the coating film to a certain extent (required irradiation amount) or more. However, the irradiation area of the apparatus that irradiates the active energy ray is usually fixed, and therefore, if the coating speed (transport speed) is increased, the irradiation time of the active energy ray is shortened.
當即便活性能量線的照射時間縮短，仍要照射必要照射量時，只有提高活性能量線的照射中的照度，但是尤其在塗佈膜的硬化的初期，當照射至塗佈膜的活性能量線的照度增大時，存在塗佈膜的硬化收縮加劇，從而捲曲增大的問題。 When the irradiation time of the active energy ray is shortened and the necessary irradiation amount is irradiated, only the illuminance in the irradiation of the active energy ray is increased, but especially in the initial stage of curing of the coating film, the active energy ray which is irradiated to the coating film When the illuminance is increased, there is a problem that the hardening shrinkage of the coating film is increased and the curl is increased.
因此，已提出了各種方案：例如在專利文獻2中提出了精心設計活性能量線的照射方式，或者在專利文獻3~專利文獻5中提出了精心設計捲曲的矯正方法。 Therefore, various proposals have been made. For example, Patent Document 2 proposes an irradiation method in which the active energy ray is carefully designed, or Patent Document 3 to Patent Document 5 proposes a method of correcting the curl.
[先前技術文獻] [Previous Technical Literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本專利特開2003-167314號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-167314
[專利文獻2]日本專利特開2006-15592號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2006-15592
[專利文獻3]日本專利第4011911號公報 [Patent Document 3] Japanese Patent No. 4011911
[專利文獻4]日本專利第2782795號公報 [Patent Document 4] Japanese Patent No. 2782795
但是，當如專利文獻1所述，使用體積收縮率小的活性能量硬化性樹脂時，通常表面硬度降低。而且，尤其在厚度薄的支撐物中，藉由如專利文獻2~專利文獻5所述的利用活性能量線的照射方式或捲曲的矯正方法的對策，則效果有限，捲曲依然成為大問題。 However, when an active energy curable resin having a small volume shrinkage ratio is used as described in Patent Document 1, the surface hardness generally decreases. In addition, the effect of the irradiation method using the active energy ray or the method of correcting the curl described in Patent Document 2 to Patent Document 5 is limited, and the curl is still a big problem.
本發明是由於如上所述的情況而開發，目的在於提供一種帶塗佈膜的支撐物的製造方法，在製造帶塗佈膜的支撐物時，不存在表面硬度降低等問題，可減少由塗佈膜的收縮所引起的薄膜寬度方向上的捲曲。 The present invention has been made in view of the above circumstances, and an object of the invention is to provide a method for producing a support having a coating film. When a support having a coating film is produced, there is no problem such as a decrease in surface hardness, and the coating can be reduced. Curl in the width direction of the film caused by shrinkage of the film.
為了達成所述目的，本發明提供一種帶塗佈膜的支撐物的製造方法，包括：搬送步驟，以20m/分以上的搬送速度搬送厚度為59μm以下的支撐物；塗佈步驟，將塗佈液塗佈於被搬送的支撐物上；乾燥步驟，使所塗佈的塗佈液的溶劑乾燥；以及硬化步驟，在使支撐物的長邊方向上的張力小於800N/m，且支撐物的長邊方向上的伸長率ε1與塗佈膜的收縮率ε2滿足ε1>ε2/4的狀態下，藉由照射多個燈的活性能量線的裝置，對使溶劑乾燥後的塗佈膜照射150mW/cm2以上的活性能量線，使其硬化而形成塗佈膜。 In order to achieve the above object, the present invention provides a method for producing a support having a coating film, comprising: a conveying step of conveying a support having a thickness of 59 μm or less at a conveying speed of 20 m/min or more; and a coating step of coating The liquid is applied to the supported support; the drying step is to dry the solvent of the applied coating liquid; and the hardening step is such that the tension in the longitudinal direction of the support is less than 800 N/m, and the support is In a state in which the elongation ε1 in the longitudinal direction and the shrinkage ratio ε2 of the coating film satisfy ε1>ε2/4, the coating film after drying the solvent is irradiated with 150 mW by means of irradiating the active energy ray of the plurality of lamps. The active energy ray of /cm 2 or more is hardened to form a coating film.
本申請發明人通過潛心研究發現，當對塗佈於以20m/分以上的速度被搬送的且厚度為59μm以下的支撐物上的塗佈膜，利用多個燈照射150mW/cm2以上的活性能量線而使其硬化時，設為如下狀態，即，使支撐物的長邊方向上的張力小於800N/m，且支撐物的長邊方向上的伸長率ε1與塗佈膜的收縮率ε2滿足ε1>ε2/4，照射活性能量線而使塗佈膜硬化，由此可降低由塗佈膜的收縮所引起的薄膜寬度方向上的捲曲。 The inventors of the present invention have found that the coating film applied to a support having a thickness of 59 μm or less which is applied at a speed of 20 m/min or more is irradiated with an activity of 150 mW/cm 2 or more by a plurality of lamps. When the energy line is hardened, the tension in the longitudinal direction of the support is less than 800 N/m, and the elongation ε1 in the longitudinal direction of the support and the shrinkage ratio ε2 of the coating film are set. When ε1>ε2/4 is satisfied, the active energy ray is irradiated to cure the coating film, whereby the curl in the film width direction caused by the shrinkage of the coating film can be reduced.
再者，ε1=TE/A(T：長邊方向上的張力(N/m)，A：支撐物的剖面積(m2)，E：支撐物的長邊方向上的彈性模量(Young's modulus) (GPa))。此外，ε2是根據多層層疊膜的彎曲理論而算出(參照日本機械學會論文集，59-563，A(1993)，1777.)。 Furthermore, ε1=TE/A (T: tension in the longitudinal direction (N/m), A: sectional area of the support (m 2 ), E: elastic modulus in the longitudinal direction of the support (Young's Modulus) (GPa)). Further, ε2 is calculated from the bending theory of the multilayer laminated film (refer to Proceedings of the Society of Mechanical Engineers, 59-563, A (1993), 1777.).
在本發明中，在硬化步驟中，優選的是在滿足ε1>ε2/3的狀態下對使溶劑乾燥後的塗佈膜照射活性能量線而進行硬化。 In the present invention, in the hardening step, it is preferred that the coating film obtained by drying the solvent is irradiated with an active energy ray to be cured while satisfying ε1>ε2/3.
本發明中，優選的是長邊方向上的張力為350(N/m)以上。 In the present invention, it is preferable that the tension in the longitudinal direction is 350 (N/m) or more.
如果長邊方向上的張力為350(N/m)以上，那麼可進一步減少由塗佈膜收縮(塗膜收縮率)所引起的寬度方向上的捲曲。如果提高長邊方向上的張力，那麼在薄層的支撐物中會產生褶皺，從而在硬化步驟中產生故障，因此需要使長邊方向上的張力維持在小於800N/m的程度。 If the tension in the longitudinal direction is 350 (N/m) or more, the curl in the width direction caused by shrinkage of the coating film (shrinkage rate of the coating film) can be further reduced. If the tension in the longitudinal direction is increased, wrinkles are generated in the support of the thin layer, and a failure occurs in the hardening step, so it is necessary to maintain the tension in the longitudinal direction to a level of less than 800 N/m.
可藉由提高長邊方向上的張力來減少由塗佈膜收縮所引起的寬度方向上的捲曲的機理尚不明確。但是可認為，當照射活性能量線時，以高張力在伸長方向(長邊方向)上施加有應力的支撐物在塗佈液硬化後，在變為低張力時會收縮，由此與利用活性能量線進行硬化時所產生的寬度方向上的收縮應力相抵消。 The mechanism by which the tension in the width direction caused by the shrinkage of the coating film can be reduced by increasing the tension in the longitudinal direction is not clear. However, it is considered that when the active energy ray is irradiated, the support to which the stress is applied in the elongation direction (longitudinal direction) with high tension is shrunk when the coating liquid is hardened, and becomes a low tension, thereby utilizing the activity. The shrinkage stress in the width direction generated when the energy line is hardened is offset.
再者，當塗佈速度加快至20m/分以上時，為了以有限的活性能量線的照射燈數獲得所需的照射量，需要提高每個燈的輸出。這時照射至塗佈膜的照度增強，硬膜反應急劇推進，因此收縮應力增大，寬邊方向上的捲曲增大。在本發明中，即便在這種條件下，藉由提高長邊方向上的張力，也具有減少寬邊方向捲曲的效果。 Further, when the coating speed is increased to 20 m/min or more, in order to obtain a desired irradiation amount with a limited number of irradiation lamps of the active energy ray, it is necessary to increase the output of each lamp. At this time, the illuminance which is irradiated to the coating film is enhanced, and the hard film reaction is rapidly advanced, so that the shrinkage stress is increased and the curl in the widthwise direction is increased. In the present invention, even under such conditions, the effect of reducing the curl in the wide-side direction is enhanced by increasing the tension in the longitudinal direction.
本發明在支撐物的厚度薄的情況下特別有效，在支撐物的厚度為40μm以下時減少捲曲的效果尤其大，在支撐物的厚度為25μm以下的情況下，減少捲曲的效果更大。 The present invention is particularly effective in the case where the thickness of the support is small, and the effect of reducing curl is particularly large when the thickness of the support is 40 μm or less, and the effect of reducing curl is greater when the thickness of the support is 25 μm or less.
在本發明中，優選的是支撐物為塑料薄膜。 In the present invention, it is preferred that the support be a plastic film.
根據本發明的帶塗佈膜的支撐物的製造方法，可減少由塗佈膜的收縮所引起的薄膜寬度方向上的捲曲。 According to the method for producing a support with a coating film of the present invention, curl in the width direction of the film caused by shrinkage of the coating film can be reduced.
10‧‧‧光學薄膜的製造裝置 10‧‧‧Manufacturer for optical film
12‧‧‧薄膜捲材 12‧‧‧ film coil
14‧‧‧送出機 14‧‧‧Send machine
16‧‧‧薄膜基材 16‧‧‧film substrate
18‧‧‧導輥 18‧‧‧guide roller
20‧‧‧除塵器 20‧‧‧Dust collector
22‧‧‧塗佈裝置(塗佈步驟) 22‧‧‧ Coating device (coating step)
24‧‧‧乾燥步驟 24‧‧‧ drying step
26‧‧‧硬化步驟 26‧‧‧ Hardening step
30‧‧‧捲繞機 30‧‧‧Winding machine
圖1是表示帶塗佈膜的薄膜的生產線的整體構成的概念圖。 Fig. 1 is a conceptual view showing the overall configuration of a production line of a film with a coating film.
圖2是說明本發明的帶塗佈膜的支撐物的製造方法的曲線圖。 Fig. 2 is a graph for explaining a method of producing a support with a coating film of the present invention.
以下，根據附圖，說明本發明的帶塗佈膜的支撐物的製造方法的優選實施方式。 Hereinafter, a preferred embodiment of the method for producing a support with a coating film of the present invention will be described with reference to the accompanying drawings.
圖1是表示帶塗佈膜的薄膜的製造裝置的一例的概略圖。 FIG. 1 is a schematic view showing an example of a manufacturing apparatus of a film with a coating film.
藉由送出機14，從薄膜捲材12送出長條狀的薄膜基材16(也包括形成有某些功能層的薄膜基材)。薄膜基材16的移動速度例如可設為0.1m/秒~1.5m/秒。 The elongated film substrate 16 (including the film substrate on which certain functional layers are formed) is fed from the film web 12 by the feeder 14. The moving speed of the film substrate 16 can be, for example, 0.1 m/sec to 1.5 m/sec.
薄膜基材16經導輥18引導而送入至除塵器20。除塵器20可去除附著於薄膜基材16的表面上的灰塵。在除塵器20的下游，設置有塗佈單元即擠壓(extrusion)方式的塗佈裝置22，可將塗佈液塗佈至纏繞於支承輥(back-up roller)上的薄膜基材16上。 The film substrate 16 is guided by the guide roller 18 and sent to the dust remover 20. The dust remover 20 can remove dust adhering to the surface of the film substrate 16. Downstream of the precipitator 20, there is provided a coating unit, that is, an extrusion type coating device 22, which can apply a coating liquid onto a film substrate 16 wound on a back-up roller. .
作為塗佈步驟22，也可以使用浸塗(dip coat)法、氣刀塗佈(air knife coat)法、幕式塗佈(curtain coat)法、斜板式塗佈(slide coat)法、輥塗(roller coat)法、繞線棒塗佈(wire bar coat)法、凹版塗佈(gravure coat)、微型凹版(micro gravure)塗佈法等。塗佈裝置22設置於潔淨室(clean room)等清潔的環境中即可。這時，清潔度優選的是1000級以下，更優選的是100級以下，進而更優選的是10級以下。 As the coating step 22, a dip coating method, an air knife coating method, a curtain coating method, a slide coating method, and a roll coating method may be used. (roller coat) method, wire bar coat method, gravure coat, micro gravure coating method, and the like. The coating device 22 may be installed in a clean environment such as a clean room. At this time, the degree of cleanliness is preferably 1000 or less, more preferably 100 or less, and still more preferably 10 or less.
在塗佈步驟22的下游，設置有乾燥步驟24。在乾燥步驟24 中，對所形成的塗佈液的表面利用乾燥風使溶劑蒸發，使大部分溶劑蒸發而使塗佈液乾燥。 Downstream of the coating step 22, a drying step 24 is provided. In the drying step 24 In the surface of the coating liquid to be formed, the solvent is evaporated by dry air, and most of the solvent is evaporated to dry the coating liquid.
在所述乾燥步驟24中，在規定溫度(例如，60℃)下使塗佈液的溶劑蒸發。例如，也可以根據溶劑的沸點，例如，在40℃~120℃左右的溫度下使塗佈液乾燥。 In the drying step 24, the solvent of the coating liquid is evaporated at a predetermined temperature (for example, 60 ° C). For example, the coating liquid may be dried at a temperature of, for example, about 40 ° C to 120 ° C depending on the boiling point of the solvent.
作為乾燥步驟24中所使用的乾燥裝置，並沒有特別限定，可使用熱風乾燥裝置(例如，日本專利特開2001-314799中所記載的乾燥裝置等)等。 The drying device used in the drying step 24 is not particularly limited, and a hot air drying device (for example, a drying device described in JP-A-2001-314799) or the like can be used.
在乾燥步驟的下游，作為塗佈液的硬化步驟26，藉由活性能量線(紫外線或電子束等)，而使塗佈液硬化或交聯。作為硬化方法，可根據硬化性化合物的種類來選擇，例如，優選使用紫外線照射裝置。藉由所述紫外線照射，可形成所需的硬化、交聯。 Downstream of the drying step, as a hardening step 26 of the coating liquid, the coating liquid is hardened or crosslinked by an active energy ray (ultraviolet rays, electron beams, or the like). The curing method can be selected depending on the kind of the curable compound, and for example, an ultraviolet irradiation device is preferably used. By the ultraviolet irradiation, the desired hardening and crosslinking can be formed.
紫外線照射可使用汞燈、金屬鹵化物燈(metal halide lamp)等各種市售的紫外線照射燈來實施。再者，還優選的是在實施紫外線照射時，在使氧氣濃度降低的環境下進行交聯反應或聚合反應。這時，優選的是在氧氣濃度為10體積%以下的環境下實施紫外線照射。藉由在氧氣濃度為10體積%以下的環境下形成，可形成物理強度及耐化學品性優異的硬化層。更優選的是在氧氣濃度為6體積%以下的環境下藉由游離輻射硬化性化合物的交聯反應或聚合反應來形成硬化層，更優選的是氧氣濃度為2體積%以下，特別優選的是氧氣濃度為1體積%以下，最優選的是氧氣濃度為0.1體積%以下。 The ultraviolet irradiation can be carried out using various commercially available ultraviolet irradiation lamps such as a mercury lamp or a metal halide lamp. Further, it is also preferred to carry out a crosslinking reaction or a polymerization reaction in an environment where the oxygen concentration is lowered during the ultraviolet irradiation. At this time, it is preferred to carry out ultraviolet irradiation in an environment having an oxygen concentration of 10% by volume or less. By forming in an environment having an oxygen concentration of 10% by volume or less, a hardened layer excellent in physical strength and chemical resistance can be formed. More preferably, the hardened layer is formed by a crosslinking reaction or a polymerization reaction of the free radiation curable compound in an environment having an oxygen concentration of 6 vol% or less, more preferably an oxygen concentration of 2% by volume or less, and particularly preferably The oxygen concentration is 1% by volume or less, and most preferably the oxygen concentration is 0.1% by volume or less.
作為使氧氣濃度為10體積%以下的方法，優選的是利用其它氣體對大氣(氮氣濃度約為79體積%，氧氣濃度約為21體積%)進行置換，特別優選的是利用氮氣進行置換(氮氣清洗(nitrogen purge))。 As a method of setting the oxygen concentration to 10% by volume or less, it is preferred to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with other gases, and it is particularly preferable to replace with nitrogen (nitrogen gas). Nitrogen purge).
並且，還優選的是在利用光化射線進行硬化時，對被照射的塗佈液的溫度進行控制。作為對塗佈液的放射線照射時的溫度進行控制的方法，有對照射光化射線的室內的環境溫度進行控制的方法，將捲材設置於與照射之側相反之側，藉由所述捲材的溫度來進行控制的方法等。 Further, it is also preferred to control the temperature of the applied coating liquid when it is cured by actinic rays. As a method of controlling the temperature at the time of radiation irradiation of the coating liquid, there is a method of controlling the ambient temperature of the room in which the actinic ray is irradiated, and the coil is placed on the side opposite to the side irradiated by the coil. The temperature to control the method, etc.
將塗佈液已硬化的帶塗佈膜的薄膜，藉由捲繞機30纏繞成捲狀。 The film with a coating film which has been hardened by the coating liquid is wound into a roll shape by the winder 30.
在如上所述而製造的帶塗佈膜的薄膜中，在本實施形態中，當對塗佈於以20m/分以上的速度被搬送且厚度為59μm以下的支撐物(薄膜基材16)上的塗佈膜，利用多個燈照射150mW/cm2以上的活性能量線而使其硬化時，在如下狀態下照射活性能量線而使其硬化，即，使支撐物的長邊方向上的張力小於800(N/m)，並且在將支撐物的長邊方向上的伸長率設為ε1，將塗佈膜的收縮率設為ε2時，滿足ε1>ε2/4。 In the film with a coating film produced as described above, in the present embodiment, it is applied to a support (film substrate 16) which is conveyed at a speed of 20 m/min or more and has a thickness of 59 μm or less. When the coating film is cured by irradiating an active energy ray of 150 mW/cm 2 or more with a plurality of lamps, the active energy ray is irradiated and cured in the following state, that is, the tension in the longitudinal direction of the support is obtained. When the elongation of the coating film is ε1 and the shrinkage ratio of the coating film is ε2, it is less than 800 (N/m), and ε1>ε2/4 is satisfied.
藉由在所述條件下進行製造，即使對以20m/分以上的高速度被搬送且厚度為59μm以下的薄支撐物，進行150mW/cm2以上的活性能量線的高照射，也可以減少由塗佈膜的收縮所引起的薄膜寬度方向上的捲曲。 By performing the production under the above conditions, even if a thin support having a thickness of 59 μm or less is conveyed at a high speed of 20 m/min or more, high-intensity irradiation of an active energy ray of 150 mW/cm 2 or more can be reduced. Curl in the width direction of the film caused by shrinkage of the coating film.
再者，藉由改變賦予至活性能量線照射裝置的輸出、或活性能量線照射裝置與塗佈膜的距離，可改變照射至塗佈膜的活性能量線的照度。關於活性能量線的照度，需要以不會因塗佈膜收縮而引起斷裂的強度進行照射，優選的是800mW/cm2以下。 Further, the illuminance of the active energy ray irradiated to the coating film can be changed by changing the output given to the active energy ray irradiation device or the distance between the active energy ray irradiation device and the coating film. The illuminance of the active energy ray is required to be irradiated with an intensity that does not cause breakage due to shrinkage of the coating film, and is preferably 800 mW/cm 2 or less.
而且，ε1=TE/A(T：長邊方向上的張力(N/m)，A：支撐物的剖面積(m2)，E：支撐物的長邊方向上的彈性模量(GPa))。並且，ε2是根據多層層疊膜的彎曲理論而算出(參照日本機械學會論文集，59-563，A(1993)，1777.)。 Further, ε1 = TE / A (T: tension in the longitudinal direction (N / m), A: sectional area (m 2 ) of the support, E: elastic modulus (GPa) in the longitudinal direction of the support ). Further, ε2 is calculated from the bending theory of the multilayer laminated film (see Proceedings of the Society of Mechanical Engineers, 59-563, A (1993), 1777.).
再者，在本實施形態中，在硬化步驟中，更優選的是在滿足ε1>ε2/3的狀態下對使溶劑乾燥後的塗佈膜照射活性能量線而進行硬化。 Furthermore, in the present embodiment, in the curing step, it is more preferable that the coating film obtained by drying the solvent is irradiated with an active energy ray and cured in a state where ε1 > ε2 / 3 is satisfied.
而且，在本實施形態中，在支撐物(薄膜基材)的厚度為40μm以下時減少捲曲的效果尤其大，當支撐物的厚度為25μm以下時，減少捲曲的效果更大。當支撐物(薄膜基材)的厚度薄時，本實施形態尤其有效。再者，支撐物厚度如果過薄，那麼有可能在拉力(tension)的作用下發生斷裂，從而優選的是5μm以上。 Further, in the present embodiment, the effect of reducing curl when the thickness of the support (film substrate) is 40 μm or less is particularly large, and when the thickness of the support is 25 μm or less, the effect of reducing curl is greater. This embodiment is particularly effective when the thickness of the support (film substrate) is thin. Further, if the thickness of the support is too thin, it is likely to be broken by the tension, and it is preferably 5 μm or more.
此外，本實施形態中，在照射活性能量線時，長邊方向上的張力T優選的是350(N/m)以上，並且需要設為小於800(N/m)。 Further, in the present embodiment, when the active energy ray is irradiated, the tension T in the longitudinal direction is preferably 350 (N/m) or more, and is required to be less than 800 (N/m).
藉由長邊方向上的張力T設為350(N/m)以上，可進一步減少由塗佈膜收縮所引起的寬度方向上的捲曲。 By setting the tension T in the longitudinal direction to 350 (N/m) or more, it is possible to further reduce the curl in the width direction caused by the shrinkage of the coating film.
可藉由提高長邊方向上的張力來減少由塗佈膜收縮所引起的寬度方向上的捲曲的機理尚不明確，但是可認為，當照射活性能量線時，以高張力在伸長方向(長邊方向)上施加有應力的支撐物在塗佈液硬化後，在變為低張力時會收縮，由此與利用活性能量線進行硬化時所產生的寬度方向上的收縮應力相抵消。 The mechanism for reducing the curl in the width direction caused by the shrinkage of the coating film by increasing the tension in the longitudinal direction is not clear, but it can be considered that when the active energy ray is irradiated, the direction of elongation is high with a high tension (long The support to which the stress is applied in the side direction is shrunk when the coating liquid is hardened and becomes low tension, thereby canceling the shrinkage stress in the width direction which is generated when hardened by the active energy ray.
再者，當塗佈速度加快至20m/分以上時，為了以有限的活性能量線的照射燈數獲得所需的照射量，需要提高每個燈的輸出。這時照射至塗佈膜的照度增強，硬膜反應急劇推進，因此收縮應力增大，寬邊方向捲曲增大。在本實施形態中，即便在這種條件下，藉由提高長邊方向上的張力，也具有減少寬邊方向捲曲的效果。 Further, when the coating speed is increased to 20 m/min or more, in order to obtain a desired irradiation amount with a limited number of irradiation lamps of the active energy ray, it is necessary to increase the output of each lamp. At this time, the illuminance which is irradiated to the coating film is enhanced, and the hard film reaction is rapidly advanced, so that the shrinkage stress is increased and the curl in the wide-side direction is increased. In the present embodiment, even under such conditions, the effect of reducing the curl in the wide-side direction is improved by increasing the tension in the longitudinal direction.
以下，對本發明的塗佈液等進行說明。 Hereinafter, the coating liquid and the like of the present invention will be described.
本發明的塗佈液中，作為紫外線硬化性化合物，是含有藉由活性能量線(紫外線)而反應的官能基的化合物，可使用能夠藉由活性能 量線進行交聯而形成樹脂(特別是硬化樹脂或交聯樹脂)的各種紫外線硬化性化合物。 In the coating liquid of the present invention, the ultraviolet curable compound is a compound containing a functional group reactive by an active energy ray (ultraviolet rays), and can be used by active energy. The amount of the wire is crosslinked to form various ultraviolet curable compounds of a resin (particularly, a cured resin or a crosslinked resin).
作為紫外線硬化性化合物，可例示能夠藉由光化射線(紫外線)而進行硬化的紫外線硬化性化合物(紫外線硬化性單體、低聚物、預聚物等紫外線硬化性化合物等)等。再者，也可以是紫外線硬化性單體、低聚物或低分子量體。有時將紫外線硬化性樹脂等紫外線硬化性化合物僅稱為“紫外線硬化性樹脂”。紫外線硬化性化合物可單獨使用，或者組合使用兩種以上。 The ultraviolet curable compound which can be cured by actinic rays (ultraviolet rays) (an ultraviolet curable compound such as an ultraviolet curable monomer, an oligomer or a prepolymer) or the like can be exemplified. Further, it may be an ultraviolet curable monomer, an oligomer or a low molecular weight body. The ultraviolet curable compound such as an ultraviolet curable resin may be simply referred to as "ultraviolet curable resin". The ultraviolet curable compounds may be used singly or in combination of two or more.
紫外線硬化性化合物通常含有紫外線硬化性基，例如，聚合性基(乙烯基、烯丙基、(甲基)丙烯醯基等)或感光性基(肉桂醯氧基等)，特別優選的是含有聚合性基的紫外線硬化性化合物(例如，單量體、低聚物(或樹脂，特別是低分子量樹脂))。 The ultraviolet curable compound usually contains an ultraviolet curable group, and is, for example, a polymerizable group (such as a vinyl group, an allyl group or a (meth)acryl fluorenyl group) or a photosensitive group (such as a cinnamyloxy group), and particularly preferably contains A polymerizable group of ultraviolet curable compounds (for example, a monolith, an oligomer (or a resin, particularly a low molecular weight resin)).
含有聚合性基的紫外線硬化性化合物中，作為單量體，例如可例示：單官能性單量體[(甲基)丙烯酸酯等(甲基)丙烯酸系單量體，例如，(甲基)丙烯酸烷基酯((甲基)丙烯酸甲脂等C1-6(甲基)丙烯酸烷基脂等)、(甲基)丙烯酸環烷基脂、含有交聯環式烴基的(甲基)丙烯酸酯((甲基)丙烯酸異莰基脂、(甲基)丙烯酸金剛烷基脂等)、(甲基)丙烯酸縮水甘油基脂；乙酸乙烯酯等乙烯酯、乙烯吡咯烷酮等乙烯系單量體等]、包括至少兩個聚合性不飽和鍵的多官能性單量體[乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯等亞烷基二醇二(甲基)丙烯酸酯；二乙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、聚氧四亞甲基二醇二(甲基)丙烯酸酯等(聚)氧化亞烷基二醇二(甲基)丙烯酸酯；三環癸烷二甲醇二(甲基)丙烯酸酯、金剛烷二(甲基)丙烯酸酯等含有交聯環式烴基的二(甲基)丙烯酸酯；三羥甲基丙 烷三(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯等含有3個~6個左右的聚合性不飽和鍵的多官能性單量體]。 In the ultraviolet curable compound containing a polymerizable group, a monofunctional one may, for example, be a monofunctional monomeric [meth)acrylic acid monovalent, such as (meth) An alkyl acrylate (such as a C1-6 (meth)acrylic acid alkyl ester such as methyl (meth) acrylate), a (meth)acrylic acid cycloalkyl ester, or a (meth) acrylate containing a crosslinked cyclic hydrocarbon group. ((meth)acrylic acid isodecyl lipid, (meth)acrylic acid adamantyl ester, etc.), (meth)acrylic acid glycidyl lipid; vinyl acetate, vinyl acetate, etc., vinyl monovalent body such as vinylpyrrolidone, etc.] a polyfunctional monolith comprising at least two polymerizable unsaturated bonds [ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, new An alkylene glycol di(meth)acrylate such as pentanediol di(meth)acrylate or hexanediol di(meth)acrylate; diethylene glycol di(meth)acrylate, dipropylene glycol II (poly)oxyalkylene glycol di(meth)acrylate such as (meth) acrylate or polyoxytetramethylene glycol di(meth)acrylate; tricyclic Di (meth) acrylate dimethanol di (meth) acrylate, adamantane di (meth) acrylate containing a crosslinked cyclic hydrocarbon group; trimethylolpropane Alkane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate A polyfunctional monomeric body containing three to six or more polymerizable unsaturated bonds.
紫外線硬化性化合物可與光聚合起始劑組合使用。 The ultraviolet curable compound can be used in combination with a photopolymerization initiator.
作為光聚合起始劑，例如可使用苯乙酮類或苯丙酮類、苯偶醯類、苯偶姻(benzoin)類、二苯甲酮類、噻噸酮類、醯基膦氧化物類等。光聚合起始劑的含量可相對於硬化性化合物而設為0.1重量份~20重量份左右。 As the photopolymerization initiator, for example, acetophenone or propiophenone, benzoin, benzoin, benzophenone, thioxanthone, mercaptophosphine oxide, or the like can be used. . The content of the photopolymerization initiator may be from about 0.1 part by weight to about 20 parts by weight based on the curable compound.
作為所使用的溶劑，可根據所使用的聚合物、硬化性化合物等的種類及溶解性來選擇，在為混合溶劑的情況下，只要至少一種為可均勻地溶解固體成分(多個聚合物及硬化性化合物、反應起始劑、其它添加劑)的溶劑即可。作為此種溶劑，例如可例示酮類(丙酮、甲基乙基酮、甲基異丁基酮(methyl isobutyl ketone)、環己酮等)、醚類(二噁烷、四氫呋喃等)、脂肪族烴類(己烷等)、脂環式烴類(環己烷等)、芳香族烴類(甲苯、二甲苯等)、鹵化碳類(二氯甲烷、二氯乙烷等)、酯類(乙酸甲酯、乙酸乙酯、乙酸丁酯等)、水、醇類(乙醇、異丙醇、丁醇、環己醇等)、溶纖劑類(甲基溶纖劑、乙基溶纖劑等)、乙酸溶纖劑類、亞碸類(二甲基亞碸等)、醯胺類(二甲基甲醯胺、二甲基乙醯胺等)等。這些溶劑可單獨使用，或者組合使用兩種以上。 The solvent to be used can be selected depending on the type and solubility of the polymer or curable compound to be used, and in the case of a mixed solvent, at least one of them can uniformly dissolve the solid component (multiple polymers and The solvent of the curable compound, the reaction initiator, and other additives may be used. Examples of such a solvent include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), and aliphatic groups. Hydrocarbons (such as hexane), alicyclic hydrocarbons (such as cyclohexane), aromatic hydrocarbons (such as toluene and xylene), halogenated carbons (such as dichloromethane and dichloroethane), and esters (such as Methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolve (methyl cellosolve, ethyl cellosolve) Etc.), cellosolve acetate, sulfonium (dimethyl hydrazine, etc.), guanamine (dimethylformamide, dimethylacetamide, etc.). These solvents may be used singly or in combination of two or more.
並且，也可以根據薄膜基材的種類，選擇不使薄膜基材溶解、侵蝕或膨脹的溶劑。例如，當使用三乙醯纖維素薄膜作為薄膜基材時，例如可優選使用四氫呋喃、甲基乙基酮、異丙醇、甲苯等作為塗佈液的溶劑。 Further, depending on the type of the film substrate, a solvent that does not dissolve, erode, or swell the film substrate may be selected. For example, when a triacetonitrile cellulose film is used as the film substrate, for example, tetrahydrofuran, methyl ethyl ketone, isopropyl alcohol, toluene or the like can be preferably used as the solvent of the coating liquid.
而且，作為溶質，還可以使用填充劑(例如，二氧化矽 (silica)、含氟粒子(氟化鎂、氟化鈣、氟化鋇)等無機化合物、有機微粒子等)、界面活性劑等。 Moreover, as a solute, a filler (for example, cerium oxide) can also be used. (silica), inorganic compounds such as fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride, organic fine particles, etc.), surfactants, and the like.
再者，防眩性的塗佈膜形成用液可藉由對溶劑、粒子、樹脂材料、紫外硬化性化合物、光聚合起始劑進行調整來製作。 In addition, the anti-glare coating film forming liquid can be produced by adjusting a solvent, a particle, a resin material, an ultraviolet curable compound, and a photopolymerization initiator.
作為可使用的粒子並沒有特別限制，但是特別優選的是二氧化矽粒子、氧化鋯粒子。粒徑優選的是1μm~15μm左右。 The particles which can be used are not particularly limited, but particularly preferred are cerium oxide particles and zirconia particles. The particle diameter is preferably about 1 μm to 15 μm.
再者，可使用的紫外硬化性化合物、光聚合起始劑及溶劑與上述相同。 Further, the ultraviolet curable compound, the photopolymerization initiator, and the solvent which can be used are the same as described above.
[實施例] [Examples]
以下，舉出實施例對本發明進行更具體的說明，但是本發明的範圍不應藉由以下所示的具體例來作限定性的解釋。 The present invention will be more specifically described by the following examples, but the scope of the present invention should not be construed as limited by the specific examples shown below.
利用在塑料薄膜上設置硬塗層的示例，進行本發明的說明。 The description of the present invention is made using an example in which a hard coat layer is provided on a plastic film.
利用模塗機(die coater)塗佈9μm的厚度的塗佈液A，並進行60℃、1分鐘的乾燥之後照射照射量為300mJ/cm2的紫外(ultraviolet，UV)光，使其成硬膜，而製作硬塗薄膜。硬化後的層厚為5μm。塑料薄膜的搬送速度設為20m/分。 The coating liquid A having a thickness of 9 μm was applied by a die coater, and dried at 60 ° C for 1 minute, and then irradiated with ultraviolet (UV) light having an irradiation amount of 300 mJ/cm 2 to make it hard. The film is made into a hard coated film. The layer thickness after hardening was 5 μm. The conveying speed of the plastic film was set to 20 m/min.
作為塗佈液A，是將二季戊四醇五丙烯酸酯與二季戊四醇六丙烯酸酯的混合物(DPHA，日本化藥股份有限公司製)1000g、以及季戊四醇三丙烯酸酯(日本化藥股份有限公司製“PET-30”(商品名))1500g加以混合，而溶解於甲基乙基酮2500g中。然後，混合IRGACURE 127(IRGACURE為注冊商標，日本汽巴(Ciba Japan)股份有限公司製)7.5g而製備塗佈液A。 The coating liquid A is a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), 1000 g, and pentaerythritol triacrylate ("PET-", manufactured by Nippon Kayaku Co., Ltd. 30" (trade name)) 1500 g was mixed and dissolved in 2500 g of methyl ethyl ketone. Then, 7.5 g of IRGACURE 127 (IRGACURE is a registered trademark, manufactured by Ciba Japan Co., Ltd.) was mixed to prepare a coating liquid A.
作為塑料薄膜，是使用厚度為15μm、50μm的聚對苯二甲酸乙二醇酯(polyethylene terephthalate，PET)薄膜(例如東麗公司製的 LUMIRROR(LUMIRROR為注冊商標))、以及厚度為25μm、40μm、60μm、80μm的三乙醯纖維素(triacetyl cellulose，TAC)薄膜(富士軟片公司製)。 As a plastic film, a polyethylene terephthalate (PET) film having a thickness of 15 μm and 50 μm is used (for example, manufactured by Toray Industries, Inc.). LUMIRROR (LUMIRROR is a registered trademark)), and a triacetyl cellulose (TAC) film (manufactured by Fujifilm Co., Ltd.) having a thickness of 25 μm, 40 μm, 60 μm, and 80 μm.
再者，硬塗薄膜的捲曲的曲率的計算方法如下。首先，從硬塗薄膜切取長邊方向上的長度為5mm的狹縫狀的薄膜。其次，向寬度方向以150mm間隔切割狹縫狀的薄膜，獲得多個測定薄膜(縱長5mm，橫長150mm)。然後，在平臺上，以硬塗層朝向下側的方式而配置測定薄膜。這時，測定薄膜從橫向觀察時(從厚度方向觀察時)，以呈向上凸出的方式而彎曲成圓弧狀。測定連結橫方向上的測定薄膜的兩端的線段的長度L、以及從平臺到測定薄膜中的最高位置的高度H。然後，根據長度L及高度H，算出層疊薄膜的寬度方向上的捲曲的曲率半徑。並且，關於各支撐物的長邊方向彈性模量，PET支撐物為4GPa，TAC支撐物為3.6GPa。 Further, the calculation method of the curvature of the curl of the hard coat film is as follows. First, a slit-shaped film having a length of 5 mm in the longitudinal direction was cut out from the hard coat film. Next, a slit-shaped film was cut at intervals of 150 mm in the width direction to obtain a plurality of measurement films (length 5 mm, width 150 mm). Then, on the stage, the measurement film was placed with the hard coat layer facing the lower side. At this time, when the film was observed from the lateral direction (when viewed from the thickness direction), the film was bent in an arc shape so as to protrude upward. The length L of the line segment connecting the both ends of the measurement film in the lateral direction and the height H from the platform to the highest position in the measurement film were measured. Then, the radius of curvature of the curl in the width direction of the laminated film was calculated from the length L and the height H. Further, regarding the longitudinal elastic modulus of each support, the PET support was 4 GPa and the TAC support was 3.6 GPa.
將在所述條件下，對UV照射時的拉力進行變更時的實驗結果示於表1中。並且，將所述實驗中的支撐物的長邊方向上的伸長率ε1與塗佈膜的收縮率(塗膜收縮率)ε2的關係繪成曲線圖而示於圖2。再者，表1中所記載的ε2的值是以帶塗佈膜的薄膜的曲率半徑相一致的方式，對ε2進行各種改變而得出。 The experimental results when the tensile force at the time of UV irradiation was changed under the above conditions are shown in Table 1. Further, the relationship between the elongation ε1 in the longitudinal direction of the support in the experiment and the shrinkage ratio (coating film shrinkage ratio) ε2 of the coating film is plotted in FIG. 2 . In addition, the value of ε2 shown in Table 1 is obtained by variously changing ε2 such that the radius of curvature of the film with a coating film coincides.
如由表1所知，藉由增加照射時的拉力，使ε1/ε2大於1/4，可確認塗佈膜的曲率半徑增大，塗佈膜的收縮受到抑制。而且可知，當增加支撐物的厚度，或減少硬膜時的拉力時，塗膜收縮率的抑制並不充分。 As is known from Table 1, by increasing the tensile force at the time of irradiation, ε1/ε2 was made larger than 1/4, and it was confirmed that the radius of curvature of the coating film was increased, and shrinkage of the coating film was suppressed. Further, it is understood that when the thickness of the support is increased or the tensile force at the time of the hard film is reduced, the suppression of the shrinkage rate of the coating film is not sufficient.
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| JP2013073945A JP2014198282A (en) | 2013-03-29 | 2013-03-29 | Method of producing coating-film-provided support |
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| JP (1) | JP2014198282A (en) |
| KR (1) | KR20140118923A (en) |
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| JP2782795B2 (en) * | 1989-06-16 | 1998-08-06 | 大日本印刷株式会社 | Manufacturing method of composite film |
| JP4649892B2 (en) * | 2004-07-01 | 2011-03-16 | コニカミノルタオプト株式会社 | Method for producing hard coat film |
| JP2009280645A (en) * | 2008-05-20 | 2009-12-03 | Toyobo Co Ltd | Biaxial stretched polyethylene terephthalate based resin film |
| JP2010064013A (en) * | 2008-09-11 | 2010-03-25 | Toppan Printing Co Ltd | Method of manufacturing lamination film, and apparatus for manufacturing lamination film |
| WO2010041520A1 (en) * | 2008-10-10 | 2010-04-15 | コニカミノルタオプト株式会社 | Hardcoat film, process for producing same, and antireflection film comprising same |
| JP2012159691A (en) * | 2011-01-31 | 2012-08-23 | Fujifilm Corp | Antiglare film, polarizing plate, image display device, and method for manufacturing antiglare film |
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| KR20140118923A (en) | 2014-10-08 |
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