KR101968786B1 - Laminate film and manufacturing method thereof - Google Patents

Abstract

The laminated film has a first base material, a first coating film, a second coating film, and first and second base pairs. The first coating film is formed by applying the first coating liquid onto the first base material. The second coating film is formed by applying the second coating liquid onto the first coating film. The first pair of ridges and the second pair of ridges protrude from both ends in the width direction of the first coated film and the second coated film. Either one of the first pair of stones and the second pair of stones is on the other side of the other. The first pair of ridges and the second pair of ridges are at least 1 탆 higher than the film surface in the widthwise center of the laminated film.

Description

TECHNICAL FIELD [0001] The present invention relates to a laminated film,

The present invention relates to a laminated film and a manufacturing method thereof.

Recently, demand for thin and transparent laminated films as optical materials has been increasing. Examples of the optical material include an optical reflection member of a heat shield member for automobiles and building materials, a protective film of a polarizing plate of a liquid crystal display, an optical compensation film such as a retardation plate, a plastic substrate, a photographic support, a moving cell or an optical filter, Film and the like.

Such a laminated film is obtained by forming a film on a transparent film base made of, for example, cellulose triacetate (TAC) serving as a support. As a main film-forming method, there is known a vacuum film-forming method such as sputtering or plasma CVD, a coating film-forming method in which a solution is coated and dried, and the like. The solution of the film-forming method (film-forming method) is obtained by adding a solvent or various additives to a main component such as a metal or a polymer. By these film forming methods, continuous film formation is performed on a long film substrate in order to efficiently form a film by ensuring high productivity.

In recent years, there has been a high demand for industrial products for energy saving from the heightened interest in the environment and energy. One of them is the heat insulation of the window glass of houses and automobiles, that is, Glass and film are required. Such a glass and a film are required to have properties that transmit sunlight in the visible light region in the sunlight spectrum and prevent transmission of sunlight in the infrared region.

As a method for obtaining the characteristics of such glass for heating and film, there is known a method using a cholesteric liquid crystal layer. For example, as described in Japanese Patent No. 4109914, there is known a method of forming a cholesteric liquid crystal layer which functions in the near-infrared to infrared region and circularly polarized light in the same rotation direction on both sides of a? / 2 plate .

As a facility for carrying out a film-forming method for producing a laminated film, a roll-to-roll film-forming apparatus is known. In a roll-to-roll film-forming apparatus, a take-up shaft made of a supply roll and a take-up roll is used. The supply roll is formed by winding a long film substrate in a roll form. On the take-up shaft, the film base after the film formation, that is, the laminated film is wound into a roll to form a take-up roll. This roll-to-roll film-forming apparatus is provided with a film-forming chamber which is formed between the supply roll and the take-up shaft by a vacuum film forming method or a coating film forming method. Then, in this film formation chamber, a long film substrate extending from the supply roll toward the take-up shaft is inserted, and the film substrate is fed from the supply roll and the film substrate after film formation by the take-up shaft is wound in synchronization , Film formation is continuously performed on the film substrate to be transported in the film formation chamber.

When the film is formed in this manner, the film surfaces rolled up in a rolled state and overlapping with each other may excessively come into contact with each other or come in close contact with each other. Or, at the time of winding, there is a case where dust adheres between the film and the film. As a result, there arises a problem that a winding roll is deformed during winding or after winding and, as a result, a problem occurs such as a scratch on the film surface or a wrinkle on the film, or a black band is visible on the circumferential surface of the winding roll May occur. Further, the deformation of the winding roll may occur as a result of a wound on the film surface or wrinkles of the film. On the other hand, there is a method in which the tension at the time of winding is lowered so as not to cause such a problem. However, if the tension at the time of winding is lowered, the retention force between the films is weak, and lateral displacement occurs, which may cause a problem as a product. The transverse shift is a phenomenon in which the film is shifted in the width direction.

Japanese Patent No. 3226190 and Japanese Unexamined Patent Application Publication No. 2002-211803 disclose a method in which when a film made of plastic which is continuously conveyed is rolled up in a rolled state by embossing called nulling, A method of imparting minute convex portions has been proposed. According to these methods, it is possible to prevent transverse misalignment and winding-up during winding, and to secure a gap between the back surface of the film and the surface at the time of winding, thereby reducing the occurrence of problems due to contact or close contact.

In order to achieve the above effect, it is necessary that the convex portion formed by the knurling be higher than the height of the film surface of the central portion in the width direction of the coating film to some extent. However, the height of the convex portion that can be formed by knurling has a limitation because it affects the thickness and rigidity of the film substrate. Therefore, the height of the convex portion of the knurling is insufficient, so that a desired effect may not be obtained. In addition, the convex portions formed by knurling are often deformed by the pressure after the winding, and there is a problem that the above-mentioned effect can not be obtained due to a variation in the height. In addition, in order to form a knurling, there is a problem that productivity is decreased and manufacturing cost is increased because a new process is increased.

As a result of intensive investigations by the inventors, it has been found that when the coating film forming method is used, a ridge is formed at both ends of the substrate and the coating liquid under certain conditions. Also, it was found that this loop can be controlled by setting the conditions.

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a laminated film which does not undergo knurling, does not deform the winding roll, and does not cause lateral displacement, and a manufacturing method thereof.

In order to attain the above object, the laminated film of the present invention comprises a first base material, a first coating film, a second coating film, a first base pair, and a second base pair. The first substrate is web. The first coating film is formed by applying the first coating liquid onto the first base material. The second coating film is formed by applying the second coating liquid onto the second substrate. The second substrate has a first substrate and a first coating film. The first pair of ridges and the second pair of ridges are formed at both ends in the width direction of the first coated film and the second coated film. The first pair of stones and the second pair of stones are 1 占 퐉 or more higher than the film surface in the widthwise central portion of the laminated film. Either one of the first pair of stones and the second pair of stones is located on the side of the side of the laminated film (side end).

It is preferable that the first coating liquid and the second coating liquid each have a polymer liquid crystal compound, a fluorinated alignment control agent and a solvent.

Fluorine of 90% or more of the total fluorine content contained in the first coating film is present in the region from the surface of the first coating film to the depth of 500 nm and the fluorine content of the second coating film is increased to the depth of 500 nm from the surface of the second coating film It is preferable that at least 90% of the total fluorine content contained is present.

The difference between the heights of the first pair of stones and the second pair of stones is preferably 3 m or less. It is preferable that the distance between the first and second stamper pairs is 1 mm or more. The thicknesses of the first coating film and the second coating film are preferably 1 mu m or more, respectively. It is preferable that the first coating film and the second coating film respectively represent cholesteric phases.

Each surface energy of the first base material and the second base material is preferably 40 mN / m or less. The surface tension of each of the first coating liquid and the second coating liquid is preferably in the range of 20 mN / m or more and 40 mN / m or less. It is preferable that the viscosity of each of the first coating liquid and the second coating liquid after solvent volatilization is 0.5 Pa s or less.

The method for producing a laminated film of the present invention comprises the steps of: a first coating step (step A); a first drying step (step B); a first curing step (step C); a second coating step (step D) A second drying step (step E), and a second curing step (step F). In the step A, the first coating liquid is applied to the first coating area on the first substrate on the web to form the first wet film. The surface energy of the first substrate is 40 mN / m or less. The surface tension of the first coating liquid is in the range of 20 mN / m to 40 mN / m. In the step B, the solvent is evaporated from the first wet film to form the first dry film. In the step C, the first dried film is cured to form the first coated film. In the step D, the second coating liquid is applied to the second coating area having a width different from the first coating area on the second substrate to form the second wet film. The second substrate has a first substrate and a first coating film. The surface energy of the second substrate is 40 mN / m or less. The surface tension of the second coating liquid is in the range of 20 mN / m to 40 mN / m. In Step E, the solvent is evaporated from the second wet film to obtain a second dried film. In step F, the second dried film is cured to form a second coated film.

The production method of the laminated film preferably further comprises a first orientation step (G step) and a second orientation step (H step). Step G aligns the polymer liquid crystal compound between steps B and C. The first coating liquid has a polymer liquid crystal compound, a fluorinated alignment control agent and a solvent. Step H aligns the polymer liquid crystal compound between Step E and Step F. The second coating liquid has a polymer liquid crystal compound, a fluorinated alignment control agent and a solvent.

It is preferable that the first coating film and the second coating film respectively represent cholesteric phases. The viscosity of each of the first coating liquid and the second coating liquid after solvent volatilization is preferably 0.5 Pa s or less. It is preferable that the distance between the first application region and the second application region is 1 mm or more. The thickness of the first coating film and the thickness of the second coating film are preferably 1 mu m or more, respectively.

According to the laminated film of the present invention, although the knurling is not carried out, the winding roll is not deformed and the lateral deviation does not occur.

According to the method for producing a laminated film of the present invention, it is possible to produce a laminated film without knurling, without causing deformation of the winding roll and without causing lateral displacement.

1 is a schematic sectional view of a laminated film according to an embodiment of the present invention.
2 is a plan view schematically showing an apparatus for producing a laminated film of the present invention.
3 is a schematic view showing a coating apparatus used in a coating process.
4 is a sectional view taken along the line IV-IV in Fig.
5A is a partial cross-sectional view schematically showing a drying apparatus used in a drying process, and is a cross-sectional view taken along a section perpendicular to the width direction of the first substrate.
5B is a partial sectional view taken along the line BB 'in FIG. 5A.
Fig. 6A is a schematic view of a heating apparatus used in an alignment step, and is a cross-sectional view taken along a section perpendicular to the width direction of the first substrate. Fig.
6B is a cross-sectional view taken along line BB 'of FIG. 6A.
7A is a schematic view of a UV irradiation device used in a curing process, and is a cross-sectional view taken along a section perpendicular to the width direction of the first substrate.
7B is a cross-sectional view taken along line BB 'of FIG. 7A.
8 is a schematic view for explaining the shape change until the coating liquid becomes the coating film under the condition of the formula (5).
9 is a schematic view for explaining the shape change until the coating liquid becomes a coating film under the condition of the formula (6).
10 is a schematic view for explaining the shape change until the coating liquid becomes a coating film under the condition of the formula (7).
11 is an explanatory view for explaining conditions under which a pair of ridges is formed.
12 is a graph showing the results of ESCA analysis of fluorine in the second coating film of the laminated film of the present invention.
Fig. 13A is a schematic view showing a first coated layer, a second coated layer and a film substrate of the laminated film of the present invention. Fig. 13B is a view showing a profile of the surface shape of the area b surrounded by the broken line in Fig. to be.

(Laminated film)

As shown in (A1) to (A3), (B1) to (B3), and (C1) to (C6) in FIG. 1, the laminated film 2 is a laminated film 1 coating layer 11, the second coating layer 12, and the third coating layer 13 are superimposed in this order. 1, the thickness of each of the film substrate 10 and the first application layer 11 to the third application layer 13 is greatly exaggerated with respect to the width. The laminated film 2 is a long film stretched in the depth direction of the paper surface of Fig.

The laminated film (2) has a first pair of ridges (16) and a second pair of ridges (17) on one side of the film surface. The first pair of tumblers 16 and the pair of tumblers 17 are provided at both ends of the side end portion in the width direction Y of the laminated film 2 (hereinafter sometimes simply referred to as " side end portions & (Hereinafter sometimes simply referred to as " center portion ") in the direction Y. Either one of the first pair of pawl joints 16 and the second pair of pawl joints 17 is located on the outer side in the width direction Y than the other. By the first pair of pawl pairs 16 and the pair of second pawl pairs 17, a gap is secured between the laminated films which are overlapped with each other when the laminated film 2 is wound. The laminated film of the present invention is not limited to the example of the laminated film 2 shown in Fig. 1, and any laminated film may be used as long as the laminated film has the first pair of ridges 16 and the pair of ridges 17 near both ends of the width- It may be in form.

The coating layer serving as a factor for forming the first coating film and the second rubbing pair 17 is called the second coating film. The coating layer serving as a factor for forming a pair of stones means the following (I) and (II).

(I) a coating layer on which a stone pair itself is formed

(II) The surface of the pair of stones is covered with another coating layer, but the coating layer formed with convex portions of a cross-section (horn)

The convex portion serving as a base of the pair of pairs of stones in the above-mentioned (II) is hereinafter referred to as a base portion, the reference numeral 16a is assigned to the base portion of the first pair of pawl joints 16, do. As shown in the above (II), the first pair of ridges 16 and the second pair of ridges 17 comprise different coating layers, but the protruding shape is substantially the same as that of the base portions 16a and 17a May be formed.

In the laminated film 2 of (A1), (A2) and (A3) in FIG. 1, the first coating layer 11 is the first coating film and the second coating layer 12 is the second coating film . In the laminated film 2 of (B1), (B2) and (B3) in FIG. 1, the first coating layer 11 is the first coating film and the third coating layer 13 is the second coating film . In the laminated film 2 of (C1), (C2), (C3), (C4), (C5) and (C6) of FIG. 1, the second coating layer 12 is the first coating film , And the third coating layer 13 is the second coating film. It is sufficient that the laminated film 2 has the first pair of ridges 16 and the second pair of ridges 17 in the vicinity of both ends of the lateral end in the width direction and that the film formation layer by any other application layer and the other film- Or may be formed.

The coating liquid serving as a raw material of the first coating film is used as the first coating liquid and the coating liquid serving as the raw material of the second coating film is used as the second coating liquid. As the first coating liquid and the second coating liquid, those having a surface tension in the range of 20 mN / m or more and 40 mN / m or less are used. The base material to which the first coating liquid is applied is referred to as a first base material, and the base material to which the second coating liquid is applied is referred to as a second base material. For example, the first base material in the laminated film 2 of (A1), (A2) and (A3) in FIG. 1 is the film base 10, and the second base material is the film base material 10 and a first coating layer 11. The first base material in the laminated film 2 of (B1), (B2) and (B3) in FIG. 1 is the film base 10, and the second base material is the film base 10 and the first coating layer 11 ) And a second coating layer (12). The first base material in the laminated film 2 of (C1), (C2), (C3), (C4), (C5) 11, and the second substrate is composed of the film substrate 10, the first coating layer 11, and the second coating layer 12.

In any of the laminated films 2 of (A1) to (A3), (B1) to (B3), and (C1) to (C6) of FIG. 1, the first and second pairs of ridges 16 and 17 ) Is at least 1 占 퐉 or more higher than the film surface at the center of the laminated film (2). The height H1 of the first pair of ridges and the height H2 of the second pair of ridges are preferably larger than the height Hf of the center portion in the range of 1 占 퐉 to 200 占 퐉 and more preferably in the range of 2 占 퐉 to 50 占 퐉 It is more preferable to be large within the range. The height H1 of the first pair of ridges 16 and the height H2 of the second pair of ridges 17 may be equal to each other and either one of them may be higher than the other. The difference | H1 - H2 | between the heights of the first pair of tumblers 16 and the second pair of tumblers 17 is preferably not more than 3 占 퐉. The first pair of tumblers 16 at one of the side ends, It is preferable that the distance D between the two pairs of stones 17 is 1 mm or more. The distance D between the first pair of pawl pairs 16 and the second pair of pawl pairs 17 at one side end portion is set to be smaller than the distance D between the top portion of the first pawl pair 16 and the top portion of the second pair of pawls 17. [ .

The laminated film 2 of (A1) to (A3) in FIG. 1 is a laminated film in which both side edges of the first coated layer 11 are located on the inner side of both side edges of the film base 10, on both side edges of the second coated layer 12 Are located on the inner side of both side edges of the first application layer 11. It is to be noted that both side edges of the third application layer 13 are located on both sides of the side edge of the second coating layer 12 in the laminated film 2 of A1 and in the laminated film 2 of the A2 2 Outside of both side edges of the coating layer 12 and inside of the first coating layer 11 In the laminated film 2 in A3 Outside of the first coating layer 11 Both sides of the film base 10 It is medial to the edge.

The laminated film 2 of (B1) to (B3) in FIG. 1 is a laminated film 2 in which both side edges of the first coated layer 11 are located on the inner side of both side edges of the film base 10, on both side edges of the third coated layer 13 Are located on the inner side of both side edges of the first application layer 11. It should be noted that both side edges of the second coating layer 12 are located on both sides of the third coating layer 13 on the outer side and on the inner side of the first coating layer 11 in the laminated film 2 of (B1) In the laminated film 2 of the first coating layer 11 and in the width direction Y of the laminated film 2 of the first coated layer 11, And is located on the inner side of both side edges of the substrate 10.

The laminated films 2 of (C1) to (C6) in FIG. 1 are common in that the both side edges of the first coated layer 11 are inwardly located on both side edges of the film base 10. The laminated films (2) of (C1) to (C3) are common in that both side edges of the third coated layer 13 are inwardly located on both side edges of the second coated layer 12. It should be noted that both side edges of the second coating layer 12 are located on both sides of the side edges of the first coating layer 11 in the laminated film 2 of the C1 and in the laminated film 2 of C2, 1 of the laminated film 2 of the laminated film 3 in the width direction Y and the edges of both sides of the first substrate layer 11 are substantially coincident with each other, As shown in Fig. The laminated film (2) of (C4) to (C6) is common in that both side edges of the third coated layer 13 are located outside the opposite side edges of the second coated layer 12. It is to be noted that both side edges of the second coating layer 12 are located on both sides of the side edges of the first coated layer 11 in the laminated film 2 of C4 and in the laminated film 2 of C5 1 of the laminated film 2 in the width direction Y and the edges of both sides of the film base 10 are substantially coincident with each other, As shown in Fig.

When the first coating layer 11 is used as the first coating film, the film base 10 having a surface energy of 40 mN / m or less is used as described later. For example, when each laminated film 2 of (A1) to (A3), (B1) to (B3), and (C6) in FIG. 1 is produced, 10) is used. In the case where TAC having a surface energy of more than 40 mN / m is used as the film substrate 10, for example, as in the case of the laminated film 2 shown in Fig. 1 (C1) The pair of stones 16 is not formed. Hereinafter, a mode for carrying out the invention for the laminated film (2) shown in Fig. 1 (C1) is described, but for the invention for the laminated film (2) other than the laminate film (C1) . In the laminated film 2 shown in Fig. 1 (C1), the first coating layer 11 is a layer not having the first pair of ridges 16, and the second coating layer 12 is a layer of the first ridges 16), and the third coating layer 13 is a second coating film which is a factor for forming the second pair of stones 17. The first substrate 11A (see Fig. 2) is formed with the first coating layer 11 on the film base 10.

(Laminated film production facility)

As shown in Fig. 2, the laminated film production equipment 20 has the film formation devices 22A, 22B, and 22C in order from the upstream side. The film forming apparatus 22A includes a coating apparatus 24A, a drying apparatus 26A, a heating apparatus 28A and a UV irradiation apparatus 30A in this order from the upstream side. The film forming apparatus 22B and the film forming apparatus 22C are configured similarly to the film forming apparatus 22A. Specifically, the film forming apparatus 22B includes a coating device 24B, a drying device 26B, a heating device 28B, and a UV irradiation device 30B in this order from the upstream side. The film forming apparatus 22C includes a coating device 24C, a drying device 26C, a heating device 28C and a UV irradiation device 30C in this order from the upstream side. The application devices 24A, 24B, and 24C apply a coating liquid containing a polymer liquid crystal compound, a fluorinated alignment control agent, and a solvent to the film substrate 10 to form a wetting layer. The drying apparatus 26A, 26B, 26C evaporates the solvent from the wetting layer to form a drying layer. The heating devices 28A, 28B, and 28C align the polymer liquid crystal compound in the dry layer to form an alignment layer. The UV irradiation devices 30A, 30B and 30C irradiate the alignment layer with UV to cure the UV-curable material to form a coating layer. 2, an arrow X is provided in the transport direction of the film substrate 10. [

This laminated film production equipment 20 is an apparatus for forming a film by coating by roll-to-roll. The film base material 10 on the belt (web) is loaded on the supply shaft 32 as a supply roll 34, and is deposited by coating while being transported in the longitudinal direction. The laminated film 2 thus formed is wound on the take-up shaft 36 as a take-up roll 38. The conveying roller 40 is appropriately formed so that the film can stably pass through the film forming apparatuses 22A, 22B, and 22C.

3 and 4, the coating apparatus 24B has, for example, an application head 42, a coating liquid supply tank 44, and a coating liquid supply line 46. [ The application head 42 applies the first coating liquid to the first base material 11A to form the first wetting layer 12A. The application liquid supply tank 44 supplies the application liquid to the application head 42. The coating liquid supply line 46 connects the coating head 42 and the coating liquid supply tank 44 to each other. The coating head 42 is provided with a coating opening 42A for coating, a coating slit 42B and a coating pocket 42C. The coating supply port 42A supplies the coating liquid guided to the coating liquid supply line 46 to the inside of the coating head 42. [ The application slit 42B is a flow path that is a bottleneck for applying the application liquid to the first application region R1 of the first base material 11A without fail. The application pocket 42C temporarily stores the application liquid supplied from the application supply port 42A before supplying it to the application slit 42B. The application head 42 is installed such that the application slit 42B is located near the first base material 11A toward the path side of the first base material 11A.

The application devices 24A and 24C have the same configuration as the application device 24B. It is to be noted that the application device 24A applies the application liquid for forming the first application layer 11 to the film substrate 10 and the application device 24C applies the application liquid for forming the third application layer 13 to the second coating layer 12, as shown in FIG. Since the laminated film 2 shown in FIG. 1 (C1) has the first coated layer 11 wider than the second coated layer 12, the coating slit of the coating head of the coating head 24A The length in the width direction Y is longer than the application slit 42B. Since the laminated film 2 shown in Fig. 1 (C1) has the third coated layer 13 narrower than the second coated layer 12, the coating slit 2 of the coating head of the coating device 24C of the coating device 24C, (Not shown) has a shorter length in the width direction Y than the application slit 42B.

As shown in Figs. 5A and 5B, the drying apparatus 26B includes, for example, a chamber 47, a hot air fan 48, and a solvent recovery device 50. Fig. The chamber 47 covers the path of the first wet film 12B composed of the first substrate 11A and the first wetting layer 12A. The hot air blower 48 is disposed on the side of the first wet film 12B on which the first coating liquid is applied, and allows the first wetting layer 12A to be exposed to hot air. The solvent recovery device 50 is formed in the lower part of the chamber 47, and recovers the solvent. In the chamber 47 of the drying device 26B, a regulator (not shown) for regulating the environment such as temperature and humidity is provided. With this adjuster, the interior of the chamber 47 is being conditioned to an optimum for drying the first wetting layer 12A to form the first drying layer. And the first dry film 12C is delivered from the drying device 26B. The drying apparatuses 26A and 26C have the same configuration as the drying apparatus 26B, and therefore the description thereof is omitted.

As shown in Figs. 6A and 6B, the heating apparatus 28B includes, for example, a chamber 51 and a heater 52. [ The chamber 51 covers the path of the first dry film 12C. The heaters 52 are arranged, for example, two so as to face the respective film surfaces of the first dry film 12C. Each of the heaters 52 heats the first dry film 12C from the thickness direction. The chamber 51 of the heating device 28B is provided with a regulator (not shown) for controlling the environment such as temperature and humidity. With this adjuster, the inside of the chamber 51 is controlled to an optimum condition for forming the first alignment layer by orienting the polymer liquid crystal compound in the first drying layer. And the first orientation film 12D is delivered from the heating device 28B. Since the heating devices 28A and 28C have the same configuration as the heating device 28B, their description is omitted.

As shown in Figs. 7A and 7B, the UV irradiation device 30B includes, for example, a chamber 53 and a UV irradiation lamp 54. [ The chamber 53 covers the path of the first orientation film 12D. The UV irradiation lamp 54 is formed so as to face the side of the first orientation film 12D coated with the first coating liquid, and irradiates the side coated with the first coating liquid on the UV side. The chamber 53 of the UV irradiation device 30B is provided with a regulator (not shown) for controlling the environment such as temperature and humidity. With this adjuster, the interior of the chamber 53 is adjusted to an optimum condition for curing the first alignment layer to form the first coating film. And the first cured film 12E is delivered from the heating device 28B. Since the UV irradiation devices 30A and 30C have the same configuration as the UV irradiation device 30B, their description is omitted.

(Coating liquid)

In the present invention, the coating liquid for forming the first to third coating layers (11) to (13) is at least one kind of a polymerizable liquid crystal compound, an alignment control agent, a polymerization initiator, Solvent. It is possible to use the compounds as shown below.

In the present invention, a rod-like curable cholesteric liquid crystal compound such as a rod-shaped nematic liquid crystal compound or the like is used for the polymerizable liquid crystal compound. Examples thereof include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, Alkoxy-substituted phenylpyrimidines, phenyl dioxanes, tolans and alkenylcyclohexyl benzonitriles are used.

Further, a polymerizable cholesteric liquid crystal compound obtained by introducing a polymerizable group into a cholesteric liquid crystal compound may be used as a polymerizable liquid crystal compound. Examples of the polymerizable group include an unsaturated polymerizable group, an epoxy group, and an aziridinyl group, among which an unsaturated polymerizable group is preferable, and an ethylenically unsaturated polymerizable group is particularly preferable. The number of polymerizable groups in the polymerizable cholesteric liquid crystal compound is preferably 1 to 6, more preferably 1 to 3. Examples of polymerizable cholesteric liquid crystal compounds are described in Makromol. Chem., 190, 2255 (1989), Advanced Materials 5, 107 (1993), U.S. Patent No. 4683327, U.S. Patent No. 5622648, U.S. Patent No. 5770107, International Publication WO95 / 22586, 95/24455, 97/00600, 98/23580, 98/52905, 1-272551, 6-16616, 7-110469, 11-80081 , And JP-A-2001-328973, and two or more polymerizable cholesteric liquid crystal compounds may be used in combination.

The temperature range of the cholesteric phase of these polymerizable liquid crystal compounds is in the range of 20 占 폚 to 150 占 폚. Therefore, the conditions such as the hot air 48 can be set so that the temperatures in the drying devices 26A, 26B, and 26C do not exceed the upper limit of the temperature range in which this cholesteric phase is obtained. In the present embodiment, the temperature in the heating step is set at 85 占 폚.

In the present invention, a compound as described in paragraphs 0016 to 0050 of Japanese Laid-Open Patent Publication No. 2005-099248 is used as the alignment control agent. For example, a compound represented by the formula (1) is used. The alignment control agent is not limited to these compounds, and the compounds having the same functions as those described above may be used alone, or two or more of them may be used in combination.

[Chemical Formula 1]

In the present invention, the polymerization initiator to be used is preferably a photopolymerization initiator capable of initiating the polymerization reaction by irradiation with ultraviolet rays in the mode of carrying out the polymerization reaction by ultraviolet irradiation. For example, there may be mentioned α-carbonyl compounds (described in US Patents Nos. 2367661 and 2367670), acyloin ethers (described in US Patent No. 2448828), α-hydrocarbon substituted aromatic acyloin compounds A combination of triarylimidazodime and p-aminophenyl ketone (described in U.S. Patent No. 3549367), a polynuclear quinone compound (described in U.S. Patent Nos. 3046127 and 2951758) (Described in Japanese Patent Application Laid-Open No. 60-105667, US Patent No. 4239850), and oxadiazole compounds (described in US Patent No. 4212970), and the like are used. The polymerization initiator is not limited to these compounds, and the compounds having the same functions as those described above may be used alone, or two or more of them may be used in combination.

In the present invention, as the chiral agent, a horizontal alignment agent as described in paragraphs 0057 to 0096 of Japanese Patent Laid-Open No. 2002-179668 is used. For example, a compound represented by formula (2) is used. The chiral agent is not limited to these compounds, and the compounds having the same functions as those described above may be used alone or in combination of two or more.

(2)

In the present invention, the solvent is not particularly limited, and a known solvent for dissolving the curable cholesteric liquid crystal compound can be used. Examples of the solvent include ketones (acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone and the like), ethers (dioxane and tetrahydrofuran), aliphatic hydrocarbons (hexane and the like), alicyclic hydrocarbons Hexane and the like), aromatic hydrocarbons (toluene, xylene and trimethylbenzene), halogenated carbons (dichloromethane, dichloroethane, dichlorobenzene and chlorotoluene), esters (methyl acetate, ethyl acetate and butyl acetate) Water, alcohols (ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolve (methylcellosolve, ethylcellosolve etc.), cellosolve acetates, sulfoxides (dimethylsulfoxide etc.) (Dimethylformamide, dimethylacetamide, etc.) and the like. The solvent is not limited to these compounds, and the compounds having the same functions as those described above may be used alone, or two or more of them may be used in combination.

(Mechanism of forming stones)

Hereinafter, the mechanism of forming the first pair of ridges 16 will be described with respect to the first wetting layer 12A formed by applying the first coating liquid on the first base material 11A. The shape of the first wetting layer 12A is determined such that the energy E represented by the formula 1 is minimized. The interfacial energy of the first substrate 11A and the atmosphere per unit area is referred to as the surface energy of the first substrate 11A and the interfacial energy of the first wetting layer 12A and the atmosphere per unit area is referred to as the first wetting layer 12A, Quot; surface tension " The terms surface energy and surface tension are defined in the same way as these.

gamma_SG : The interfacial energy of the first substrate (11A) and the atmosphere per unit area

gamma_SL : The interface energy between the first base material 11A and the first wetting layer 12A per unit area

gamma_LG : The interfacial energy of the first wetting layer 12A per unit area and the atmosphere

S_SG : The contact area of the first base material 11A with the atmosphere

S_SL : The contact area between the first base material 11A and the first wetting layer 12A

S_LG : The contact area of the first wetting layer 12A and the atmosphere

m (x): mass of the molecule at coordinate X

g: gravitational acceleration

h (x): height at coordinate X

The first term of the formula (1) represents the interfacial energy amount between the first base material 11A and the atmosphere. The second term of Equation 1 represents the amount of interfacial energy between the first base material 11A and the first wetting layer 12A. The third term of Equation 1 represents the interfacial energy between the first wetting layer 12A and the atmosphere. The fourth term of Equation 1 represents the gravitational potential energy of the first wetting layer 12A. From Equation (1), it can be said that the factor determining the system is constituted by three interface energy and gravitational potential energy.

The sum of the area where the first base material 11A and the atmosphere are in contact and the area where the first base material 11A and the first wetting layer 12A are in contact is dependent on the shape of the first wetting layer 12A It is politic without politics. That is, Equation 2 holds.

Further, the energy E can be considered as Equation 3 and Equation 4 by dividing it into two as follows.

Considering Equation 2, it can be seen that elements of the wetting angle largely contribute to the determination of the shape of the first wetting layer 12A with respect to Equation 3. A, A, B, and C are defined as A, A, C, respectively.

As for the element of the image of the other first wetting layer (12A) other than the milk is negative, it can be seen that the consideration for E ₂ in the formula (4). Therefore, the process of determining the shape of the first wetting layer 12A will be described by dividing the conditions shown in the following equations (5) to (7).

The process of determining the shape of the first wetting layer 12A under the condition of Formula 5 will be described with reference to FIG. From the condition of the expression (5), the shape immediately after the application of the first wetting layer (12A) is determined so as to minimize the interfacial energy of the first wetting layer (12A) and the atmosphere. In short, the shape immediately after the application of the first wetting layer 12A is determined so as to minimize the contact area between the first wetting layer 12A and the atmosphere. The shape immediately after application of the first wetting layer 12A determined to minimize the contact area of the first wetting layer 12A and the atmosphere differs depending on the wetting angle?. For example, as shown in (A1) of Fig. 8, in a system in which the wiping angle [theta] is larger than 90 degrees, the contact with the first base material 11A as compared with the system in which the wiping angle [ The height of the both end portions in the width direction Y of the first wetting layer 12A is high along with the small area. As shown in (C1) of FIG. 8, in the system in which the wiping angle? Is less than 90 degrees, the contact area with the first base material 11A is smaller than that in the system in which the wiping angle? The height of both end portions in the width direction Y of the first wetting layer 12A is low.

The area of the first wetting layer 12A in contact with the outside air in the width direction Y is largest at both ends so that the solvent at both ends is more efficiently blown than the solvent at the center in the width direction Y. [ As described above, both end portions of the first wetting layer 12A are liable to be dried. Therefore, as shown in (A2), (B2), and (C2) of FIG. 8, in both of the systems A to C, the first dried initial dry area 12AS .

When the first initial drying region 12AS is formed, the first wetting layer 12A is formed so as to form a proper wetting angle &thetas; with respect to the first base 11A as well as the first initial drying region 12AS, There is a possibility that the shape is further changed so that the energy E shown in Fig. 8 (A3), 8 (B3), and 8 (C3) in that the contact area between the first wetting layer 12A and the atmosphere is minimized, As can be seen, it can be seen that the shape of the first wetting layer 12A substantially does not change with the shape of (A2), (B2), and (C2) in FIG. That is, under the condition of the expression (5), it can be said that the first pair of ridges 16 is not formed.

The process of determining the shape of the first wetting layer 12A under the condition of the expression (6) will be described with reference to Fig. From the condition of Equation 6, the shape immediately after application of the first wetting layer 12A is determined so as to minimize the gravitational potential energy of the first wetting layer 12A. The shape immediately after application of the first wetting layer 12A determined to minimize the gravitational potential energy of the first wetting layer 12A is determined so as to minimize the interface energy of the first wetting layer 12A and the atmosphere The thickness becomes smaller than that under the condition of the expression (5), and the shape becomes extremely wet and diffused. For example, in a system in which the wiping angle? Is larger than 90 degrees, as shown in (A1) of Fig. 9, the first wetting layer 12A is formed by the first wetting layer 12A in Fig. The thickness becomes smaller, and the shape becomes extremely wet and diffused. Similarly, in the system of (B1) of Fig. 9 where the wiping angle [theta] is 90 degrees, in the system of (C1) of Fig. 9 where the wiping angle is smaller than 90 degrees, The first wetting layer 12A is formed to have an extremely wetted and diffused shape.

Under the condition of the formula 6, since the both end portions of the first wetting layer 12A are in contact with the outermost air, the area of the first wetting layer 12A is large, Both ends are easy to dry. Therefore, as shown in (A2), (B2), and (C2) in FIG. 9, the first initial drying region 12AS is formed at both ends of the first wetting layer 12A in any of A to C do.

When the first initial drying area 12AS is formed, the first wetting layer 12A is formed so as to form an appropriate wetting angle with respect to the first substrate 11A as well as the first initial drying area 12AS, There is a possibility of changing the shape so that the energy E represented is minimized. 9 (A3), 9 (B3), and 9 (C3) in that it is determined to minimize the gravitational potential energy of the first wetting layer 12A, As can be seen, the shape of the first wetting layer 12A substantially does not change with the shape of (A2), (B2), and (C2) in FIG. That is, under the condition of the expression (6), it can be said that the first protrusion pair 16 is not formed.

The process of determining the shape of the first wetting layer 12A under the condition of the expression (7) will be described with reference to Fig. From the condition of the expression (7), the shape immediately after the application of the first wetting layer (12A) has a tendency to minimize the contact area between the first wetting layer (12A) and the atmosphere, Is determined so as to minimize the energy E in Equation (1) by the balance of the tendency to minimize the energy. Therefore, the shape immediately after the application of the first wetting layer 12A is set so that the shape of the first wetting layer 12A is in a range of 90 degrees or more and 90 degrees or less, B1), and as shown in Fig. 10 (C1), the shape is intermediate between the condition of the expression (5) and the condition of the expression (6). Concretely, under the condition of the formula (7), the first wet layer (12A) immediately after coating has a thickness smaller than the condition of the formula (5) and larger than the condition of the formula (6) And is smaller than the condition of Eq. (6).

Under the conditions of the formula 7, the solvent is efficiently flown because the both end portions of the first wetting layer 12A are in contact with the outermost air in a large area, similarly to the conditions of the equations 5 and 6, The both end portions of the heat sink 12A are liable to be dried. Therefore, as shown in (A2), (B2) and (C2) in FIG. 10, the first initial drying region 12AS is formed at both ends of the first wetting layer 12A in any of A to C do.

When the first initial drying region 12AS is formed, the first wetting layer 12A is formed so as to form a proper wetting angle &thetas; with respect to the first substrate 11A as well as the first initial drying region 12AS, There is a possibility of changing the shape so that the energy E shown in Fig. Due to the balance with the tendency to minimize the gravitational potential energy of the first wetting layer 12A at the point where the wetting angle &thetas; of the first wetting layer 12A and the first initial drying region 12AS is substantially zero degrees The solution that minimizes the energy E in Equation 1 changes, and as shown in each of Figs. 10 (A3), 10 (B3) and 10 (C3), the first wetting layer 12A Is changed under the influence of the first initial drying region 12AS. As a result, the first pair of ridges 16 is formed. In other words, it can be said that the first protrusion pair 16 is formed only under the condition of the expression (7). Particularly, as shown in (B1), (B2) and (B3) in FIG. 10, the conditions under which the wiping angle θ is 90 degrees or about 90 degrees are the conditions in which the first pair of ridges 16 are inclined relative to the film surface of the laminated film 2 It is a condition that occurs in almost vertical direction. The mechanism for forming the second pair of pawl pairs 17 is also the same as the mechanism for forming the first pair of pawl pairs 16. [

The conditions under which the first pair of ridges 16 are formed will be described with reference to Fig. Claim 1 as stone condition that one trillion pairs 16 are formed, there may be mentioned a negative θ milk and m (x) gh (x) / S γ _{LG LG.} The vertical axis in Fig. 11 is the wetting angle? Of the substrate and the wetting layer. The horizontal axis is the m (x) gh (x) / γ LG S LG, m (x) gh (x) / γ LG S LG is greater larger toward right in Fig. In Fig. In the 11, m (x) gh ( x) / γ LG S As for the _LG, to give a first wetting layer (12A) is a code (A) region of strain as shown in Fig. 10, Fig. 8 As shown, the reference numeral B is given to a region where the first wetting layer 12A is deformed and the reference numeral C is given to a region where the first wetting layer 12A is deformed, as shown in Fig.

As shown in Fig. 11, the system using the polymer liquid crystal compound, the fluorine-based alignment control agent, and the solvent in the present invention generally satisfies the condition indicated by the region 58 (hatched region in Fig. 11). Also, when the condition indicated by the region 60 (the cross hatching region in Fig. 11) is satisfied, a pair of ridges occurs. In particular, as in the conditions of (B1), (B2) and (B3) in FIG. 10, when the wiping angle? Is 90 degrees, a pair of ridges substantially perpendicular to the surface of the substrate is generated, desirable. Therefore, by designing the surface energy of the first base material 11A as small as possible in the region 58, the conditions are changed according to the arrow 62, and the first pair of ridges 16 is generated in a substantially vertical direction It gets easier. Similarly, by designing the surface tension of the first wetting layer 12A as large as possible, the condition shifts along the arrow 64, and the first pair of ridges 16 is likely to occur in a substantially vertical direction. In addition, by increasing the film thickness of the first wetting layer 12A, the height of the first pair of ridges 16 can be increased. Although the mechanism of the shape determination of the first wetting layer 12A on the first base material 11A has been described here, this mechanism is suitable for determining the shape of the wetting layer on all the substrates.

Next, the operation of the above configuration will be described. As shown in Fig. 2, in the laminated film production facility 20, the supply roll 34 wound with the film base 10 on the supply shaft 32 is set. The film base material 10 supplied from the supply roll 34 is sequentially guided to the film forming apparatuses 22A, 22B, and 22C. The first coating layer 11 is formed by the film forming apparatus 22A and the second coating layer 12 is formed by the film forming apparatus 22B and the third coating layer 13 is formed by the film forming apparatus 22C. The laminated film 2 on which the first to third applied layers 11 to 13 are formed is wound on the take-up shaft 36 as a take-up roll 38.

When the film substrate 10 is guided to the coating device 24A, a coating liquid for forming the first coated layer 11 is applied to one of the film surfaces. The film base 10 coated with the coating liquid is guided to the drying device 26A, and the wet layer (not shown) formed by application of the coating liquid is dried to become a dried layer. When the coating liquid forming the first coating layer 11 contains the polymer liquid crystal compound, the film base 10 on which the drying layer is formed is guided to the heating device 28B. By the heating by the heating device 28B, the drying layer becomes an alignment layer (not shown) in which the polymer liquid crystal compound contained in the wetting layer is oriented. The film base 10 on which the alignment layer is formed is guided to the UV irradiation device 30A. By the UV irradiation by the UV irradiation apparatus, the alignment layer is cured to become the first coating layer 11. When the polymer liquid crystal compound is not used in the coating liquid, there is no alignment step by the heating device 28B and no curing step by the UV irradiation device 30A. Therefore, when the polymer liquid crystal compound is not used in the coating liquid, the film base 10 from which the drying device 26A is removed can be adhered to the film forming device 22B without interposing the heating device 28A and the UV irradiation device 30A. .

The first substrate 11A obtained by forming the first coating layer 11 with the film forming apparatus 22A is guided to the coating apparatus 24B of the film forming apparatus 22B. 3 and 4, the coating device 24B is formed by applying the first coating liquid to the first coating layer 11 of the first base material 11A supplied from the film forming apparatus 22A, To form the wetting layer 12A. The first coating liquid is supplied from the coating liquid supply tank 44 through the coating liquid supply line 46 to the coating head 42 from the coating supply port 42A and is once held in the coating pocket 42C And then flows out from the application slit 42B. The first wetting layer 12A is formed on the first base material 11A by the first coating liquid continuously flowing out to the first base material 11A during transportation to obtain the first wet film 12B. In this embodiment, since the third coating layer 13 having the second pair of protrusions 17 is formed on the second coating layer 12, the first coating layer 12 forming the second coating layer 12 The liquid is a prescription in which the second coating layer 12 having a surface energy of 40 mN / m or less is formed.

The first coating liquid is applied so that the side edges of the first wetting layer 12A are inward in the width direction Y from the side edges of the first coating layer 11, The first wetting layer 12A is formed on the first coating layer 11. By forming the first wetting layer 12A in this way, the second coated layer 12 narrower than the first coated layer 11 is formed. A second coating layer 12 having a width substantially equal to that of the first coating layer 11 is formed on the first coating layer 11 as in the case of the laminated film 2 shown in Fig. The first coating liquid may be applied so that the side edges of the first wetting layer 12A are substantially on the respective side edges of the first coating layer 11. [ The second coating layer 12, which is wider than the first coating layer 11 like the laminated film 2 shown in FIG. 1 (C3), may be used as the first coating layer 11 and the film substrate 10 The first coating liquid is applied so that the side edges of the first wetting layer 12A are located outside the respective side edges of the first coating layer 11 in the width direction Y. In this case, do.

5A and 5B, the first wet film 12B coated with the first wetting layer 12A on the first coated layer 11 of the first base material 11A is dried by the drying device 26B . The solvent contained in the first wetting layer 12A is evaporated from the hot air 48 provided in the drying device 26B and the first wetting layer 12A becomes the first drying layer 12F. In this manner, the first dry film 12C in which the first dry layer 12F is superposed on the first coated layer 11 of the first base material 11A is obtained. At the same time, the evaporated solvent is recovered by the solvent recoverer 50 and reused.

In the drying device 26B, since both ends of the first wetting layer 12A are in contact with the outermost air at a large area, the solvent is efficiently blown, and both ends of the first wetting layer 12A are liable to be dried . Therefore, by designing the surface energy of the first base material 11A and the surface tension of the first wetting layer 12A so as to satisfy the condition of the equation (7) and adjusting the drying conditions of the drying device 26B, To form the first initial drying region 12AS of the stone bath as shown in Fig. Thereby, the first dry film 12C having the first dry layer 12F in which the first pair of ridges 16 is formed is obtained.

In the case of using a coating liquid having a polymer liquid crystal compound, a fluorine-based alignment control agent and a solvent, the surface energy of the substrate is 40 mN / m or less and the surface tension of the coating liquid is 20 mN / m or more and 40 mN / m or less 10 (B1), (B2), and (B3) in the area 60 are satisfied. Therefore, in the case of forming a coating layer having a pair of protrusions, for example, in the present embodiment, in the case of forming the second coating layer 12 as the first coating film and the third coating layer 13 as the second coating film The film formation is carried out under these conditions. On the other hand, in the case of forming a coating layer without a pair of stones, for example, in the case of forming the first coating layer 11 in this embodiment, it is necessary to perform film formation under conditions that do not satisfy this requirement.

When a coating liquid having a polymer liquid crystal compound, a fluorinated alignment control agent and a solvent is used, the organic compound used in the fluorinated alignment control agent has a lower surface tension than other organic compounds not containing fluorine. Therefore, in a coating film on which a coating liquid having a polymer liquid crystal compound, a fluorinated alignment control agent and a solvent is formed, fluorine is localized near the surface. Therefore, in the case of using the fluorine-based alignment control agent, it becomes easy to control the pair of protrusions. Further, the fluorine-based organic material is softer than the fluorine-free organic material. For example, when the Rockwell hardness test is conducted under the test conditions of the scale R, the polypropylene content is about 90 to 95, while the poly (tetrafluoroethylene) content is about 58 and the polyfluorinated ethylene / propylene content is about 25. Therefore, the first and second pairs of ridges 16 and 17 become a little softer than the rear of the film substrate 10. Therefore, when the film is wound, damage such as scratches or wrinkles is imparted to the film surface or the film due to excessive contact, adhesion, or dust between the back surface and the surface of the laminated film 2 at the time of winding, The black band is not visually observed, and the laminated film 2 is wound without lowering the tension at the time of winding.

As shown in Figs. 6A and 6B, the first dry film 12C having passed through the drying device 26B is guided to the heating device 28B. The first dry film 12C is oriented such that the polymer liquid crystal compound contained in the first dry layer 12F becomes a cholesteric liquid crystal layer by the heater 52 provided in the heating device 28B. Since the heating device 28B is designed not to generate a temperature difference in the film width direction Y, it is suitable for orientation. This alignment condition is adjusted so as to be a cholesteric liquid crystal layer having properties to prevent transmission of sunlight in the infrared region depending on each material. Thereby, the first orientation film 12D having the desired characteristics is obtained which overlaps with the first application layer 11 of the first base material 11A. When the polymer liquid crystal compound is not used in the coating liquid, this alignment step by the heating device 28B is not necessary.

The viscosity of the first coating liquid after solvent volatilization is preferably 0.5 Pa s or less. In this case, the viscosity is lowered at the temperature of the heating device 28B, and the first drying layer 12F flows as if the first drying layer 12F slightly flare with respect to the first base material 11A, As shown in FIG.

As shown in Figs. 7A and 7B, the first orientation film 12D having passed through the heating device 28B is guided to the UV irradiation device 30B. The first alignment film 12D is UV-irradiated from the top of the film by the UV irradiation device 30B and the first alignment layer 12G is cured to form a second coating layer 12 on the first substrate 11A . Thus, the first cured film 12E is obtained.

The first cured film 12E is guided to the coating device 24C of the film forming apparatus 22C to apply the second coating liquid. The second coating liquid is applied so that the side edges of the second wetting layer (not shown) formed by the second coating liquid become inward in the width direction Y from the side edges of the second coating layer 12, 2 A second wetting layer, which is narrower than the application layer 12, is formed on the second application layer 12. By forming the second wetting layer in this manner, the third coated layer 13 narrower than the second coated layer 12 is formed. In addition, the second coating film is applied so that the second wetting layer is formed inside the first pair of ridges 16. It is also possible to form a third coated layer 13 having a width substantially equal to that of the second coated layer 12 on the second coated layer 12 like the laminated film 2 shown in Fig. , The second coating liquid may be applied so that each side edge of the second wetting layer is substantially on each side edge of the second coating layer 12. In the case of forming the third coating layer 13 wider than the second coating layer 12 like the laminated film 2 shown in (C4) to (C6) of Fig. 1, for example, The second coating liquid is applied so that each side edge of the layer is located outside of each side edge of the second coating layer 12 in the width direction Y. [

The film substrate 10 on which the second wetting layer is formed is guided to the drying device 26C. In the drying apparatus 26C, both end portions of the second wetting layer are dried to form a second initial drying region (not shown) of the same ridge as the first initial drying region 12AS. Thereby, a second dry film (not shown) having a second dry layer (not shown) on which the second pair of ridges 17 is formed is obtained.

The second dried film is guided to the heating device 28C. By the heating by the heating device 28C, the second drying layer becomes the second alignment layer (not shown) in which the polymer liquid crystal compound contained in the second drying layer is oriented. The film substrate 10 on which the second alignment layer is formed is guided to the UV irradiation device 30A. By the UV irradiation by the UV irradiation apparatus, the second alignment layer is cured to become the third coating layer 13. Thus, a laminated film 2 is obtained. When the polymer liquid crystal compound is not used in the coating liquid forming the third coating layer 13, there is no alignment step by the heating device 28C and no curing step by the UV irradiation device 30C. Therefore, when the polymer liquid crystal compound is not used for the coating liquid, the second dry film obtained by the drying device 26A is the laminated film 2. The laminated film 2 is guided by a take-up shaft 36 and wound in a roll shape to obtain a take-up roll 38 of the laminated film 2.

The first coating layer 11, the second coating layer 12 and the third coating layer 13 preferably have a thickness of 1 占 퐉 or more. In this case, it has a characteristic of preventing transmission of sunlight in the infrared region. If the difference | H1 - H2 | between the heights of the first pair of tumblers 16 and the second pair of tumblers 17 is less than 3 占 퐉 and the interval between the first pair of tumblers 16 and the pair of tumblers 17 is 1 mm or more. The gap between the back surface of the film and the surface of the film is further secured by the first pair of pawl pairs 16 and the pair of pairs of pawls 17 during the lateral displacement at the time of winding and during the winding prevention. Therefore, damage such as scratches and wrinkles is imparted to the film surface or the film due to contact or close contact between the back surface of the film and the film surface at the time of winding, dust adhering to the film, lateral displacement or winding up, The laminated film 2 is wound so that the black band is not more clearly visible.

In the thus obtained laminated film 2 as shown in Fig. 1 (C1), the surface of the second coated layer 12 can be treated with argon ions by ESCA (electron spectroscopy for chemical analysis) Nm / min. And the calculation is carried out, for example, an analysis result of fluorine as shown in Fig. 12 is obtained. As shown in Fig. 12, fluorine of 90% or more of the total fluorine content is present in a region from the surface of the second coating layer 12 to a depth of 500 nm (hereinafter also referred to as surface layer). As described above, the second coating layer 12 is segregated with fluorine. Further, the tendency of segregation of fluorine is almost the same in all the coating layers using the fluorine-based alignment control agent, not limited to the second coating layer 12.

In the same laminated film (2), when the shape is measured using a film thickness meter on one side of the end having a pair of ridges, for example, a profile as shown in Fig. 13 (B) is obtained. In the graph shown in Fig. 13 (B), the vertical axis indicates the height (unit: 占 퐉) from the lower end of the region (b) surrounded by the broken line in (A). The abscissa is the distance from the right end of the area (b) surrounded by the broken line in (A). In the graph of FIG. 10 (B), reference numeral R10 is assigned to a region showing the height of the film substrate 10, reference numeral R11 is assigned to a region showing the height of the first coated layer 11, The reference numeral R12 is assigned to a region indicating the height of the layer 12 and the reference numeral R16 is assigned to a region indicating the height of the first pair of ridges 16. [ As shown in the graph of FIG. 5 (B), the first pair of protrusions 16 is reliably formed by the above-described manufacturing method. It is also confirmed by the film thickness gauge that the second pair of protrusions 17 is reliably formed by the above-described manufacturing method. In FIG. 13 (A), hatching is omitted.

The present embodiment is a first coating layer in which the first coating layer 11 is a layer having no pair of stones and the second coating layer 12 is a factor for forming the first pair of stones 16, And the third coating layer 13 is a second coating film which is a factor for forming the second pair of stones 17. However, the present invention is not limited to this. For example, as shown in (A1), (B1), (B2), (C2), and (C3) of FIG. 1, the first coating layer 11, the second coating layer 12, 13) may be formed on any two layers. Alternatively, even if the base portion of the pair of stones is formed on any two of the first coating layer 11, the second coating layer 12 and the third coating layer 13 as shown in Fig. 1A, do. Alternatively, the first coating layer 11, the second coating layer 12, the third coating layer 13, and the third coating layer 14 may be formed as in the case of (A2), (B3), (C4), (C5) Or a base pair of a pair of stones may be formed on any one of the other layers. As described above, the combination of the first coating layer 11, the second coating layer 12, the third coating layer 13 and the first coating film and the second coating film may be any combination as shown in Fig. However, in the case where the first coating layer 11 is used as the first coating film, it is necessary to select the film substrate 10 having the surface energy of 40 mN / m or less as the first base material.

The coating widths of the first coating layer 11, the second coating layer 12 and the third coating layer 13 are set as shown in Fig. 1 (A1), (B1), and It is preferable that the first coating layer 11, the second coating layer 12 and the third coating layer 13 are formed in the order of increasing the coating width. This is because the control of the first and second pair of stalk rods 16 and 17 is facilitated.

In the present embodiment, the film substrate 10 and the three-layer coating layers 11, 12, and 13 are described. However, the present invention is not limited to this. For example, even if the application layer has only two layers, and the coating layer is increased to make the surface energy of the base material easier to form the base pairs so as to form the base pairs, even if the total application layer is four or more layers, 2) It may be a structure having these two pairs of protruding portions in the lateral direction side end portions. In addition, for example, any layer formed on the film substrate 10 or on each coating layer by a vacuum film forming process or the like may be formed for the purpose equivalent to, for example, four or more coating layers. In the present embodiment, two layers of the right-handed circularly polarized light reflection layer and one layer of the right-handed circular reflection layer are formed in order to make the film a laminated film for heat storage. However, The coating layer may be appropriately added.

Example

Next, an embodiment of the present invention will be described. Hereinafter, the characteristics of the present invention will be described in more detail with reference to Examples and Comparative Examples (and Comparative Examples are not known). The materials, the amounts used, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the following specific examples.

The present embodiment and this comparative example are different from the first embodiment in that the first coating layer 11, the second coating layer 12 and the third coating layer 13 are formed on the film substrate 10 under various conditions, And the laminated film was taken up by a take-up shaft 36 and evaluated according to the following criteria. The following " deformation " in the evaluation of winding includes both the case where the winding roll is deformed before the winding is completed, i.e., the winding roll is deformed during winding, and the case where the winding roll after the winding is completed is deformed later.

1. Coiling evaluation

A: No wound shape change

B: With some winding shape variation

C: Overall wound shape variation

2. Evaluation of lateral displacement

A: No lateral deviation

B: Some lateral misalignment

C: Overall offset

In the examples and comparative examples, a polyethylene terephthalate film (PET, manufactured by Fuji Film Co., Ltd.) having a thickness of 75 占 퐉 was used for the film substrate 10. In all the examples and comparative examples, the conveying speed of the film substrate 10 was 10 m / min, the drying time in the drying step was 30 seconds, the heating temperature in the heating step was 85 degrees And the heating time was 4 minutes. In the UV irradiation step, the atmosphere in the apparatus was replaced with nitrogen, the oxygen concentration was set to 300 ppm, the temperature was set to 30 DEG C, the output was adjusted with an eyelash-made metal halide lamp, and UV irradiation was performed at 500 mJ / The polymer liquid crystal compound was hardened to improve the performance.

For all coating layers, a coating liquid (A) and a coating liquid (B) each having a polymer liquid crystal compound, a fluorinated alignment control agent, and a solvent were used. The compositions of the coating liquid (A) and the coating liquid (B) are the compositions shown in Tables 1 and 2, respectively.

The combinations of the coating liquids used for forming the respective coating layers are shown in Table 3 below. Table 3 also shows the reflection characteristic of each layer and the peak of the reflection wavelength.

Table 4 shows the conditions of execution and evaluation results of this embodiment, and Table 5 shows the conditions and evaluation results of this comparative example. For the laminated film 2 obtained in the example, the number of pairs of ridges in one side end portion, the height of each ridged pair in the central portion of the laminated film 2 from the film surface, and the cross- , And " the shape of the number of tooth pairs (height) " in Table 4. The laminated film obtained as a comparative example is shown in the column of " the number of pairs of stones (height) in Table 5 ". In the drawings inside these columns, the height of the film surface in the center portion is indicated by a broken line. In Tables 4 and 5, hatching is omitted in the drawing of the sectional shape of the side end portion.

As shown in Table 4, for the laminated film 2 having the first and second pairs of ridges 16 and 17 having a height of 1 占 퐉 or more and a difference in height of 3 占 퐉 or less, both of the winding evaluation and the lateral displacement evaluation Good results were obtained. On the other hand, as shown in Table 5, in the laminated film having only the first pair of ridges having a height of 1 占 퐉 or more, the results were obtained in both the winding evaluation and the lateral displacement evaluation. In the case of a laminated film having no stamper pile having a height of 1 占 퐉 or more, the result in the winding evaluation and the evaluation result in the lateral deviation were bad.

From this, it can be seen that the laminated film 2 having the first and second pairs of ridges 16 and 17 having a height of 1 m or more higher than the film surface in the middle in the width direction solves this problem. It has also been found that the laminated film 2 having the first and second pairs of ridges 16 and 17 having the height difference | H1 - H2 | of 3 占 퐉 or less solves this problem more effectively. It was also found that when the surface energy of the base material was 40 mN / m or less and the surface tension of the coating liquid was 20 mN / m or more and 40 mN / m or less,

Claims (16)

A first substrate on the web;
A first coating film formed by applying a first coating liquid on the first base material, wherein the first coating liquid has a polymer liquid crystal compound, a fluorinated alignment control agent and a solvent;
A second coating film formed by applying a second coating liquid on a second substrate, wherein the second substrate has the first substrate and the first coating film, and the second coating liquid comprises a polymer liquid crystal compound and a fluorinated alignment agent And a second coating film having a solvent and a different width from the first coating film;
A first pair of stones formed on the first coated film along both side edges of the first coated film; And
And second stamper pairs formed on the second coating film along both side edges of the second coated film and provided at either the center side or the side end side in the width direction of the wet film than the first stamper pair,
Wherein the first ridge pair and the second ridge pair are 1 占 퐉 or more higher than the film surface in the widthwise central portion of the laminated film. The method according to claim 1,
Wherein at least 90% of the total fluorine content contained in the first coating film is present in a region from the surface of the first coating film to a depth of 500 nm, and in the region from the surface of the second coating film to the depth of 500 nm, 2 A laminated film wherein at least 90% of the total fluorine content contained in the coating film is present. The method according to claim 1,
Wherein the difference between the heights of the first pair of ridges and the second pair of ridges is 3 占 퐉 or less. 3. The method of claim 2,
Wherein the difference between the heights of the first pair of ridges and the second pair of ridges is 3 占 퐉 or less. The method according to claim 1,
And the interval between the first pair of ridges and the second pair of ridges is at least 1 mm. The method according to claim 1,
Wherein the first coating film and the second coating film have thicknesses of 1 占 퐉 or more, respectively. The method according to claim 1,
Wherein the first coating film and the second coating film respectively represent a cholesteric phase. The method according to claim 1,
Wherein the surface energy of each of the first substrate and the second substrate is 40 mN / m or less. The method according to claim 1,
Wherein the surface tension of each of the first coating liquid and the second coating liquid is in the range of 20 mN / m or more and 40 mN / m or less. The method according to claim 1,
Wherein the viscosity of each of the first coating liquid and the second coating liquid after solvent volatilization is not more than 0.5 Pa s. (A) applying a first coating liquid to a first coating area on a first substrate on a web to form a first wet film, wherein the surface energy of the first substrate is 40 mN / m or less, Wherein the surface tension of the first wet film is in the range of 20 mN / m to 40 mN / m;
(B) evaporating the solvent from the first wet film to form a first dry film;
(C) curing the first dried film to form a first coated film;
(D) applying a second coating liquid to a second coating area on the second substrate having a width different from that of the first coating area to form a second wet film, wherein the second substrate comprises a first substrate, Wherein the surface energy of the second substrate is 40 mN / m or less and the surface tension of the second coating liquid is in a range of 20 mN / m or more and 40 mN / m or less; forming the second wet film ;
(E) evaporating the solvent from the second wet film to form a second dry film; And
(F) curing the second dried film to form a second coated film. 12. The method of claim 11,
(G) orienting a first polymer liquid crystal compound between the step (B) and the step (C), wherein the first coating liquid contains the first polymer liquid crystal compound, the fluorinated alignment control agent and a solvent, Orienting the liquid crystal compound; And
(H) orienting a second polymer liquid crystal compound between the step (E) and the step (F), wherein the second coating liquid contains the second polymer liquid crystal compound, the fluorinated alignment control agent and a solvent, A method for producing a laminated film, comprising the steps of: orienting a liquid crystal compound. 13. The method of claim 12,
Wherein the first coating film and the second coating film are in a cholesteric phase, respectively. 12. The method of claim 11,
Wherein the viscosity of each of the first coating liquid and the second coating liquid after solvent volatilization is 0.5 Pa s or less. 12. The method of claim 11,
Wherein a distance between the first application region and the second application region is 1 mm or more. 12. The method of claim 11,
Wherein the thickness of the first coating film and the thickness of the second coating film are 1 占 퐉 or more, respectively.

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