TWI821421B - Film manufacturing method and equipment, film - Google Patents

Abstract

The present invention provides a film manufacturing method and equipment capable of efficiently producing a long film having a plurality of larger convex portions, and a film obtained thereby. The film manufacturing method includes a discharging process and a hardening process, and forms a plurality of convex portions on a long film material. The discharge device (45) is filled with the photocurable composition (15), and includes a casing and an opening and closing member. The photocurable composition (15) is filled into the shell in a pressurized state. The opening and closing member discharges the photocurable composition (15) in the form of droplets (41) and causes them to fly toward the moving film material (11). In the hardening process, the light source (47) is used to harden the photocurable compound of the droplet (41) to form the convex portion (12) of the droplet (41).

Description

Film manufacturing method and equipment, film

The invention relates to a film manufacturing method and equipment, and a film.

There are known window films that have both visibility prevention and design properties and are attached to windows of buildings (for example, high-rise buildings, shop buildings, houses, etc.). In such a window film, a plurality of convex portions are formed on the surface of the film, thereby preventing visibility when viewing the other from the exterior and interior of the building or improving the design of the window.

In addition, it is known that a plurality of convex portions are formed on a light functional film used for digital signage or screen projection. This type of optically functional film is required to have both light transmittance and light scattering properties, and further improvements in these functions are required.

As a method of forming the convex portion on the film material, there are a method using screen printing (for example, refer to Patent Document 1) and a method using inkjet (for example, refer to Patent Documents 2 and 3). There is also a so-called needle suspenser method in which the tip of a nozzle that sprays the solution for forming the convex portion is placed very close to the film material, and the solution is sprayed from the tip to spread over the film material. And make it adhere to the film material (for example, refer patent document 4). [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2014-012388 [Patent Document 2] Japanese Patent Application Publication No. 2013-227515 [Patent Document 3] International Publication No. 2010/143524 [Patent Document 4] Japanese Patent Application Publication No. 2017-109481

However, although the method described in Patent Document 1 can form convex portions on a sheet-like (single piece) film material, it cannot continuously form convex portions on a long film material. Therefore, it is difficult to produce a long film having a plurality of convex portions.

Furthermore, in the methods described in Patent Documents 2 and 3, the size of the droplets that can be formed is very small. Therefore, the size of the convex portion that can be formed by one droplet is limited, and it is not possible to achieve the above-mentioned window film and /or the level of the above-mentioned properties required for optically functional films. Furthermore, when the convex portion is formed into a large size, in order to form one convex portion, it is necessary to discharge the liquid droplets a plurality of times in a state where they overlap, which results in poor efficiency. In addition, it is also very difficult to adjust the overlapping state of droplets. Therefore, it is difficult to produce films for use in each of the above-mentioned applications. In this way, if the convex portion can be formed larger and the film can be produced in an elongated shape, the application can be expected to expand.

Therefore, an object of the present invention is to provide a film manufacturing method and equipment that can form larger convex portions and efficiently produce a long film having a plurality of convex portions, and a film obtained thereby.

In order to achieve the above object, the film manufacturing method of the present invention has a discharge process and a hardening process, and forms a plurality of convex portions on a long film material that moves in the longitudinal direction. In the discharging process, the discharging process includes a casing filled with a solution containing a photocurable compound, a through-hole formed in the casing with one end exposed to the inside and the other end serving as a discharging port for the solution, and an opening and closing member that opens and closes the one end. The casing of the device is filled with the solution in a pressurized state, and the interior is filled by repeatedly moving an opening and closing member that moves between an open position for opening the one end and a closed position for closing the one end from the closed position to the open position. The above-mentioned solution is discharged in the form of droplets from the discharge port, and is allowed to fly toward the moving film material. In the curing process, the photocurable compound attached to the droplets of the film material is cured by using a light source, which is provided downstream of the discharge device in the moving direction of the film material, to form convex portions of the droplets. And emits light that hardens the photocurable compound.

The opening and closing member has a piezoelectric element, a contact portion fixed to the piezoelectric element and in contact with the discharge port, and a voltage application portion that applies voltage to the piezoelectric element, and by increasing or decreasing the voltage applied to the piezoelectric element by the voltage application portion It is preferable to move the contact portion between the open position and the closed position.

In the discharge process, it is preferable to discharge droplets with a volume in the range of 0.8×10 ^-12 m ³ or more and 100.0×10 ^-12 m ³ or less.

The viscosity of the above solution is 20mPa. s or more and 1000mPa. The range below s is preferred.

It is preferable to adjust the shape of the convex portion by adjusting the movement time of the film from the discharge device to the light source.

The light is preferably ultraviolet light, and the photocurable compound is preferably an ultraviolet curable compound. The ultraviolet curable compound is preferably an acrylamide compound.

The photocurable compound preferably contains a light stabilizer. Furthermore, the photocurable compound preferably contains a monofunctional acrylic compound. Furthermore, the photocurable compound preferably contains a polyfunctional acrylate compound.

The film material is preferably formed of cellulose chelate.

Furthermore, the film manufacturing equipment of the present invention includes a moving mechanism, a discharge device, and a light source, and forms a plurality of convex portions on a long film material that moves in the longitudinal direction. The moving mechanism moves the elongated film material along the length direction. The discharge device is disposed with the discharge port of the solution containing the photocurable compound facing the moving path of the film material, and discharges the solution. The light source is provided downstream of the discharge device in the moving direction of the film material, and emits light for curing the photocurable compound. The discharge device has a housing formed with a through hole and an opening and closing member. The casing is filled with the above-mentioned solution in a pressurized state inside. One end of the through hole formed in the casing is exposed to the inside and the other end serves as an outlet. The opening and closing member repeatedly moves between the open position and the closed position. In the open position, the one end is opened, and the solution is discharged in the form of droplets from the discharge port and flies toward the moving film material, thereby causing it to adhere. In the film material, the above-mentioned one end is blocked at the blocking position to stop the discharge of droplets.

The film of the present invention includes a film material formed of a cellulose acyl compound, and one surface of the film material is provided with any one of a plurality of spherical crown convex portions, a convex portion with a flat top, and a convex portion with a depression formed on the top. .

It is preferable that the plurality of convex parts are arranged regularly. [Effects of the invention]

According to the present invention, the protrusions are formed to be larger and a long film having a plurality of protrusions is obtained efficiently.

In FIG. 1 , a film 10 as an embodiment of the present invention is formed in a long shape. The film 10 includes a long film material 11 and a plurality of convex portions 12 . The film 10 can be used as a window film with both visual recognition prevention and design properties attached to the windows of buildings (such as high-rise buildings, shop buildings, houses, etc.) and as a light-transmitting film used in digital signage or screen projection. And/or light-scattering light functional films, etc.

The thin film material 11 is formed into a so-called flat film shape with both sides flat. The thickness T11 (unit: μm) of the film material 11 is not particularly limited, but from the viewpoint of handleability (workability) and rollability of the film 10, it is preferably in the range of 10 μm or more and 300 μm or less. .

The material of the film material 11 is not particularly limited, but when used as a window film or a photofunctional film, it is preferably made of a transparent polymer. In addition to the polymer, the film material 11 may contain one or more kinds of various additives such as plasticizers, ultraviolet absorbers, or microparticles.

As the polymer forming the film material 11, a thermoplastic resin is preferable. As the thermoplastic resin, cellulose chelate, polyethylene terephthalate, acrylic resin, cyclic polyolefin resin (for example, ARTON (manufactured by JSR Corporation) Registered trademark)), etc. are better. Among these, cellulose chelates are more preferred. Examples of cellulose chelates include triacetyl cellulose (TAC), diacetyl cellulose (DAC), cellulose acetate propionate, and butyl acetate. Acid cellulose, etc. Among cellulose chelates, TAC is particularly preferred. This is because among cellulose acyl compounds, the transparency of TAC, the function of forming the convex portion 12 into a target shape (convex portion formability), and the relationship with the convex portion 12 formed of a photocurable resin as described later. The adhesive strength (adhesive strength) is particularly excellent.

The plurality of convex portions 12 are formed to be distributed over the entire area of one surface (hereinafter, referred to as the first surface) 11A of the film material 11 . However, only a part of the plurality of convex portions 12 is depicted in FIG. 1 . In this example, the plurality of convex portions 12 are formed only on the first surface 11A, but they may also be formed on the other surface 11B (see (B) of FIG. 2 ). The plurality of convex portions 12 are arranged regularly, and in this example, they are arranged squarely as shown in FIG. 1 . However, the arrangement pattern of the plurality of convex portions 12 is not particularly limited. For example, it may be in a matrix form, or may be a so-called irregular arrangement (random arrangement) without regularity.

As shown in FIG. 2 , in the film 10 of this example, the convex portion 12 has a spherical crown, that is, a semicircular cross section or an arcuate cross section. Accordingly, when light is incident on the surface of the film 10 on which the convex portion 12 is formed, the light is reflected and scattered by the circular or arcuate shape of the convex portion 12 , thereby providing excellent design and/or visual recognition resistance. The protrusions 12 are arranged in a separated state from each other, but may also be in contact with each other. In addition, if the centers of the convex portions 12 are separated from each other when the first surface 11A is viewed from the vertical direction, the convex portions 12 may overlap each other. In this example, the pitch PW12 (unit: mm) between the convex portions 12 in the width direction of the film 10 (also the width direction of the film material 11, hereinafter referred to as the "width direction") is constant, and in the longitudinal direction ( The distance PL12 (unit: mm) between the protrusions 12 in the longitudinal direction of the film material 11 (hereinafter referred to as the "longitudinal direction") is also set to be constant. The pitch PW12 is the distance between the centers of the convex portions 12 in the width direction when the first surface 11A is viewed from the vertical direction, and the pitch PL12 is the distance between the centers of the convex portions 12 in the length direction. In the following description, when the pitch PW12 and the pitch PL12 are not distinguished, they are described as the pitch P12 (unit: mm).

The plurality of convex portions 12 are formed to have the same size, but may also be formed to have different sizes. In addition, the convex portions 12 with different sizes can be arranged with a certain regularity. The diameter RP (unit: μm) of the convex portion 12 when the first surface 11A is viewed from the vertical direction is preferably in the range of 50 μm or more and 2000 μm or less. When the diameter RP is 50 μm or more, for example, when the film 10 is used as a window film, the visual recognition resistance when viewing the other from the outside and the inside of the window is higher than when the diameter RP is less than 50 μm. When the diameter RP is 2000 μm or less, compared to the case where it is larger than 2000 μm, as mentioned above, when used as a window film, the unevenness seen due to the plurality of convex portions 12 is smaller (thin), so the design is excellent. . In addition, the shape of the convex portion 12 when the first surface 11A is viewed from the vertical direction is circular, but it does not necessarily need to be a strict circle. In this case, the equivalent circle diameter is the above-mentioned diameter D12. The equivalent circle diameter is the diameter of a circle of the same area.

When the height of the convex portion 12 is HP (unit: μm), the ratio HP/RP of the height HP divided by the diameter RP is preferably in the range of 0.01 or more and 0.5 or less. When the ratio HP/RP is 0.01 or more, compared with the case where it is less than 0.01, the light scattering property due to the convex portion 12 is improved, and the visibility prevention property is improved. When the ratio HP/RP is 0.5 or less, a part of the convex portion 12 is less likely to be chipped off and detached during the processing of the film 10 than when it is greater than 0.5. In addition, by performing the above-mentioned complicated processing, even if a part of the convex portion 12 is shaved off or the convex portion 12 is detached, the film portion is less likely to be observed as uneven, and the design of the film 10 is excellent. . In addition, compared with the case where the ratio HP/RP is greater than 0.5, when the convex portion 12 is formed to a ratio HP/RP of 0.5 or less, there is an advantage that even when the convex portion 12 is connected to the curing unit 34 described below and the roll When the rollers 37B between the picking portions 35 are in contact, they are more difficult to be chipped off and less likely to come off. In addition, the height HP is the distance from the first surface 11A to the top of the convex portion 12 .

The convex portion 12 is formed of a cured resin (polymer) which is a polymerization (crosslinked) product obtained by curing the photocurable compound contained in the photocurable composition 15 (see FIG. 3 ) described below. The photocurable compound is a compound that is cured (including cross-linked) by irradiation with light, and the details will be described later. As the cured resin, a cured resin obtained by curing an ultraviolet curable resin is more preferred.

The film manufacturing equipment 30 shown in FIG. 3 is an example of equipment for manufacturing the film 10. In this film manufacturing equipment 30, the film 10 is obtained in the form of a film roll 31 wound into a roll shape. The film manufacturing equipment 30 includes a delivery unit 32 , a discharge unit 33 , a curing unit 34 and a winding unit 35 in order from the upstream side in the movement direction Dc of the film material 11 . The movement path for moving the film material 11 is provided with rollers 37A and 37B. The rollers that come into contact with the surface of the film material 11 on which the convex portions 12 are not formed and the surface side on which the convex portions 12 are not formed are marked with a symbol 37A. The roller is marked with symbol 37B. In addition, in the following description, when the roller 37A and the roller 37B are not distinguished, they are described as roller 37. Among the plurality of rollers 37 , there may be a driving roller equipped with a rotation mechanism (not shown) and rotated in the circumferential direction by the rotation mechanism.

The film material roll 38 in which the film material 11 is wound in a roll shape is mounted on the feeding part 32 . The feeding unit 32 is provided with a rotating shaft 32 a for wrapping the film roll 38 . The rotating shaft 32 a is rotated by a rotating mechanism (not shown) to continuously feed out the elongated film material 11 from the film roll 38 . The moving speed of the film material 11 is adjusted by adjusting the rotation speed of the rotating shaft 32a. In this way, the feeding part 32 constitutes a moving mechanism that moves the film material 11 in the longitudinal direction.

The moving speed of the film material 11 is appropriately set according to the target pitch PL12 and/or the shape of the convex portion 12, but from the viewpoint of forming the convex portion 12 at the target position and in the target shape more reliably, it is 2 m/min or more and 200 m/min. The following range is preferred.

The discharge part 33 is used to form the liquid droplets 41 that become the convex parts 12 (see FIGS. 1 and 2 ) on the first surface 11A of the film material 11 . The discharge part 33 is composed of a support roller 42 that supports the film material 11, a discharge unit 44 that discharges the photocurable composition 15 in the form of droplets 41, and the like. The support roller 42 serves as a driven roller, has the film material 11 wound around the circumferential surface, and rotates when the circumferential surface comes into contact with the film material 11 moving in the longitudinal direction. In addition, a rotation mechanism (not shown) may be provided on the support roller 42, and the rotation shaft 42a may be rotated by the rotation mechanism (not shown).

The discharge unit 44 includes a plurality of discharge devices 45 that discharge the photocurable composition 15 and a plate-shaped support member 46 that supports the plurality of discharge devices 45 . The number of the discharge devices 45 is determined depending on the arrangement aspect of the formed convex portions 12 and the like, and there may be only one discharge device 45 .

The discharge device 45 is disposed in an attitude such that the discharge port 45 a (see FIGS. 4 and 5 ) for discharging the photocurable composition 15 faces the peripheral surface of the support roller 42 which is part of the movement path of the film material 11 . When focusing on one of the plurality of discharge devices 45, the photocurable composition 15 is intermittently discharged in the form of droplets from the discharge port 45a toward the moving film material 11, so that the droplets 41 are sequentially distributed in the length direction. Attachment (discharge process). In this way, the film 10 is manufactured through the discharge process in the discharge part 33 . The details of the discharge device 45 will be described later using another drawing.

The photocurable composition 15 is an example of a solution containing a photocurable compound. In this example, it is a mixture containing a liquid or solid photocurable compound. The photocurable compound may be a liquid, in which case only the photocurable compound may be used. Furthermore, a mixture of a plurality of liquid or solid photocurable compounds may be used as the photocurable composition 15 . The liquid photocurable compound may be any of a monomer, an oligomer, and a polymer, and may be used in a solvent-free state, that is, without using a solvent. Examples of the photocurable compound include compounds containing a photocurable vinyl double bond group such as an acrylic group or a styrene group.

As the photocurable compound, an ultraviolet curable compound that is cured by irradiation of ultraviolet rays (a region with a wavelength of 100 nm or more and 400 nm or less) is preferable, and this is also defined in this example. This is because, compared with other photocurable compounds, the curing time of the ultraviolet curable compound is shorter, it is easier to form the convex portion 12 of the target shape, and the curing process described below is performed by the curing unit 34 more efficiently. Damage to the film material 11 is reliably suppressed.

As the ultraviolet curable compound, a polyfunctional acrylate compound, an acrylamide compound, a monofunctional acrylic compound, or the like can be used.

Examples of the polyfunctional acrylate compound include polyfunctional alcohol (meth)acrylate compounds, including alkoxylated polyfunctional (meth)acrylate compounds, and oligomers. For example, neopenterythritol tri(meth)acrylate, neopenterythritol tetra(meth)acrylate, dineopenterythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate Ester, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate , tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, bis(4-acrylyloxypolyethoxyphenyl)propane or neopentyl Glycol di(meth)acrylate and the like are preferred.

As an alkoxylated polyfunctional (meth)acrylate compound, ethoxylated (3) trimethylolpropane tri(meth)acrylate (trimethylolpropane ethylene oxide 3 molar addition A compound formed by tri(meth)acrylation of a substance), propoxylated (3) trimethylolpropane tri(meth)acrylate (addition of 3 moles of trimethylolpropane epoxypropane A compound formed by tri(meth)acrylation), ethoxylated (2) neopentyl glycol di(meth)acrylate (2 molar adduct of neopentyl glycol ethylene oxide A compound obtained by diacrylation) or propoxylated (2) neopentyl glycol di(meth)acrylate (a compound obtained by diacrylation of a 2 molar adduct of neopentyl glycol propylene oxide). Compounds formed) are preferred.

In addition, as the oligomer, polyester (meth)acrylate, urethane (meth)acrylate, etc. are preferred. In addition, preferred examples include modified glycerol tri(meth)acrylate, modified Bisphenol A di(meth)acrylate, bisphenol A’s propylene oxide (PO) adduct di(meth)acrylate, bisphenol A’s ethylene oxide (EO) adduct di(methyl) ) acrylate or caprolactone modified dineopenterythritol hexa(meth)acrylate, etc.

As acrylamide compounds, hydroxyethylacrylamide, dimethylacrylamide, isopropylacrylamide, diethylacrylamide, dimethylaminopropylacrylamide, N-vinyl Lactams, specifically N-vinylpyrrolidone or N-vinylcaprolactam, are also preferred.

As monofunctional acrylic compounds, isopentyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, ( Decyl methacrylate, isopentystyrene (meth)acrylate, isostearyl (meth)acrylate, 2-ethylhexyldiglycol (meth)acrylate, (meth)acrylic acid 2 -Methoxyethyl ester, butoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypropylene glycol (Meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isocamphenyl (meth)acrylate, 2-(meth)acryloxyethylsuccinate, 2-(meth)acrylyl Oxyethyl-2-hydroxyethyl phthalate, lactone modified flexible (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, (meth)acrylic acid 2 -(2-ethoxyethoxy)ethyl ester, cyclopentenyl (meth)acrylate, cyclopentenoxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate, (meth)acrylate ) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate or cyclic trimethylolpropane formal (meth)acrylate are preferred.

In addition, monofunctional acrylic compounds having a cyclic structure in the molecule are also preferred. Specific examples include acryloylmorpholine, benzyl acrylate, (meth)acrylic acid tetrahydrofurfuryl ester, and (methyl)acrylic acid. Isocamphenyl acrylate, cyclopentenyl (meth)acrylate, cyclopentenyloxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate or cyclic trimethylolpropane formal (methyl ) acrylate, etc. These monofunctional acrylic compounds having a cyclic structure in the molecule can improve the solubility of the photopolymerization initiator and the like into the photocurable composition 15 and also improve the heat resistance of the cured convex portion 12 .

Multifunctional acrylate compounds can improve the hardness and strength of the cured resin as a product. The acrylamide compound shortens the time required for hardening and forms the convex portion 12 with further improved adhesion to the film material 11 . The monofunctional acrylic compound adjusts the physical properties of the photocurable composition 15 and adjusts the light scattering properties such as the refractive index of the convex portion 12 .

The photocurable composition 15 preferably contains an acrylamide compound as an ultraviolet curable compound. Therefore, when the film material 11 is formed of a cellulose acyl compound, it is particularly preferable that the convex portion 12 contains an acrylamide-based compound among the above-mentioned ones because the adhesive force with the cellulose acyl compound is high.

In addition, the photocurable composition 15 preferably contains an acrylamide compound and a polyfunctional acrylate compound as the ultraviolet curable compound. Thereby, the discharged droplets are rapidly hardened by light irradiation, and the hardened convex portions have sufficient strength. Therefore, the rollers will not be contaminated due to the convex portions falling off when the rollers are in contact, and the rollers can be formed continuously. Good convex shape. Moreover, it is preferable to use two or more types of polyfunctional acrylate compounds. This is because by this, the viscosity of the photocurable composition can be adjusted to a preferable range, and the shape of the convex portion can be easily adjusted. Moreover, it is also preferable that the photocurable composition 15 further contains a monofunctional acrylic compound. This is because the photopolymerization initiator or light stabilizer for improving rapid hardening or stability can be uniformly dissolved in the photocurable composition 15 , and the viscosity can be adjusted to a preferred range, and further, Improves the strength, durability, and heat resistance of the hardened convex portion.

The viscosity of the photocurable composition 15 is 20 mPa. s or more and 1000mPa. The range below s is preferred. With the viscosity of 20mPa. s or more, and less than 20mmPa. Compared with the case of s, the shape of the droplets 41 is less likely to change during the period after being attached to the film material 11 and then being cured by the curing unit 34 . Therefore, the timing of hardening can be easily adjusted, and the convex portion 12 of the target shape can be easily formed. With the viscosity of 1000mPa. s or less, and greater than 1000mPa. Compared with the case of s, it is easier to adjust the volume of the discharged droplets 41. Therefore, it is easy to form the convex portion 12 of the target size. The viscosity of the photocurable composition 15 is 30 mPa. s or more and 500mPa． The range below s is better, 40mPa. s or more and 300mPa. A range of s or less is further preferred.

In order to shorten the curing time or improve the strength of the convex portion 12 and/or the adhesiveness with the film material 11 , it is preferable to add a photopolymerization initiator or the like to the photocurable composition 15 . Examples of photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-Dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfonium compounds, rrophene dimers, onium salts, borates, active esters, active halogens , inorganic complexes, coumarins, etc.

Moreover, in order to improve the stability of the solution containing the photocurable compound (in this example, the photocurable composition 15), it is preferable to add a light stabilizer. Examples of light stabilizers include nitroso-based polymerization inhibitors, hydroquinone, methoxyhydroquinone, benzoquinone, p-methoxyphenol, or TEMPO (2,2,6,6-tetramethylpiperidine1 -oxy), hydroxy TEMPO (hydroxy-2,2,6,6-tetramethylpiperidine 1-oxy), cupferine Al or hindered amine, etc.

Among these light stabilizers, those having a secondary amine or tertiary amine structure as hindered amine light stabilizers (HALS, Hindered Amine Light Stabilizers) are preferred. For example, structures in which the 1-position of the nitrogen atom is substituted with an oxygen radical (TEMPO, hydroxy-TEMPO, etc.) are preferred, 4-hydroxy TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine 1 -oxygen group) is particularly preferred.

The amount of the light stabilizer is preferably in the range of 0.05 mass % or more and 1.0 mass % or less based on the photocurable composition 15, and is particularly preferably in the range of 0.1 mass % or more and 0.8 mass % or less. If it is within this range, the stability of the photocurable composition in the discharge device can be improved and the change in viscosity or hardening in the discharge device can be suppressed. Furthermore, the photocurability of the liquid droplets after discharge is sufficient, so it is relatively suitable. good. The photocurable compound can be in the state of a mixed liquid mixed with other compounds by adjusting the amount of the polyfunctional acrylate compound, the acrylamide compound, or the monofunctional acrylic compound, and can also adjust the viscosity. As viscosity regulators for adjusting viscosity, there are high-viscosity regulators that further increase the viscosity and low-viscosity regulators that further reduce the viscosity. In this example, a high-viscosity regulator is used.

The above viscosity is the viscosity at the temperature during the discharging process. In this example, the discharging is performed at room temperature (25°C), so the viscosity is set as the viscosity at 25°C. In this example, the viscosity is measured using a tuning fork type small vibration viscometer CJV5000 (A&D Company, Limited).

The hardening unit 34 is used to form the convex portion 12 from the liquid droplets 41 . The curing unit 34 is provided with a plurality of light sources 47 disposed downstream of the discharge portion 33 in the moving direction of the film material 11 and emits light, and a plate-shaped support member 48 that supports the plurality of light sources 47 . The number of light sources 47 is determined depending on the arrangement of the convex portions 12 to be formed, the type of the photocurable composition 15 , the moving speed of the film material 11 , etc., and there may be only one light source 47 . The wavelength of the light source 47 is determined according to the photocurable composition 15 used. In this example, since an ultraviolet curable compound is used as a component of the photocurable composition 15 as described above, the light source 47 that emits ultraviolet rays is used. By emitting light from the light source 47, the photocurable compound contained in the liquid droplets 41 attached to the film material 11 is cured, whereby the liquid droplets 41 become the convex portions 12 (hardening process).

The film material 11 on which the convex portion 12 is formed moves downstream by the roller 37A and/or the roller 37B, and is conveyed to the winding portion 35 . In addition, the roller 37 arranged downstream of the curing unit 34 is appropriate in order to improve the flatness of the film material 11 passing through the curing unit 34 or to adjust the conveyance of the film material 11 in the film manufacturing equipment 30 . configured locally.

The winding part 35 has a brick tower arm 56, and winds the film 10 on a winding core 58 set on the winding shaft 57. The brick tower arm 56 intermittently rotates 180 degrees by an arm drive unit (not shown) to selectively switch the winding core 58 between the winding position PS1 and the core replacement position PS2. In addition, a guide arm 59 is provided at an intermediate position in the rotation direction of the brick tower arm 56, and a guide roller 61 is attached to each front end of the guide arm 59. When the brick tower arm 56 rotates, the guide roller 61 supports the film 10 in a state where the film 10 does not come into contact with the brick tower arm 56 and the arm mounting shaft 62 .

The winding shaft 57 is provided at each front end of the brick tower arm 56, and a winding core 58 is mounted on the winding shaft 57. The winding shaft 57 has a rotating mechanism (not shown), and the film 10 is wound around the set core 58 by rotating the rotating mechanism. In this way, the take-up shaft 57 forms a moving mechanism together with the feeding part 32, and cooperates with the feeding part 32 to move the film material 11 in the longitudinal direction. However, the moving mechanism is not limited to this example. As mentioned above, at least a part of the plurality of rollers 37 arranged in the moving path may be configured as a driving roller.

At the winding position PS1, the film 10 conveyed from the roller 37 is wound on the winding core 58. In addition, at the core replacement position PS2, the film 10 of a constant length is wound, the film roll 31 of the roll is removed from the take-up shaft 57 together with the core 58, and a new empty roll is installed on the take-up shaft 57. to replace the core 58.

At the winding position PS1, the front end in the moving direction Dc is used as the one end 12A (see Figure 1), and the film 10 is wound on the winding core 58 from the one end 12A side. When the film roll 31 becomes a roll close to the predetermined length, In this state, the brick tower arm 56 rotates 180 degrees, so that the film roll 31 close to the roll is located at the core replacement position PS2. Furthermore, the empty winding core 58 is positioned at the winding position PS1. When the film roll 31 reaches a predetermined length, a rewinding device (not shown) is activated and the film 10 is cut. The leading film 10 that is cut uses the rear end in the moving direction Dc as the other end 12B, and the other end 12B is wound on the film roll 31 at the core replacement position PS2. In addition, the film 10 in the row after being cut is wound around the empty core 58 at the winding position PS1 from the one end 12A, using the front end as the one end 12A.

Hereinafter, the film 10 is similarly wound around the core 58 to obtain the film 10 continuously conveyed in the form of the film roll 31 .

The thin film manufacturing equipment 30 further includes a pulse generator 66 , a driver (drive circuit) 67 provided in the discharge device 45 , and a system controller 68 . The pulse generator 66 is connected to the most downstream one of the plurality of rollers 37 , that is, the one closest to the winding part 35 . The pulse generator 66 generates a pulse every time the connected roller 37 rotates at a constant angle, that is, every time the film material 11 is conveyed by a constant length.

In FIG. 3 , only one driver 67 is shown, but in this example, it is provided for each discharge device 45 . The driver 67 is an example of a voltage application unit that applies a voltage to a piezoelectric element 84 (see FIG. 5 ) of the discharge device 45 which will be described later. The driver 67 drives the discharge device 45 to start and stop the discharge of the liquid droplets 41 . Start spitting out refers to starting repeated spitting out within a certain period of time, and stopping spitting out refers to stopping repeated spitting out. Repeated discharging is carried out in a preset cycle. Therefore, when the set cycle is more than the above-mentioned certain time, the number of discharges from the start of discharge to the stop of discharge becomes one. In this way, repeated discharging also includes the case where the number of discharging times is one.

The system controller 68 centrally controls each part of the film manufacturing equipment 30 and forms the target convex portion 12 at the target position of the film material 11 by this control. Each time a pulse is generated from the pulse generator 66 , the system controller 68 obtains the movement length (conveyance length) of the film material 11 . The length of the moving path from the discharge port 45a (see FIGS. 4 and 5 ) of the discharge device 45 to the roller 37 connected to the pulse generator 66 is input to the system controller 68, and the sum of the length and the length is calculated as described above. The position of the front end (equivalent to one end 12A (see FIG. 1 )) of the film material 11 passing through the discharge port 45a in the longitudinal direction is detected based on the movement length of the film material 11. The system controller 68 further inputs the position in the film material 11 on which the convex portion 12 is formed in advance, and when the film material 11 passing through the discharge port 45a reaches the target position, the discharge device 45 is driven via the driver 67 .

The system controller 68 can determine the length of the film 10 wound on the take-up shaft 78 and/or the radius of the film roll 31 based on the above-mentioned pulses. In these cases, when the film material 11 passing through the discharge port 45a reaches the target position, the discharge device 45 is driven via the driver 67 based on the calculated length and/or radius.

The system controller 68 further inputs the cycle of discharging the liquid droplets 41 , the flow rate of the photocurable composition 15 supplied to the discharge device 45 , the volume of the liquid droplets 41 , the moving speed of the film material 11 , and the speed of the film material 11 in the winding section 35 . Each part of the film manufacturing equipment 30 is controlled based on these input signals, such as the cutting timing of the film 10 and/or the rotation timing of the tower arm 56 .

As shown in FIG. 4 , a plurality of discharge devices 45 of the discharge unit 44 are arranged in a row in the width direction. In this example, since the size of each discharge device 45 in the width direction is larger than the pitch PW12, it is impossible to arrange all the discharge devices 45 in a row in the width direction. Therefore, the discharge devices 45 used are arranged in two rows in the longitudinal direction. In this way, the arrangement method of the discharge device 45 can be appropriately determined based on the size and pitch PW12 of the discharge device 45 , and the discharge device 45 can be arranged so that the pitch PW45 of the discharge port 45 a in the width direction is the same as the pitch PW. Can.

In this example, as described above, the film 10 is formed to have the convex portions 12 over the entire width direction, so the discharge device 45 is disposed over the entire width direction. Moreover, even in the case of manufacturing the film 10, by disposing the discharge device 45 freely in the width direction and using a displacement mechanism (not shown) that moves the discharge device 45 in the width direction, the discharge device can be 45 is displaced in the width direction, so it is not necessary to provide a plurality of discharge devices 45 over the entire area in the width direction.

The light sources 47 of the curing unit 44 are similarly arranged in a plurality of arrays in the width direction. The light sources 47 are respectively arranged at positions in the width direction of the discharge openings 45a of each discharge device 45. Thereby, each droplet 41 formed on the thin film material 11 is reliably irradiated with light.

The shape of the liquid droplets 41 on the film material 11 changes until hardening. For example, the shape changes such as flattening (the height becomes lower and the diameter R41 becomes larger), the top of the droplet 41 becomes flat, or the top of the droplet 41 becomes dented. Furthermore, the shape of the convex portion 12 formed by hardening depends on the shape of the droplet 41 . As described above, the film 10 of this example has the plurality of convex portions 12 having the same shape, and therefore the hardening of the liquid droplets 41 also starts at a certain timing.

Therefore, the light sources 47 are each arranged in a state where the distance from the discharge port 45a of the discharge device 45 of the liquid droplets 41 to be irradiated is constant. For example, in this example, the light source 47 that emits light toward the droplets 41 formed by the discharge devices 45 of one row on the upstream side in the movement direction among the plurality of discharge devices 45 emits light toward the other rows on the downstream side. The light source 47 for emitting light from the droplets 41 formed by the discharge device 45 is disposed at a position shifted to the downstream side by a distance PL45 from the discharge port 45 a in the longitudinal direction. Thereby, the irradiation of each droplet 41 starts within a certain period of time after formation, thereby forming the convex portion 12 with a uniform shape. In FIG. 4 , the number of light sources 47 arranged along the moving direction is illustrated as three. However, the number of light sources 47 should be determined according to the moving speed of the film material 11 , the viscosity of the photocurable composition 15 (see FIG. 3 ), The time required for hardening, etc. may be appropriately determined.

As described above, the shape of the convex portion 12 changes depending on the start timing of hardening of the liquid droplets 41 on the film material 11. Therefore, by utilizing this, the shape of the convex portion 12 can be adjusted. That is, by adjusting the movement time of the film material 11 from the discharge device 45 to the light source 47, the shape of the convex portion 12 can be adjusted. When the convex portion 12 with a flatter spherical crown is formed, when the convex portion 91 with a flat top is formed (see FIG. 6 ), and when the convex portion 96 with a concave top is formed (see FIG. 7 ), the distance from the discharge device 45 to The movement time to the light source 47 is sufficient. Furthermore, when the convex portion of the spherical crown is formed to have a higher height and a smaller base area, the moving time from the discharge device 45 to the light source 47 can be further shortened.

The method of changing the movement time of the film material 11 from the discharge device 45 to the light source 47 may be any of a method of changing the movement speed of the film material 11 and a method of changing the distance L between the discharge device 45 (discharge port 45a) and the light source 47 a method. For example, by displacing the light source 47 upstream in the moving direction, the convex portion 12 with a higher height and smaller base area can be formed, and by displacing the light source 47 downstream, a flatter convex portion 12 can be formed.

As shown in FIG. 5 , the discharge device 45 includes a housing 71 and an opening and closing member 72 . The housing 71 is composed of a housing body 73, a bottom member 74, a pressing member 75, O-rings 77a and 77b, a sealing member (gasket) 78, and the like, and is filled with the photocurable composition 15 in a pressurized state. The housing body 73 has a supply port 73a for the photocurable composition 15 formed in a side surface thereof, and a supply part 81 for supplying the photocurable composition 15 at a predetermined flow rate is connected to the supply port 73a.

The bottom surface and the top surface of the housing body 73 are open, a bottom member 74 is fixed to the open part of the bottom surface, and a pressing member 75 is fixed to the open part of the top surface. The sealing member 78 is provided on the inner surface of the pressing member 75 , and together with the O-ring disposed between the sealing member 78 and the pressing member 75 , prevents the photocurable composition 15 filled inside from leaking. A through hole 82 is formed in the bottom member 74 . One end of the through hole 82 is exposed to the interior filled with the photocurable composition 15 and the other end becomes the discharge port 45 a. The diameter (unit: μm) of the discharge port 45a is preferably in the range of 30 to 300, and more preferably in the range of 50 to 150.

The opening and closing member 72 is used to open and close the inner end of the through hole 82 . The opening and closing member is movable between an open position in which the one end of the through hole 82 is opened as shown in FIG. 5(B) and a closed position in which the one end is blocked as shown in FIG. 5(A) . The opening and closing member 72 has a contact portion 83, a piezoelectric element (piezo element) 84, and the actuator 67 (see FIG. 3). The contact portion 83 provided at the front end is in contact with the bottom member 74 in a state of closing the one end in the closed position. .

The contact portion 83 is fixed to the piezoelectric element 84 deformed by the applied voltage via the shaft 85 . The contact portion 83 moves between the open position and the closed position by increasing or decreasing the voltage applied by the driver 67 (see FIG. 3 ). In addition, the shaft 85 is inserted into the respective centers of the pressing member 75 and the sealing member 78 .

The photocurable composition 15 is supplied from the supply part 81 to the inside of the casing 71 at a predetermined flow rate. The supply part 81 supplies the photocurable composition 15 into the inside of the casing 71 until the photocurable composition 15 is filled in a pressurized state. . Furthermore, for example, even when the photocurable composition 15 is discharged from the discharge port 45a, the supply part 81 supplies the photocurable composition 15 and maintains the pressurized state of the photocurable composition 15 inside. In this way, the supply part 81 also functions as a pressurizing mechanism.

By moving the opening and closing member 72 located in the closed position to the open position, the photocurable composition 15 filled in the pressurized state passes through the one end and heads toward the discharge port 45a. Then, a small amount of the photocurable composition 15 in the through hole 82 is discharged in the form of droplets 41 by moving the opening and closing member 72 located in the open position to the closed position. The moving path between the discharge port 45a and the film material 11 (see FIG. 3 ) is set to a distance significantly farther than the size of the liquid droplet 41 so that the liquid droplet 41 can fly in space. Thereby, the liquid droplets 41 discharged from the discharge port 45a fly toward the film material 11 from the discharge port 45a and adhere. By moving the opening and closing member 72 in the closed position to the open position again and then returning to the closed position, new droplets 41 are attached to another position in the longitudinal direction of the moving film material 11 . As described above, by repeatedly moving the opening and closing member 72 from the closed position to the open position, the photocurable composition 15 filled in the pressurized state is discharged from the discharge port 45a in the form of droplets 41 toward the moving film material. 11Fly (discharge process).

In addition, the driver 67 (see FIG. 3 ) adjusts the cycle of discharging each droplet 41 , the flow rate of the photocurable composition 15 supplied to the discharge device 45 , and the volume of the droplet 41 . The volume of the droplet 41 can be adjusted by adjusting the movement timing of the opening and closing member 72 . Specifically, the volume of the droplet 41 can be adjusted by adjusting the time until the opening and closing member 72 located in the blocking position moves to the open position and returns to the blocking position again. In addition, the volume of the droplet 41 can also be adjusted by adjusting at least one of the viscosity of the photocurable composition 15 (see FIG. 3 ) and the pressure of the photocurable composition 15 inside the housing 71 . In the discharge process, the droplets 41 are discharged with a volume in the range of 0.8×10 ^-12 m ³ or more and 100.0×10 ^-12 m ³ , that is, in a volume of 0.8×10 ^-12 m ³ or more and 100.0×10 ^-12 It is preferable to discharge the photocurable composition 15 with a volume within the range of m ³ or less. Within this range, it is easier to adjust the size of the convex portion 12 .

The pitch PL12 of the convex portions 12 (see FIG. 2 ) is adjusted by adjusting at least one of the period of discharge of each droplet 41 and the moving speed of the film material 11 (see FIG. 3 ).

The above example is the opening and closing member 72 including the piezoelectric element 84, but the opening and closing member is not limited to this example. For example, instead of changing the shape of the piezoelectric element 84 , the opening and closing member may be a spring-energized contact portion that is moved by a change in air pressure. This type of discharge device and discharge mechanism are called Jet Dispenser and Jet Dispensing method, which are described in Journal of Japan Institute of Electronics Packaging 2004, Vol. 7.No. 6 (page 501), and commercially available devices can be used.

In this example, the spherical crown convex portion 12 is formed, but the shape of the convex portion 12 can be changed according to the target function of the film. For example, as shown in FIG. 6 , the top portion 91 a may be a flat convex portion 91 . The top 91 a of the convex portion 91 is formed as a plane substantially parallel to the first surface 11A. In addition, as shown in FIG. 7 , the top portion 96 a may be a concave convex portion 96 . In any case, it is preferable that the ratio HP/RP is within the aforementioned range.

In addition, after the photocurable composition 15 is repeatedly discharged by the discharge device 45 a plurality of times over a long period of time, the opening and closing of the opening and closing member 72 is stopped during the repeated continuous discharge, and the number of discharges becomes insignificant. full. The mechanism is presumed to be as follows. That is, since the discharge device 45 repeatedly discharges the photocurable composition 15 a plurality of times over a long period of time, the photocurable composition 15 oozes out when the opening and closing member 72 reciprocates as shown in (A) and (B) of FIG. 5 In the gap between the sealing member 78 and the shaft 85 of the opening and closing member 72, the photocurable composition 15 is accumulated in the portion of the О-ring 77a. Furthermore, friction occurs between the sealing member 78 and the shaft 85 of the opening and closing member 72 and/or the O-ring 77 a and the shaft 85 of the opening and closing member 72 , and the photocurable composition 15 is polymerized in the housing 71 due to thermal energy or frictional energy. The reactant of the photocurable composition 15 adheres to the O-ring 77a in the housing 71, the shaft 85 of the opening and closing member 72, and/or the vicinity of the sealing member 78, so that the opening and closing member 72 cannot reciprocate.

By using the discharge device 45 and the photocurable composition 15 whose composition has been adjusted, it is possible to achieve multiple repeated discharges over a long period of time. For example, from the viewpoint of preventing the polymerization reaction from proceeding in the housing 71 , the amount of the photopolymerization initiator added to the photocurable composition 15 is reduced or 4-hydroxyTEMPO (4-hydroxy- 2,2,6,6-Tetramethylpiperidine 1-oxyl group, etc.), etc. are added in an amount. In addition, in order to provide long-term discharge durability and photocurability of the discharged droplets more appropriately, it is also preferable to use N-vinyl lactams, which are acrylamide-based compounds, as the ultraviolet curable compound. . This is because N-vinyl lactams can inhibit polymerization reactions caused by energy such as friction and have high photopolymerization reactivity compared to other acrylamide compounds. In order to improve the photopolymerization reactivity, when a mixture of a plurality of liquid photocurable compounds is used as the photocurable composition 15, the component amount of the photocurable compound in the photocurable composition 15 (acrylamide-based compound , the total amount of the monofunctional acrylic compound and/or the polyfunctional acrylate), the composition ratio of the acrylamide-based compound is within the range of 10 mass % or more and 60 mass %, more preferably 20 mass % or more and 50 mass % A range within mass % is also preferred. If it is within this range, it is preferable because the polymerization reaction in the casing caused by energy such as friction can be suppressed and the droplets imparted to the film can be quickly photohardened.

The thin film manufacturing equipment 30 (see FIG. 3 ) is not limited to the case of manufacturing the thin film 10, and can also manufacture various thin films by using the aforementioned pulse generator 66, system controller 68, and the like. For example, the film 110 shown in FIG. 8 can also be produced by the film manufacturing equipment 30 . The film 110 is provided with the convex portions 12 only in certain sections on both sides of the elongated film material 11 . In addition, the interval in the width direction where the convex portion 12 is formed is not limited to both sides. For example, in addition to or instead of both sides, it may be a certain interval in the width direction, such as the center.

When the film 110 is manufactured, the system controller 68 drives only the discharge devices 45 arranged in a certain section at both ends in the width direction through the driver 67 . Likewise, the light source 47 is driven by the system controller 68 to emit light by driving only a portion of both ends in the width direction where the droplets 41 are formed. In this way, the system controller 68 drives only part of all the ejection devices 45 and the light sources 47 in the width direction, thereby making it possible to manufacture various films in which the convex portions 12 are formed in predetermined areas in the width direction. However, the discharge device 45 and the light source 47 may be arranged only in the width direction in the section where the convex portion 12 is formed.

In addition, the film 120 shown in FIG. 9 can also be produced by the film manufacturing equipment 30 (see FIG. 3 ). The film 120 is provided with the convex portion 12 in a part of the longitudinal direction of the elongated film material 11 . Specifically, the convex portion 12 is provided for every certain section in the longitudinal direction. When manufacturing the film 120, first, the system controller 68 uses the aforementioned method to detect the position of the front end of the film material 11 that passes through the discharge port 45a. When the film material 11 passes through the discharge port 45a, it becomes the target position. At this time, the discharge device 45 is driven via the driver 67 to discharge the liquid droplets 41 (see FIG. 3 ). Also regarding the light source 47 , when the thin film 41 on which the droplets 41 are formed reaches the target position, it is driven by the system controller 68 to emit light and form the convex portion 12 . [Example]

[Example 1] ~ [Example 15] The film 10 is manufactured using the film manufacturing equipment 30 . The film material 11 is a TAC film formed of TAC. The photocurable composition 15 is mixed with a viscosity-increasing agent as a viscosity regulator, a photopolymerization initiator, etc. to prepare a mixed liquid, and is supplied from the supply part 81 to the discharge device 45 . Eight types of photocurable compositions 15 were prepared, and these are referred to as liquid mixtures A to H below.

The formulas of the liquid mixtures A to H as the photocurable composition 15 are shown in the "Mixed Liquid" column of Table 1. Table 1 shows the acrylamide compound and its viscosity, the polyfunctional acrylate compound and its viscosity, the monofunctional acrylic compound and its viscosity, and the amounts of each of these compounds and the photopolymerization initiator. The mass ratio of the photopolymerization initiator system IRGACURE (registered trademark) 907 (manufactured by BASF Japan Ltd.) and 2,4-diethylthioxanthone (KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.) is 1 than 3 mixtures. In addition, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxy (4-hydroxy TEMPO) 0.2 was added as a light stabilizer to Mixed Liquid A, Mixed Liquid D, and Mixed Liquid H. parts by mass.

In Table 1, A or B of the acrylamide compound, C or D of the polyfunctional acrylate compound, and E of the monofunctional acrylic compound are as follows. A: Dimethylacrylamide, DMAA (manufactured by KJ Chemicals Corporation) B: Hydroxyethylacrylamide, HEAA (manufactured by KJ Chemicals Corporation) C: Polypropylene glycol diacrylate, ARONIX M220 (manufactured by TOAGOSEI CO., LTD.) D: Mixture of neopentyl erythritol triacrylate and neopentyl tetraacrylate (PETA/PETTA), KAYARAD PET-30 (manufactured by Nippon Kayaku Co., Ltd.) E: Acrylylmorpholine, ACMO (manufactured by KJ Chemicals Corporation)

[Table 1] mixture Acrylamide compounds Multifunctional acrylate compounds Monofunctional acrylic compounds Photopolymerization initiator light stabilizer Kind Viscosity (mPa.s) Quantity (parts by mass) Kind Viscosity (mPa.s) Quantity (parts by mass) Kind Viscosity (mPa.s) Quantity (parts by mass) Quantity (parts by mass) Quantity (parts by mass) A A 1.3 25 D 1000 71 - - - 4 0.2 B B 280 39 C 12 20 E 12 39 2 - C B 280 39 C 12 18 E 12 39 4 - D A 1.3 20 D 1000 76 - - - 4 0.2 E - - - D 1000 57 E 12 39 4 - F - - - D 1000 96 - - - 4 - G A 1.3 20 D 1000 76 - - - 4 - H A 1.3 20 D 1000 76 - - - 4 0.6

The conditions for producing the film 10 are shown in Table 2. In addition, the discharge of the liquid droplets 41 is repeated at a certain period. “Frequency” in Table 2 is the reciprocal of the period in which droplets 41 are repeatedly discharged. The “discharged liquid amount” in Table 2 is the amount of the mixed liquid discharged from the discharge device 45 and is the volume of each droplet 41 . As the curing unit 34, a commercially available ultraviolet irradiation device HLUV-126UV365 (manufactured by CCS Inc.) equipped with a light emitting diode (LED) in the light source 47 was used. The length L from the discharge port 45a to the light source 47 is 0.4m.

[Table 2] condition Evaluation results mixture Diameter of discharge port (μm) Discharged liquid volume ×10 ^-12 (m ³ ) Discharge time (ms) Frequency (HZ) Moving speed of film material (m/min) Diameter RP (μm) Height HP (μm) Ratio HP/RP Pitch PW12 (mm) shape Roller contamination spit out durability Kind Viscosity (mPa.s) Example 1 A 42 50 3.3 0.54 67 10 600 twenty three 0.038 2.1 A B - Example 2 A 42 50 1.0 0.47 67 10 400 12 0.030 2.2 A B - Example 3 A 42 50 5.9 0.61 67 10 600 42 0.070 2.2 B B - Example 4 A 42 50 1.9 0.49 67 10 500 19 0.038 2.1 A B - Example 5 B 130 100 12.6 0.86 67 10 800 50 0.063 2.5 A C - Example 6 B 130 100 10.5 0.73 667 100 600 38 0.063 2.4 B C - Example 7 B 130 100 8.8 0.68 667 100 600 48 0.080 2.4 A C - Example 8 C 120 100 8.5 0.68 667 100 600 45 0.075 2.4 A B - Example 9 C 120 100 8.3 0.68 667 100 700 50 0.071 2.4 A B - Example 10 D 80 100 8.5 0.68 667 100 600 60 0.100 2.4 A A - Example 11 D 80 100 8.2 0.68 334 50 650 52 0.080 2.3 A A B Example 12 D 80 100 8.3 0.68 67 10 700 43 0.061 2.4 A A - Example 13 E 220 100 9.1 0.68 667 100 550 70 0.127 2.4 B C - Comparative example 1 E 220 - - - 120 10 - - - 1.4 D C - Comparative example 2 F ≤20 - - - 120 10 150 100 0.667 1.4 C C - Example 14 G 85 100 8.3 0.68 334 50 650 58 0.089 2.3 A A C Example 15 H 75 100 8.2 0.68 334 50 650 53 0.082 2.3 A B B

The diameter RP and the height HP of the convex portions 12, 91, and 96 were measured for each of the obtained films 10, and the ratio HP/RP was calculated. Furthermore, the pitch PW12 was measured. In addition, the shape of the convex portion 12 and the degree of contamination of the peripheral surface of the roller 37B between the curing unit 34 and the winding portion 35 were evaluated. Each evaluation method and standard are as follows. Each result is shown in Table 2.

(1) Diameter RP, height HP, and shape of the convex portion The diameter RP and the height HP were measured by shape analysis using a 3D laser microscope LEXT OLS4000 manufactured by Olympus Corporation. Regarding the shape, the shape of the convex portion 12 when viewed from the vertical direction of the first surface A (hereinafter, referred to as plan view shape), and when the plan view shape is circular, the shape of the cross section in the thickness direction (hereinafter, referred to as plan view shape) (called cross-sectional shape) were evaluated based on the following criteria. In the following D, a plurality of convex portions smaller than the target convex portion and having different sizes are generated by the separation of the droplets 41 . A, B and C are qualified, and D is unqualified. A: The plane shape is a circle diameter, and the cross-sectional shape is a semicircle or arc. B: The shape is circular in plan view, and the cross-sectional shape is flat as shown in Figure 6 or with a depression as shown in Figure 7. C: The shape is not circular in plan view, as shown in Figure 10, but has a deformed shape. In addition, in FIG. 10 , only the convex portion is drawn, and the convex portion is denoted by the reference numeral 150 . D: The shape cannot be said to be circular in plan view, or a plurality of convex parts smaller than the target convex part and having different sizes are confirmed.

(2) Contamination of roller 37B After the film 10 is produced, the peripheral surface of the roller 37B between the curing unit 34 and the winding unit 35 is visually observed under normal room lighting (hereinafter referred to as normal observation). When no contamination is observed by normal observation, Visual observation was performed under strong illumination light (hereinafter referred to as forced observation). This evaluation is not related to the performance of the obtained film 10 itself, so the following A to C were all regarded as passing. A: In forced observation, no contamination was confirmed on the roller. B: Minimal contamination was observed during mandatory observation. C: Contamination is observed in normal observation.

(3) Discharge durability A repeated discharge test of the photocurable composition 15 was performed using the discharge device 45 of the film manufacturing apparatus 30, and the number of consecutive discharges was measured. The number of consecutive discharges is the number of discharges from the start of discharge until just before repeated discharge stops. In the discharge durability evaluation, the repeated discharge conditions were the same as those in the respective examples except that the frequency was set to 1000 HZ. The discharge durability was evaluated as follows. The following A to C are all qualified. A: The number of times of spitting is more than 5 million times. B: The number of spits is from 500,000 to less than 5 million times. C: The number of times of spitting out is more than 10,000 times and less than 500,000 times. D: The number of spit outs is less than 10,000 times.

[Comparative Example 1]～[Comparative Example 2] Films having a plurality of convex portions were produced using a commercially available inkjet discharge device, and these were used as Comparative Examples 1 and 2. In addition, the inkjet type ejection device does not include an opening and closing member that opens and closes the ejection port 45a like the opening and closing member 72 of this example. In Comparative Example 1, the liquid mixture E shown in Table 1 was used as the photocurable composition discharged from the above-mentioned discharge device. In Comparative Example 2, the mixed liquid F of the formula shown in Table 1 was used, the total amount of the mixed liquid F was set to 100 parts by weight, and the mixed liquid F and 30 parts of propylene glycol monomethyl ether were discharged through the above-mentioned discharge device. A mixture of 100 parts by weight and 100 parts by weight of methyl ethyl ketone. The viscosity of mixed liquid F is 20mPa. s or less. In addition, a dryer was installed between the discharge device 45 and the curing unit 34 of the film manufacturing equipment 30 to produce a film, which is referred to as Comparative Example 2. In Comparative Example 2, the formed droplets were dried with a dryer at 100° C. for 20 seconds, and then irradiated with light to form convex portions. In any of the comparative examples, the film material used was a TAC film formed of TAC, which was the same as the film material 11 used in the embodiment.

For the film obtained in Comparative Example 2, the diameter RP and height HP of the convex portion were measured, and the ratio HP/RP was calculated. Furthermore, the pitch PW12 was measured. In Comparative Example 1, since convex portions of a constant shape could not be obtained, the diameter RP, height HP, and pitch PW12 of the convex portions were not measured. In addition, the shape of the convex portion and the degree of contamination of the peripheral surface of the roller 37B between the curing unit 34 and the winding unit 35 were evaluated. Each result is shown in Table 2.

[Example 16] ~ [Example 18] Film 10 was produced in the same manner as in Example 11. The film material 11 is a TAC film formed of TAC. Three types of photocurable compositions 15 were prepared, and these are referred to as liquid mixtures I to K below.

The formulas of the mixed liquids I to K as the photocurable composition 15 are shown in the "Mixed Liquid" column of Table 3. Table 3 shows the acrylamide compound and its viscosity, the polyfunctional acrylate compound and its viscosity, the monofunctional acrylic compound and its viscosity, the type and amount of the photopolymerization initiator, and the amount of the light stabilizer. Regarding the photopolymerization initiator, in Table 3, as the photopolymerization initiator A, IRGACURE (registered trademark) 907 (manufactured by BASF Japan Ltd.) and A mixture in which the mass ratio of 2-4-diethylthioxanthone (KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.) is 1:3. In addition, as the photopolymerization initiator B, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (IRGACURE (registered trademark) 819, manufactured by BASF Japan Ltd.), 2,4 , the mass ratio of 6-trimethylbenzoyldiphenylphosphine oxide (DAROCUR (registered trademark) TPO, manufactured by BASF Japan Ltd.) and isopropylthioxanthone (manufactured by LAMBSON) is 4:5:2 mixture. Moreover, as a light stabilizer, the amount of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxy (4-hydroxy TEMPO) shown in Table 3 was further added.

The F of the acrylamide compound, the G or H of the polyfunctional acrylate compound, and the I of the monofunctional acrylic compound in Table 3 are as follows respectively. In addition, since two types of polyfunctional acrylate components were used, Table 3 describes them in the columns of "first polyfunctional component" and "second polyfunctional component" divided into "polyfunctional components". F: N-vinylcaprolactam (manufactured by Tokyo Chemical Industry Co., Ltd.) G: Ethoxylated (3) trimethylolpropane triacrylate (SR454 D NS, manufactured by Sartomer Japan Inc.) H: CN964A85 (urethane acrylate oligomer, average number of functional groups 2, manufactured by Sartomer Japan Inc.) I: Cyclic trimethylolpropane formal acrylate (SR531, manufactured by Sartomer Japan Inc.)

[table 3] mixture Acrylamide compounds multifunctional ingredients Monofunctional acrylic compounds Photopolymerization initiator light stabilizer 1st multifunctional ingredient The second multifunctional ingredient Kind Viscosity (mPa.s) Quantity (parts by mass) Kind Viscosity (mPa.s) Quantity (parts by mass) Kind Viscosity (mPa.s) Quantity (parts by mass) Kind Viscosity (mPa.s) Quantity (parts by mass) Kind Quantity (parts by mass) Quantity (parts by mass) I F solid 26 G 80 3 H 8000 4 I 18 56 First 4 0.2 J F solid 26 G 80 3 H 8000 4 I 18 56 Second 11 0.3 K F solid 26 G 80 3 H 8000 19 I 18 41 Second 11 0.3

The conditions for producing the film 10 were carried out under the same conditions as in Example 11 and are shown in Table 4. In addition, the discharge durability test was evaluated under the above conditions and is shown in Table 4.

[Table 4] condition Evaluation results mixture The diameter of the spout Volume of spit out liquid spit out time Frequency Moving speed of film material diameter high Compare spacing shape Roller contamination spit out durability Kind viscosity ×10 ^-12 RP HP HP/RP PW12 (mPa.s) (μm) (m ³ ) (ms) (HZ) (m/min) (μm) (μm) (mm) Example 16 I 20 100 8.0 0.68 334 50 700 45 0.064 2.3 A B A Example 17 J twenty two 100 8.2 0.68 334 50 700 42 0.060 2.3 A A A Example 18 K 55 100 8.1 0.68 334 50 650 50 0.077 2.3 A A A

10,110,120:Thin film 11:Thin film material 11A: 1st surface 11B: 2nd surface 12,91,96,150:convex part 15: Photohardenable composition 30:Thin film manufacturing equipment 31:Film roll 32: Delivery Department 32a:Rotation axis 33: spitting part 34: Hardening unit 35: Coiling section 37A, 37B: Roller 38: Film roll 41: Droplets 42: Support roller 44: Discharge unit 45: Discharge device 45a: spit out 46:Supporting members 47:Light source 48:Supporting members 56: Brick Tower Arm 57: Take-up shaft 58: core 59: Guide arm 61: Guide roller 62:Arm mounting shaft 66:Pulse generator 67: drive 68:System controller 71: Shell 72: Opening and closing components 73: Shell body 73a: Supply port 74: Bottom component 75: Press component 77a,77b: O-ring 78:Sealing components 81:Supply Department 82:Through hole 83:Butt part 84: Piezoelectric element 85:Shaft 91a,96a: top Dc: moving direction HP:Height L: length PL12, PW12, PL45, PW45: spacing RP, R41: diameter PS1: Take-up position PS2: Core replacement position

Fig. 1 is an explanatory diagram of a film as an embodiment of the present invention. Figure 2 is an explanatory view of the film, (A) is a plan view, and (B) is a cross-sectional view along the (IIb)-(IIb) line of (A). Figure 3 is a schematic diagram of film manufacturing equipment. Fig. 4 is an explanatory diagram of the discharge device and the light source. Fig. 5 is a schematic cross-sectional view of the discharge device. Figure 6 is a schematic cross-sectional view of another convex portion. Figure 7 is a schematic cross-sectional view of another convex portion. Figure 8 is a plan view of another film. Figure 9 is a plan view of another film. Fig. 10 is an explanatory diagram of the shape of the convex portion during evaluation in the Example.

11:Thin film material

11A: 1st surface

12:convex part

15: Photohardenable composition

30:Thin film manufacturing equipment

31:Film roll

32: Delivery Department

32a:Rotation axis

33: spitting part

34: Hardening unit

35: Coiling section

37A, 37B: Roller

38: Film roll

41: Droplets

42: Support roller

42a:Rotation axis

44: Discharge unit

45: Discharge device

46:Supporting members

47:Light source

48:Supporting members

56: Brick Tower Arm

57: Take-up shaft

58: core

59: Guide arm

61: Guide roller

62:Arm mounting shaft

66:Pulse generator

67: drive

68:System controller

Dc: moving direction

PS1: Take-up position

PS2: Core replacement position

Claims (15)

A film manufacturing method that forms a plurality of convex portions on a long film material that moves in a longitudinal direction. The film manufacturing method includes: a discharging process, forming a shell having an interior filled with a solution containing a photocurable compound. The solution is filled in a pressurized state in the casing with a through hole in which one end is exposed in the interior and the other end serves as a discharge port for the solution, and a discharge device that opens and closes the opening and closing member of the one end. The opening and closing member that moves between an open position at one end and a closed position that blocks the one end repeatedly moves from the closed position to the open position, and the solution filled in the interior is discharged in the form of droplets from the discharge port, and the solution is discharged from the discharge port in the form of droplets. It flies towards the moving film material; and a curing process is performed by using a light source to harden the photocurable compound attached to the liquid droplet on the film material to form the convex portion from the liquid droplet, the light source being disposed on The opening and closing member is located downstream of the discharge device in the moving direction of the film material and emits light to harden the photocurable compound. The opening and closing member has a piezoelectric element, is fixed to the piezoelectric element, and is in contact with the discharge port. The contact portion and the voltage application portion that applies voltage to the piezoelectric element move the contact portion between the open position and the closed position by increasing or decreasing the voltage applied by the voltage application portion to the piezoelectric element. . The thin film manufacturing method of Claim 1, wherein in the discharging process, the droplets are discharged with a volume in a range of 0.8×10 ^-12 m ³ or more and 100.0×10 ^-12 m ^{3 or} less. For example, the film manufacturing method of claim 1, wherein the viscosity of the solution is 20 mPa. s or more and 1000mPa. within the range below s. The film manufacturing method of claim 1, wherein the shape of the convex portion is adjusted by adjusting the movement time of the film material from the discharge device to reaching the light source. The film manufacturing method of claim 1, wherein the light is ultraviolet light and the photocurable compound is an ultraviolet curable compound. The film manufacturing method of claim 5, wherein the ultraviolet curable compound is an acrylamide compound. The film manufacturing method of claim 1, wherein the photocurable compound contains a light stabilizer. The film manufacturing method of claim 1, wherein the photocurable compound includes a monofunctional acrylic compound. The film manufacturing method of claim 1, wherein the photocurable compound includes a multifunctional acrylate compound. The film manufacturing method of claim 1, wherein the film material is formed of cellulose chelate. A film manufacturing equipment that forms a plurality of convex portions on a long film material that moves along the length direction. The film manufacturing equipment is provided with: a moving mechanism to move the long film material along the length direction; and a discharge device to contain light. The discharge port of the solution of the curable compound is disposed toward the moving path of the film material and discharges the solution; and the light source is provided downstream of the discharge device in the moving direction of the film material and emits the light. The curing compound is cured by light, and the discharging device has: a casing, in which the solution is filled in a pressurized state; A through hole is formed in the shell, with one end exposed in the interior and the other end serving as the discharge port; and an opening and closing member that repeatedly moves between an open position and a closed position. In the open position, the one end is opened to allow the solution to flow from the The discharge port discharges liquid droplets in the form of liquid droplets and causes them to fly toward the moving film material so that they adhere to the film material. At the blocking position, the one end is blocked to stop the discharge of the liquid droplets. The opening and closing member has The piezoelectric element, the contact portion fixed to the piezoelectric element and in contact with the outlet, and the voltage application portion that applies voltage to the piezoelectric element, increase or decrease the voltage applied by the voltage application portion to the piezoelectric element. The voltage causes the contact portion to move between the open position and the closed position. A film, which has a film material formed of a cellulose acyl compound, and has a plurality of spherical crown convex portions on one surface of the film material, or a convex portion with a depression formed on the top, and the plurality of convex portions are regular arranged, the height of the convex part is in the range of 12 μm to 70 μm, and the diameter of the convex part is in the range of 550 μm to 800 μm. Let the height of the convex part be HP and the diameter of the convex part be In the case of RP, the ratio HP/RP, which is the height HP of the convex portion divided by the diameter RP, is in the range of 0.01 to 0.5. The film of claim 12, wherein the convex portion is formed of hardened resin, and the hardened resin is a polymerized product hardened by a photocurable compound. The film of claim 13, wherein the photocurable compound is an acrylamide compound. The film of claim 14, wherein the acrylamide compound has a structural part that is addition-bonded with the acrylamide compound.

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