JP7125996B2 - Film manufacturing method and equipment, film - Google Patents

Description

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

BACKGROUND ART Window films that are applied to windows of buildings (for example, buildings, store buildings, houses, etc.) and have both visibility prevention and design properties are known. Such window films have a large number of protrusions formed on the surface of the film. are doing

Optical functional films used for digital signage and screen projection are also known to have a large number of projections. Such an optical functional film is required to have both light transmittance and light scattering properties, and further enhancement of these functions has been required.

As a method of forming convex portions on a film material, there are a method using screen printing (see, for example, Patent Document 1) and a method using inkjet (see, for example, Patent Documents 2 and 3). In addition, a so-called needle dispenser method is used in which the tip of the nozzle that ejects the liquid for forming the protrusions is arranged very close to the film material, and the liquid is ejected from the tip so as to spread over the film material so that it adheres to the film material. There is also (for example, see Patent Document 4).

JP 2014-12388 A JP 2013-227515 A WO2010/143524 JP 2017-109481 A

However, the method described in Patent Document 1 can form convex portions on a sheet-like (single-leaf) film material, but continuously forms convex portions on a long film material. Can not do it. Therefore, it is difficult to manufacture a long film having a plurality of protrusions.

In addition, in the methods described in Patent Documents 2 and 3, the size of droplets that can be formed is very small. and/or does not reach the level of each of the above performances required for optical functional films. In addition, in the case of forming a convex portion with a large size, in order to form one convex portion, it is necessary to perform discharge many times in a state where droplets are overlapped, which is inefficient. Also, it is very difficult to adjust the degree of overlap of droplets. Therefore, it is difficult to produce a film for use in each of the above applications. In this way, if the projections can be formed larger and the film can be produced in a longer length, the range of applications can be expected to expand.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a film manufacturing method and equipment for efficiently manufacturing a long film having a plurality of protrusions by forming larger protrusions, and a film obtained thereby.

In order to achieve the above object, the film manufacturing method of the present invention has a discharging step and a curing step, and forms a plurality of projections on a long film material that is moving in the longitudinal direction. The ejection step includes a case filled with a liquid containing a photocurable compound, a through hole formed in the case, one end of which is exposed inside and the other end of which serves as an ejection port for the liquid, A case of a discharge device including an opening/closing member that opens and closes the one end is filled with the liquid under pressure, and the opening/closing member moves between an open position that opens the one end and a closed position that closes the one end. is repeatedly moved from the closed position to the open position, the liquid filled in the interior is ejected as droplets from the ejection port, and is caused to fly toward the moving film material. The curing step is provided downstream of the ejection device in the moving direction of the film material, and uses a light source that emits light for curing the photocurable compound to cure the photocurable compound droplets adhered to the film material. By doing so, the liquid droplet becomes a convex portion. The opening/closing member has a piezoelectric element, a contact portion fixed to the piezoelectric element and in contact with the ejection port, and a voltage applying portion for applying a voltage to the piezoelectric element. By increasing or decreasing the contact portion, the contact portion is moved between the open position and the closed position.

In the discharging step, it is preferable to discharge droplets to a volume within the range of 0.8×10 ⁻¹² m ³ or more and 100.0×10 ⁻¹² m ³ or less.

The viscosity of the liquid is preferably in the range of 20 mPa·s to 1000 mPa·s.

It is preferable to adjust the shape of the projections by adjusting the movement time of the film material from the ejection device to the light source.

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

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

The film material is preferably made of cellulose acylate.

Also, the film manufacturing equipment of the present invention includes a moving mechanism, a discharge device, and a light source, and forms a plurality of projections on a long film material that is moving in the longitudinal direction. The moving mechanism moves the long film material in the longitudinal direction. The ejection device is arranged in such a manner that the ejection port for the liquid containing the photocurable compound faces the moving path of the film material, and ejects the liquid. The light source is provided downstream of the ejection device in the movement direction of the film material, and emits light for curing the photocurable compound. The discharge device has a case in which a through hole is formed and an opening/closing member. The case is filled with the liquid pressurized inside. One end of the through hole formed in the case is exposed inside, and the other end serves as a discharge port. The opening/closing member has an open position in which the one end is opened and the liquid is ejected as droplets from the ejection port and is caused to fly toward the moving film material to adhere to the film material, and the one end is closed to allow the liquid to adhere to the film material. It repeatedly moves to and from a closed position that stops droplet ejection. The opening/closing member has a piezoelectric element, a contact portion fixed to the piezoelectric element and in contact with the ejection port, and a voltage applying portion for applying a voltage to the piezoelectric element. By increasing or decreasing the contact portion, the contact portion is moved between the open position and the closed position.

The film of the present invention comprises a film material formed of cellulose acylate, and a plurality of spherical crown-shaped projections or projections having dents formed at the top on one surface of the film material. are arranged regularly, the height of the protrusion is within the range of 12 μm or more and 70 μm or less , the diameter of the protrusion is within the range of 550 μm or more and 800 μm or less, and the projection of When the height is HP and the diameter of the projection is RP, the ratio HP/RP obtained by dividing the height HP by the diameter RP is within the range of 0.01 or more and 0.5 or less .

The projections are preferably made of a cured resin, which is a polymerization product obtained by curing a photocurable compound. The photocurable compound is preferably an acrylamide compound. The acrylamide-based compound preferably has a structural portion to which the acrylamide compound is additionally bonded.

According to the present invention, a long film having a plurality of protrusions can be efficiently obtained by forming the protrusions to be larger.

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing of the film which is embodiment of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing of a film, (A) is a top view, (B) is sectional drawing along the (IIb)-(IIb) line of (A). 1 is a schematic diagram of a film manufacturing facility; FIG. FIG. 4 is an explanatory diagram of an ejection device and a light source; It is a schematic sectional drawing of a discharge apparatus. It is a schematic sectional drawing of another convex part. It is a schematic sectional drawing of another convex part. FIG. 10 is a plan view of another film; FIG. 10 is a plan view of another film; It is explanatory drawing of the shape of the convex part in evaluation in an Example.

In FIG. 1, the film 10 which is one Embodiment of this invention is formed elongate. The film 10 includes a long film material 11 and a plurality of protrusions 12 . The film 10 is a window film that is attached to the windows of buildings (for example, buildings, store buildings, houses, etc.) and has both visibility prevention and design properties, and optical transparency and / that is used for digital signage and screen projection. Alternatively, it can be used as an optical functional film having light scattering properties.

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

Although the material of the film material 11 is not particularly limited, it is preferably made of a transparent polymer when used as a window film or an optical functional film. The film material 11 may contain one or more of various additives such as a plasticizer, an ultraviolet absorber, or fine particles, in addition to the polymer.

The polymer forming the film material 11 is preferably a thermoplastic resin, and examples of the thermoplastic resin include cellulose acylate, polyethylene terephthalate, acrylic resin, and cyclic polyolefin resin (for example, Arton (registered trademark) manufactured by JSR Corporation). ) and the like are more preferable. Among these, cellulose acylate is more preferable, and examples of cellulose acylate include cellulose triacetate (TAC), cellulose diacetate (DAC), cellulose acetate propionate, and cellulose acetate butyrate. Among cellulose acylates, TAC is particularly preferred. Among the cellulose acylates, TAC has transparency, a function of forming the projections 12 into a desired shape (projection formability), and, as will be described later, compatibility with the projections 12 formed of a photocurable resin. This is because the adhesion (adhesion) strength is particularly excellent.

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

As shown in FIG. 2, in the film 10 of this example, the projections 12 have a spherical crown shape, that is, a semicircular cross section or an arcuate cross section. As a result, when light is incident on the surface of the film 10 on which the protrusions 12 are formed, the light is reflected and scattered by the circular or arcuate portions of the protrusions 12, resulting in excellent design and/or visibility prevention. . Although the convex portions 12 are arranged in a state separated from each other, they may be in contact with each other. Moreover, if the centers of the convex portions 12 are separated from each other when the first surface 11A is viewed in 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 simply referred to as the “width direction”) is constant. A pitch PL12 (in units of mm) between the convex portions 12 in the direction (which is also the longitudinal direction of the film material 11 and will be simply referred to as the “longitudinal direction” hereinafter) is also constant. The pitch PW12 is the center-to-center distance of the protrusions 12 in the width direction when the first surface 11A is viewed from the perpendicular direction, and the pitch PL12 is the center-to-center distance of the protrusions 12 in the longitudinal direction. In the following description, when the pitch PW12 and the pitch PL12 are not distinguished from each other, they are referred to as the pitch P12 (unit: mm).

Although the plurality of protrusions 12 are formed to have the same size, they may be formed to have different sizes. Moreover, the convex portions 12 having different sizes may be arranged with a certain regularity. It is preferable that the diameter RP (unit: μm) of the projection 12 when viewed from the direction perpendicular to the first surface 11A is within the range of 50 μm or more and 2000 μm or less. When the diameter RP is 50 μm or more, when the film 10 is used as a window film, for example, when the other is viewed from the outside or the inside of the window, visibility prevention is improved compared to the case where the diameter RP is less than 50 μm. high. When the diameter RP is 2000 μm or less, compared to the case where the diameter RP is larger than 2000 μm, in the case of using the window film as described above, the unevenness observed by the plurality of convex portions 12 is small (fine). Excellent for The convex portion 12 has a circular shape when viewed from the direction perpendicular to the first surface 11A, but it may not be a strict circular shape. . The equivalent circle diameter is the diameter of a circle having the same area.

The ratio HP/RP obtained by dividing the height HP 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, the projections 12 increase the light scattering property and the visibility prevention property as compared with the case where the ratio is less than 0.01. When the ratio HP/RP is 0.5 or less, the protrusions 12 are less likely to be partly scraped and more difficult to come off during handling of the film 10 than when the ratio is greater than 0.5. In addition, even if a part of the convex portion 12 is scraped off or the convex portion 12 is detached due to rough handling more than expected, the film portion is less likely to be observed as unevenness. The design of the film 10 is excellent. It should be noted that when the projections 12 are formed at a ratio HP/RP of 0.5 or less, the projections 12 are formed in a curing unit 34 (described later) more than when they are formed at a ratio HP/RP greater than 0.5. There is also the advantage that even when it comes into contact with the roll 37B between the winding part 35 and the winding part 35, it is less likely to be scraped off and more difficult to come off. Note that the height HP is the distance from the first surface 11A to the top of the convex portion 12 .

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

A film manufacturing facility 30 shown in FIG. 3 is an example of a facility for manufacturing the film 10 . In this film manufacturing facility 30, the film 10 is obtained as a film roll 31 wound into a roll. The film manufacturing equipment 30 includes a feeding section 32, a discharging section 33, a curing unit 34, and a winding section 35 in this order from the upstream side in the movement direction Dc of the film material 11. As shown in FIG. Rollers 37A and 37B are provided on the moving path along which the film material 11 is moved. The surface of the film material 11 on which the protrusions 12 are not formed and the roller that contacts the side of the film 10 on which the protrusions 12 are not formed are denoted by reference numeral 37A. The roller contacting the surface of the is labeled 37B. In the following description, the rollers 37A and 37B are referred to as rollers 37 when not distinguished from each other. Among the plurality of rollers 37, there may be a drive roller provided with a rotation mechanism (not shown) and rotated in the circumferential direction by this rotation mechanism.

A film material roll 38 obtained by winding the film material 11 in a roll shape is set in the feeding section 32 . The delivery unit 32 has a rotating shaft 32a on which a film material roll 38 is set. By rotating this rotating shaft 32a by a rotating mechanism (not shown), the long film material 11 is continuously fed from the film material roll 38. send to The movement speed of the film material 11 is adjusted by adjusting the rotation speed of the rotating shaft 32a. In this manner, the feeding section 32 constitutes a moving mechanism for moving 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. , 2 m/min or more and 200 m/min or less.

The ejection part 33 is for forming droplets 41 on the first surface 11</b>A of the film material 11 to form the projections 12 (see FIGS. 1 and 2 ). The ejection section 33 includes a support roller 42 that supports the film material 11, an ejection unit 44 that ejects the photocurable composition 15 as droplets 41, and the like. The support roller 42 is a driven roller that has the film material 11 wrapped around its peripheral surface and rotates when the peripheral surface contacts the film material 11 moving in the longitudinal direction. A rotation mechanism (not shown) may be provided in the support roller 42, and the rotary shaft 42a may be rotated by this rotation mechanism (not shown).

The ejection unit 44 includes a plurality of ejection devices 45 for ejecting the photocurable composition 15 and, for example, a plate-shaped support member 46 for supporting the plurality of ejection devices 45 . The number of ejection devices 45 is determined based on the arrangement of the convex portions 12 to be formed, and may be one.

The ejection device 45 has an ejection port 45a (see FIGS. 4 and 5) for ejecting the photocurable composition 15, which is arranged in a posture facing the peripheral surface of the support roller 42, which is a part of the moving path of the film material 11. As shown in FIG. be done. When focusing on one of the plurality of ejection devices 45, the photocurable composition 15 is intermittently ejected as droplets from the ejection port 45a toward the moving film material 11, thereby forming droplets 41. are deposited sequentially in the longitudinal direction (discharging step). Thus, the film 10 is manufactured through the ejection process in the ejection section 33 . The details of the ejection device 45 will be described later using another drawing.

The photocurable composition 15 is an example of a liquid containing a photocurable compound, and in this example is a mixture containing a liquid or solid photocurable compound. The photocurable compound may be liquid, and in that case, the photocurable compound alone may be used. A mixture of a plurality of liquid or solid photocurable compounds may also be used as the photocurable composition 15 . The liquid photocurable compound may be a monomer, an oligomer, or a polymer, and is solvent-free, that is, it is used without the use of a solvent. Examples of photocurable compounds include compounds having photocurable ethylenic double bond groups such as acryl groups and styryl groups.

As the photocurable compound, an ultraviolet curable compound that is cured by irradiation with ultraviolet rays (with a wavelength of 100 nm or more and 400 nm or less) is preferable, and this is also the case in this example. Compared to other photo-curable compounds, the UV-curable compound has a shorter time required for curing, is easier to form the projections 12 with the desired shape, and is easier to form in the curing step described later by the curing unit 34. This is because damage to the material 11 can be suppressed more reliably.

A polyfunctional acrylate compound, an acrylamide compound, and/or a monofunctional acrylic compound can be used as the UV-curable compound.

Examples of polyfunctional acrylate compounds include (meth)acrylate compounds of polyfunctional alcohols, including alkoxylated polyfunctional (meth)acrylate compounds, and oligomers. For example, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1, 9-nonanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)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-acryloxypolyethoxyphenyl)propane, or neo Pentyl glycol di(meth)acrylate and the like are preferred.

Examples of alkoxylated polyfunctional (meth)acrylate compounds include ethoxylated (3) trimethylolpropane tri(meth)acrylate (compound obtained by tri(meth)acrylated trimethylolpropane ethylene oxide 3 mol adduct), propoxylated (3 ) trimethylolpropane tri(meth)acrylate (compound obtained by tri(meth)acrylated trimethylolpropane propylene oxide 3 mol adduct), ethoxylation (2) neopentyl glycol di(meth)acrylate (neopentyl glycol ethylene oxide 2 (2) neopentyl glycol di(meth)acrylate (a compound obtained by diacrylated a 2-mol adduct of neopentyl glycol propylene oxide), or the like.

As the oligomer, polyester (meth)acrylate, urethane (meth)acrylate, etc. are preferable, and other examples include modified glycerin tri(meth)acrylate, modified bisphenol A di(meth)acrylate, and propylene oxide (PO) addition of bisphenol A. di(meth)acrylate, ethylene oxide (EO) adduct di(meth)acrylate of bisphenol A, or caprolactone-modified dipentaerythritol hexa(meth)acrylate.

Preferred acrylamide compounds include hydroxyethylacrylamide, dimethylacrylamide, isopropylacrylamide, diethylacrylamide, dimethylaminopropylacrylamide, and N-vinyllactams, specifically N-vinylpyrrolidone, N-vinylcaprolactam, and the like.

Monofunctional acrylic compounds include isoamyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, isoamylstill (meth)acrylate, isostearyl (meth)acrylate, 2-ethylhexyldiglycol (meth)acrylate, 2-methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypropylene Glycol (meth)acrylate, Tetrahydrofurfuryl (meth)acrylate, Isobornyl (meth)acrylate, 2-(meth)acrylooxyethyl succinate, 2-(meth)acrylooxyethyl-2-hydroxyethyl phthalate, lactone Modified flexible (meth)acrylate, t-butylcyclohexyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, cyclopentenyl (meth)acrylate, cyclopentenyloxyethyl (meth)acrylate, dicyclo Pentanyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, and the like are preferred.

Also preferred are monofunctional acrylic compounds having a cyclic structure in the molecule, specifically, acryloylmorpholine, benzyl acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclo pentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, and the like. These monofunctional acrylic compounds having a cyclic structure in the molecule can increase the solubility of the photopolymerization initiator and the like in the photocurable composition 15, and can also increase the heat resistance of the projections 12 after curing. .

The polyfunctional acrylate compound can improve the hardness and strength of the resulting cured resin. The acrylamide-based compound shortens the time required for curing and forms the protrusions 12 with improved adhesion to the film material 11 . The monofunctional acrylic compound adjusts the physical properties of the photocurable composition 15 and also adjusts the light scattering property such as the refractive index of the projections 12 .

The photocurable composition 15 preferably contains an acrylamide compound as an ultraviolet curable compound. Accordingly, when the film material 11 is made of cellulose acylate, it is particularly preferable that the projections 12 contain an acrylamide-based compound among the above-mentioned compounds because of high adhesion to the cellulose acylate.

Moreover, the photocurable composition 15 preferably contains an acrylamide-based compound and a polyfunctional acrylate compound as UV-curable compounds. As a result, the ejected droplets are rapidly cured by light irradiation, and since the convex portions after curing have sufficient strength, there is no roller contamination due to the dropping of the convex portions when contacting the roll, and the convex shape is good. can form continuously. Moreover, it is preferable to use 2 or more types of polyfunctional acrylate compounds. This is because the viscosity of the photocurable composition can be adjusted within a desired 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. A photopolymerization initiator and a light stabilizer viscosity for enhancing rapid curability and stability can be uniformly dissolved in the photocurable composition 15, and the viscosity can be adjusted to a desired range. This is because the strength, durability, and heat resistance of the projections can be enhanced.

The photocurable composition 15 preferably has a viscosity in the range of 20 mPa·s to 1000 mPa·s. When the viscosity is 20 mPa·s or more, the shape of the droplets 41 is less likely to change during the period from adhering to the film material 11 to curing by the curing unit 34 compared to when the viscosity is less than 20 mmPa·s. Therefore, it is easy to adjust the timing of hardening, and it is easy to form the convex part 12 of the target shape. When the viscosity is 1000 mPa·s or less, it is easier to adjust the volume of the ejected droplets 41 than when the viscosity is greater than 1000 mPa·s. Therefore, it is easy to form the convex portion 12 of the desired size. The viscosity of the photocurable composition 15 is more preferably in the range of 30 mPa·s to 500 mPa·s, and even more preferably in the range of 40 mPa·s to 300 mPa·s.

It is preferable to add a photopolymerization initiator or the like to the photocurable composition 15 in order to shorten the curing time and to increase the strength of the projections 12 and/or the adhesion to the film material 11 . Photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins and the like.

Moreover, it is preferable to add a light stabilizer in order to increase the stability of the liquid containing the photocurable compound (the photocurable composition 15 in this example). Examples of light stabilizers include nitroso polymerization inhibitors, hydroquinone, methoxyhydroquinone, benzoquinone, p-methoxyphenol, or TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl), hydroxy TEMPO (hydroxy- 2,2,6,6-tetramethylpiperidine 1-oxyl), cupferron Al, hindered amines, and the like.

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

The amount of the light stabilizer is preferably in the range of 0.05% by mass or more and 1.0% by mass or less, and in the range of 0.1% by mass or more and 0.8% by mass or less with respect to the photocurable composition 15. Inner is particularly preferred. Within this range, the stability of the photocurable composition in the ejection device can be enhanced, changes in viscosity and hardening in the ejection device can be suppressed, and the photocurability of the droplets after ejection is sufficient. Therefore, it is preferable. The photocurable compound can adjust the amount of a polyfunctional acrylate compound, an acrylamide compound, or a monofunctional acrylic compound, be mixed with other compounds to form a mixed liquid state, and can also adjust the viscosity. Viscosity modifiers for adjusting the viscosity include a viscosity modifier that increases the viscosity and a viscosity modifier that lowers the viscosity, and the viscosity modifier is used in this example.

The above-mentioned viscosity is the viscosity at the temperature in the ejection process, and in this example, since the ejection is performed at room temperature (25°C), the viscosity at 25°C is used. In this example, the viscosity is measured by a tuning fork type compact vibrating viscometer CJV5000 (A&D Co., Ltd.).

The curing unit 34 is for forming the projections 12 from the droplets 41 . The curing unit 34 is provided downstream of the discharge section 33 in the movement direction of the film material 11 and includes a plurality of light sources 47 for emitting light and a plate-shaped support member 48 for supporting the plurality of light sources 47 . The number of light sources 47 is determined based on the arrangement of the projections 12 to be formed, the type of the photocurable composition 15, the moving speed of the film material 11, and the like, and may be one. The wavelength of the light source 47 is determined by the photocurable composition 15 used. In this example, since the UV-curable compound is used as the component of the photo-curable composition 15 as described above, the light source 47 for emitting UV rays is used. By emitting light from the light source 47, the photocurable compound contained in the droplets 41 adhering to the film material 11 is cured, whereby the droplets 41 become the projections 12 (curing step).

The film material 11 with the convex portions 12 formed thereon is moved downstream by the rollers 37A and/or the rollers 37B and sent to the winding section 35 . The roller 37 arranged downstream of the curing unit 34 is used to improve the flatness of the film material 11 passing through the curing unit 34 and to adjust the transportability of the film material 11 in the film manufacturing equipment 30. , as appropriate.

The winding section 35 has a turret arm 56 and winds the film 10 around a winding core 58 set on a winding shaft 57 . The turret arm 56 is intermittently rotated 180 degrees by an arm driving section (not shown) to selectively switch the winding core 58 between the winding position PS1 and the winding core replacement position PS2. A guide arm 58 is provided at an intermediate position in the rotation direction of the turret arm 56 , and a guide roller 61 is attached to each tip of the guide arm 58 . The guide rollers 61 support the film 10 so that the film 10 does not contact the turret arm 56 and the arm attachment shaft 62 when the turret arm 56 is rotating.

A winding shaft 57 is provided at each tip of the turret arm 56 , and a winding core 58 is set on the winding shaft 57 . The winding shaft 57 has a rotating mechanism (not shown), and is rotated by this rotating mechanism, and the film 10 is wound around the set winding core 58 . Thus, the take-up shaft 57 constitutes a moving mechanism together with the delivery section 32, and cooperates with the delivery section 32 to move the film material 11 in the longitudinal direction. However, the moving mechanism is not limited to this example, and as described above, at least some of the plurality of rollers 37 arranged on the moving path may be drive rollers, and the drive rollers may be used.

At the winding position PS1, the film 10 sent from the roller 37 is wound around the winding core 58. As shown in FIG. At the winding core replacement position PS2, the film 10 of a fixed length is wound, and the fully wound film roll 31 is removed from the winding shaft 57 together with the winding core 58. An empty winding core 58 is set and the winding core 58 is replaced.

At the winding position PS1, the film 10 is wound on the winding core 58 from the one end 12A (see FIG. 1) with the tip in the moving direction Dc as the one end 12A (see FIG. 1), and the film roll 31 is nearly fully wound with a predetermined length. In this state, the turret arm 56 rotates 180 degrees to position the nearly full film roll 31 at the core replacement position PS2. An 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) operates to cut the film 10 . The preceding film 10 that has been cut is taken up by the film roll 31 at the core replacement position PS2, with the rear end in the moving direction Dc as the other end 12B. Also, the trailing film 10 that has been cut is wound up on the empty core 58 at the winding position PS1 from the one end 12A with the leading end as the one end 12A.

Thereafter, the film 10 is wound around the winding core 58 in the same manner, so that the continuously fed film 10 is obtained as the film roll 31 .

The film manufacturing facility 30 further includes a pulse generator 66 , a driver (driving circuit) 67 provided in the ejection 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 section 35 . The pulse generator 66 generates a pulse each time the connected roller 37 rotates by a given angle, that is, each time the film material 11 is fed by a given length.

Although only one driver 67 is shown in FIG. 3, it is provided for each ejection device 45 in this example. The driver 67 is an example of a voltage applying section that applies a voltage to a piezoelectric element 84 (see FIG. 5) of the ejection device 45, which will be described later. The driver 67 drives the ejection device 45 to start and stop ejection of the droplets 41 . The start of ejection means the start of repeated ejection within a certain period of time, and the stop of ejection means the stop of repeated ejection. Repeated ejection is performed at a preset cycle. Therefore, when the set period is equal to or longer than the predetermined period of time, the number of ejections between the start and stop of ejection is one. Such repetitive ejection includes the case where the number of times of ejection is one.

The system controller 68 centrally controls each part of the film manufacturing equipment 30, and forms the target projections 12 at the target positions of the film material 11 by this control. The system controller 68 obtains the movement length (conveyance length) of the film material 11 each time a pulse is generated from the pulse generator 66 . The length of the movement path from the discharge port 45a (see FIGS. 4 and 5) of the discharge device 45 to the roller 37 to which the pulse generator is connected is input to the system controller 68. Based on the movement length of the film material 11 thus obtained, the position from the leading end (corresponding to one end 12A (see FIG. 1)) in the longitudinal direction of the film material 11 passing through the discharge port 45a is detected. Further, the position of the film material 11 forming the projections 12 is input in advance to the system controller 68, and when the film material 11 passing through the ejection port 45a reaches the desired position, the driver 67 is operated. The discharge device 45 is driven via the

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

The system controller 68 further includes information such as the cycle of ejecting the droplets 41, the flow rate of the photocurable composition 15 supplied to the ejection device 45, the volume of the droplets 41, the moving speed of the film material 11, the film 10 and/or the rotation timing of the turret arm 56 are input, and each part of the film manufacturing equipment 30 is controlled based on these input signals.

As shown in FIG. 4, the ejection devices 45 of the ejection unit 44 are arranged in a row in the width direction. In this example, since the size of each ejection device 45 in the width direction is larger than the pitch PW12, all the ejection devices 45 cannot be arranged in a line in the width direction. Therefore, the ejection devices 45 to be used are arranged in two rows in the longitudinal direction. In this manner, the arrangement of the ejection devices 45 may be appropriately determined based on the size of the ejection devices 45 and the pitch PW12. 45 should be placed.

Further, in this example, as described above, the film 10 having the protrusions 12 over the entire width direction is formed, so the ejection device 45 is arranged over the entire width direction. Further, even in the case of manufacturing the film 10, by providing the discharge device 45 movably in the width direction and using a shift mechanism (not shown) for moving the discharge device 45 in the width direction, Since it can be displaced, it is not necessary to provide a plurality of ejection devices 45 over the entire width direction.

A plurality of light sources 47 of the curing unit 44 are also arranged in a row in the width direction. The light sources 47 are arranged at positions in the width direction of the ejection ports 45 a of the ejection devices 45 . As a result, the individual droplets 41 formed on the film material 11 are reliably irradiated with light.

The shape of the droplet 41 on the film material 11 changes before it is cured. For example, the shape changes such that the droplet 41 becomes flattened (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 concave. The shape of the convex portion 12 formed by curing depends on the shape of the droplet 41 . As described above, the film 10 of this example has a plurality of protrusions 12 with uniform shapes, so that the curing of the droplets 41 is also started at a fixed timing.

For this reason, the light sources 47 are arranged in such a manner that the distance from the ejection port 45a of the ejection device 45 forming the droplet 41 to be irradiated is constant. For example, in this example, the other row of ejection devices on the downstream side of the light source 47 that emits light toward the droplets 41 formed by the ejection device 45 on the upstream side in the moving direction of the plurality of ejection devices 45 is used. A light source 47 for emitting light toward the droplets 41 formed by 45 is arranged at a position shifted downstream by a pitch PL45 of the discharge ports 45a in the longitudinal direction. As a result, all the droplets 41 are irradiated a certain time after they are formed, and the convex portions 12 having a uniform shape are formed. The number of light sources 47 arranged in the direction of movement is three in FIG. It may be determined as appropriate depending on the time and the like.

As described above, the shape of the projections 12 changes depending on the timing of starting curing of the droplets 41 on the film material 11, and by using this, the shape of the projections 12 can be adjusted. That is, the shape of the convex portion 12 can be adjusted by adjusting the movement time of the film material 11 from the ejection device 45 to the light source 47 . When forming a flatter spherical crown-shaped convex portion 12, when forming a convex portion 91 with a flat top (see FIG. 6), and when forming a convex portion 96 with a concave top (see FIG. 7) , the movement time from the ejection device 45 to the light source 47 should be longer. In addition, in the case of forming the spherical crown-shaped convex portion with a higher height and a smaller base area, the movement time from the ejection device 45 to the light source 47 should be shortened.

The movement time of the film material 11 from the discharge device 45 to the light source 47 can be determined by either a method of changing the moving speed of the film material 11 or a method of changing the distance L between the discharge device 45 (discharge port 45a) and the light source 47. It's okay. For example, by displacing the light source 47 upstream in the movement direction, a convex portion 12 having a higher height and a smaller base area can be formed, and by displacing it downstream, a flatter convex portion 12 can be formed. A portion 12 can be formed.

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

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

The opening/closing member 72 is for opening and closing one end on the inner side of the through hole 82 . The opening/closing member is positioned between an open position in which the one end of the through hole 82 is opened as shown in FIG. 5B and a closed position in which the one end is closed as shown in FIG. 5A. It is movable. The opening/closing member 72 has a contact portion 83, a piezoelectric element (piezo element) 84, and the aforementioned driver 67 (see FIG. 3). is abutted against the bottom member 74 in a state of closing the .

The contact portion 83 is fixed via a shaft 85 to a piezoelectric element 84 that is deformed by an applied voltage. 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). The shaft 85 is inserted through the center of each of the pressing member 75 and the sealing member 78 .

The photocurable composition 15 is supplied to the inside of the case 71 from the supply unit 81 at a predetermined flow rate, and the supply unit 81 fills the case 81 with the photocurable composition 15 under pressure. The photocurable composition 15 is supplied up to . For example, even when the photocurable composition 15 is discharged from the discharge port 45a, the supply unit 81 supplies the photocurable composition 15, and the photocurable composition 15 inside is pressurized. maintain state. Thus, the supply section 81 also functions as a pressure mechanism.

By moving the open/close member 72 from the closed position to the open position, the photocurable composition 15 filled under pressure passes through the one end and heads toward the discharge port 45a. Then, by moving the opening/closing member 72 from the open position to the closed position, a small amount of the photocurable composition 15 in the through hole 82 is discharged as droplets 41 . The ejection port 45a and the moving path of the film material 11a (see FIG. 3) are set at a distance larger than the size of the droplet 41, so that the droplet 41 can fly in space. As a result, the droplet 41 ejected from the ejection port 45a flies from the ejection port 45a toward the film material 11 and adheres thereto. By moving the opening/closing member 72 again from the closed position to the open position and then returning it to the closed position, a new droplet 41 adheres to another position in the longitudinal direction of the moving film material 11 . As described above, by repeatedly moving the opening/closing member 72 from the closed position to the open position, the photocurable composition 15 filled in the pressurized state is ejected as droplets 41 from the ejection port 45a, and the droplets 41 are ejected from the ejection port 45a. Fly toward the film material 11 (discharge step).

The driver 67 (see FIG. 3) adjusts the cycle of ejecting each droplet 41, the flow rate of the photocurable composition 15 supplied to the ejection device 45, and the volume of the droplet 41. FIG. The volume of the droplet 41 can be adjusted by adjusting the timing of movement of the opening/closing member 72 . Specifically, the volume of the droplet 41 can be adjusted by moving the opening/closing member 72 from the closed position to the open position and adjusting the time until it returns to the closed position. 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 case 71. . In the ejection step, the droplets 41 are ejected to a volume within the range of 0.8×10 ⁻¹² m ³ or more and 100.0×10 ⁻¹² m ³ or less. It is preferable to discharge to a volume within the range of 100.0×10 ⁻¹² m ³ or more and 100.0×10 ⁻¹² m ³ or less.

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

The above example is the opening/closing member 72 having the piezoelectric element 84, but the opening/closing member is not limited to this example. For example, it may be an opening/closing member that moves a spring-biased contact portion by changing the air pressure instead of changing the shape of the piezoelectric element 84 . Such a discharge device and discharge mechanism are called a jet dispenser and a jet dispenser system, and are described in Electronics Mounting Society Journal 2004, Vol. 7, No. 6 (page 501), and commercially available equipment can be used.

In this example, the crown-shaped projections 12 are formed, but the shape of the projections 12 may be changed according to the intended function of the film. For example, as shown in FIG. 6, a convex portion 91 having a flat top portion 91a may be used. A top portion 91a of the convex portion 91 is a plane substantially parallel to the first surface 11A. Moreover, as shown in FIG. 7, the convex part 96 with which the top part 96a was recessed may be sufficient. In any case, the ratio HP/RP should preferably be within the aforementioned range.

After the ejection device 45 repeatedly ejects the photocurable composition 15 many times over a long period of time, the opening/closing member 72 stops opening and closing during the continuous repetition of ejection, and the number of ejections is insufficient. may disappear. This mechanism is presumed as follows. That is, since the photocurable composition 15 was repeatedly discharged over a long period of time in the discharging device 45, when the opening/closing member 72 reciprocates as shown in FIGS. The photocurable composition 15 seeps into the gap between 78 and the shaft 85 of the opening/closing member 72, and the photocurable composition 15 accumulates in the O-ring 77a. Friction occurs between the sealing member 78 and the shaft 85 of the opening/closing member 72 and/or between the O-ring 77a and the shaft 85 of the opening/closing member 72, and the photocurable composition 15 is pushed into the case 73 by heat and frictional energy. , the reactant of the photocurable composition 15 adheres to the vicinity of the O-ring 77a in the case 73, the shaft 85 of the opening/closing member 72, and/or the sealing member 78, and the opening/closing member 72 can reciprocate. Gone.

By using the ejection device 45 and the photocurable composition 15 whose composition and the like are adjusted, it is possible to achieve repeated ejection properties over a long period of time. For example, from the viewpoint of preventing the polymerization reaction within the case 73, in the photocurable composition 15, the amount of the photopolymerization initiator added is reduced, or hydroxy TEMPO (4-hydroxy-2,2, 6,6-tetramethylpiperidine 1-oxyl, etc.) is added in an adjusted amount. In order to more appropriately impart long-term ejection durability and photo-curability to droplets after ejection, it is also preferable to use N-vinyllactams, which are acrylamide compounds, as the UV-curable compound. This is because N-vinyllactams are more resistant to polymerization reaction due to energy such as friction and have higher photopolymerization reactivity than other acrylamide compounds. In order to increase the photopolymerization reactivity, when a mixture of a plurality of liquid photocurable compounds is used as the photocurable composition 15, the amount of the photocurable compound in the photocurable composition 15 (acrylamide-based compound, monofunctional acrylic compound, and/or polyfunctional acrylate) is in the range of 10% by mass or more and 60% by mass, more preferably 20% by mass or more and 50% by mass or less. It is also preferable to be within the range of Within this range, the polymerization reaction in the case due to energy such as friction can be suppressed, and droplets applied to the film are rapidly photocured, which is preferable.

The film manufacturing facility 30 (see FIG. 3) is not limited to the case of manufacturing the film 10, and can manufacture various films by using the aforementioned pulse generator 66, system controller 68, and the like. For example, film 110 shown in FIG. 8 can also be manufactured by film manufacturing facility 30 . The film 110 has projections 12 only in certain sections on both sides of the long film material 11 . Note that the sections in the width direction in which the protrusions 12 are formed are not limited to both sides, and may be, for example, a certain section in the width direction in addition to or instead of both sides.

When manufacturing the film 110 , the system controller 68 drives, via the driver 67 , only the ejection devices 45 arranged in certain sections at both ends in the width direction. Similarly, the light source 47 may be driven by the system controller 68 only at a portion of both ends in the width direction where the droplet 41 is formed to emit light. In this manner, the system controller 68 drives only a part of all the ejection devices 45 and the light sources 47 in the width direction, so that various films having the protrusions 12 formed in predetermined regions in the width direction can be produced. can be manufactured. However, it is also possible to arrange the ejection device 45 and the light source 47 only in the section formed by the convex portion 12 in the width direction.

Also, the film 120 shown in FIG. 9 can be manufactured by the film manufacturing facility 30 (see FIG. 3). The film 120 has a convex portion 12 in a partial longitudinal section of the long film material 11 . Specifically, the protrusions 12 are provided at regular intervals in the longitudinal direction. When manufacturing the film 120, the system controller 68 first detects the position of the film material 11 passing through the ejection port 45a from the leading end in the longitudinal direction by the method described above, and detects the position of the film material 11 passing through the ejection port 45a. 11 reaches the target position, the ejection device 45 is driven via the driver 67 to eject droplets 41 (see FIG. 3). Similarly, the light source 47 is driven by the system controller 68 when the film 41 on which the droplets 41 are formed reaches a desired position, and emits light to form the projections 12 .

[Example 1] to [Example 15]
Film 10 was manufactured using film manufacturing equipment 30 . The film material 11 is a TAC film made of TAC. The photocurable composition 15 is a mixed liquid obtained by mixing a viscosity increasing agent as a viscosity adjusting agent, a photopolymerization initiator, and the like, and is supplied from the supply unit 81 to the ejection device 45 . Eight types were prepared as the photocurable composition 15, and these are hereinafter referred to as liquid mixtures A to H.

The formulations of mixed liquids A to H as the photocurable composition 15 are shown in the "mixed liquid" column of Table 1. Table 1 shows the acrylamide compounds and their viscosities, the polyfunctional acrylate compounds and their viscosities, the monofunctional acrylic compounds and their viscosities, and the amounts of each of these compounds and the photopolymerization initiator. The photopolymerization initiator is a mixture of Irgacure (registered trademark) 907 (manufactured by BASF Japan Co., Ltd.) and 2,4-diethylthioxanthone (KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.) at a mass ratio of 1:3. is. In addition, for the mixed solution A, the mixed solution D and the mixed solution H, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (4-hydroxy TEMPO) was further added as a light stabilizer. .2 parts by mass were added.

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)
B; hydroxyethyl acrylamide, HEAA (manufactured by KJ Chemicals)
C; polypropylene glycol diacrylate, Aronix M220 (manufactured by Toagosei Co., Ltd.)
D; a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (PETA/PETTA), KAYARAD PET-30 (manufactured by Nippon Kayaku Co., Ltd.)
E; acryloylmorpholine, ACMO (manufactured by KJ Chemicals)

The conditions for producing film 10 are shown in Table 2. Note that the ejection of the droplets 41 was repeated at a constant cycle. “Frequency” in Table 2 is the reciprocal of the cycle of repeatedly ejecting the droplets 41 . “Ejected liquid amount” in Table 2 is the amount of the mixed liquid ejected from the ejection device 45 and also the volume of each droplet 41 . As the curing unit 34, a commercially available ultraviolet irradiation device HLUV-126UV365 (manufactured by CCS Co., Ltd.) having a light emitting diode (LED) as the light source 47 was used. The length L from the discharge port 45a to the light source 47 was set to 0.4 m.

For each obtained film 10, the diameter RP and height HP of the projections 12, 91, 96 were measured to calculate the ratio HP/RP. Also, the pitch PW12 was measured. Furthermore, 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 criteria are as follows. Each result is shown in Table 2.

(1) Diameter RP, Height HP, and Shape of Protruding Portion Diameter RP and height HP were measured by shape analysis using LEXT OLS4000, a 3D laser microscope manufactured by Olympus. The shape is the shape of the convex portion 12 when viewed from the direction perpendicular to the first surface A (hereinafter referred to as the planar view shape), and when the planar view shape is circular, the shape when viewed in the cross section in the thickness direction. (hereinafter referred to as cross-sectional shape) was evaluated according to the following criteria. In D below, a plurality of protrusions that are smaller than the target protrusion and have different sizes are generated by separating the droplet 41 . A, B, and C are acceptable, and D is unacceptable.
A: The planar view shape is a circular diameter, and the cross-sectional shape is semicircular or arcuate.
B: The shape in plan view was circular, and the cross-sectional shape had a flat top as shown in FIG. 6 or a recess as shown in FIG.
C: The shape in plan view was not circular, but distorted as shown in FIG. It should be noted that FIG. 10 shows only the convex portion, and the convex portion is denoted by reference numeral 150. As shown in FIG.
D: The shape in plan view could not be said to be circular, or a plurality of protrusions smaller than the intended protrusions and having different sizes from each other were observed.

(2) Contamination of Roller 37B After manufacturing the film 10, the peripheral surface of the roller 37B between the curing unit 34 and the winding section 35 was visually observed under normal indoor lighting (hereinafter referred to as normal observation). However, when stains were not observed by normal observation, visual observation was performed under strong illumination light (hereinafter referred to as forced observation). Since this evaluation does not relate to the performance of the obtained film 10 itself, all of A to C below are accepted.
A: No contamination was observed on the roller during forced observation.
B; Stain was observed very slightly by forced observation.
C; Stain was observed by normal observation.

(3) Ejection Durability Using the ejection device 45 of the film manufacturing apparatus 30, a repeated ejection test of the photocurable composition 15 was performed to measure the number of continuous ejections. The number of continuous ejections is the number of ejections from the start of ejection until just before the repeated ejection is stopped. In the ejection durability evaluation, the repeated ejection conditions were the same as in each example except that the frequency was set to 1000 Hz. Ejection durability was evaluated as follows. All of A to C below are acceptable.
A: The number of discharge times is 5 million times or more.
B: 500,000 or more ejection times to less than 5,000,000 times.
C: 10,000 times or more and less than 500,000 discharge times.
D: Less than 10,000 discharge times.

[Comparative Example 1] to [Comparative Example 2]
Films having a plurality of protrusions were manufactured using a commercially available ink-jet type ejection device as Comparative Examples 1 and 2. It should be noted that the ink jet type ejection device does not have an opening/closing member for opening/closing the ejection port 45a like the opening/closing member 72 of this example. In Comparative Example 1, Mixture E shown in Table 1 was used as the photocurable composition discharged from the discharge device. In Comparative Example 2, a mixed liquid F having the formulation shown in Table 1 was used, the total amount of this mixed liquid F was 100 parts by weight, and this mixture F, 30 parts by weight of propylene glycol monomethyl ether, and 100 parts by weight of methyl ethyl ketone were mixed. The mixed liquid was discharged by the above-mentioned discharge device. The viscosity of the mixed liquid F was 20 mPa·s or less. Also, a dryer was provided between the discharging device 45 and the curing unit 34 of the film manufacturing equipment 30 to manufacture a film, which was designated as Comparative Example 2. In Comparative Example 2, the formed droplets were dried at 100° C. for 20 seconds in a dryer, and then irradiated with light to form protrusions. In all comparative examples, the film material used was a TAC film made of TAC, which was the same as the film material 11 used in the examples.

For the film obtained in Comparative Example 2, the diameter RP and height HP of the projections were measured, and the ratio HP/RP was calculated. Also, the pitch PW12 was measured. In Comparative Example 1, since convexes with a constant shape were not obtained, the diameter RP, height HP, and pitch PW12 of the convexes were not measured. Furthermore, 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 portion 35 were evaluated. Each result is shown in Table 2.

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

The formulations of Mixed Liquids I to K as Photocurable Composition 15 are shown in the "Mixed Liquid" column of Table 3. Table 3 shows acrylamide compounds and their viscosities, polyfunctional acrylate compounds and their viscosities, monofunctional acrylic compounds and their viscosities, types and amounts of photopolymerization initiators, and amounts of light stabilizers. . As the photopolymerization initiator, in Table 3, as the photopolymerization initiator a, the same as those used in the above-described mixed solutions A to D, Irgacure (registered trademark) 907 (manufactured by BASF Japan Co., Ltd.) and 2 A mixture with 4-diethylthioxanthone (KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.) at a mass ratio of 1:3 was used. Further, as a photopolymerization initiator B, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Irgacure (registered trademark) 819, manufactured by BASF Japan Ltd.) and 2,4,6-trimethylbenzoyldiphenylphosphine A mixture of oxide (DAROCUR (registered trademark) TPO, manufactured by BASF Japan Ltd.) and isopropylthioxanthone (manufactured by LAMBSON) in a mass ratio of 4:5:2 was used. Further, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (4-hydroxy TEMPO) was added as a light stabilizer in the amount shown in Table 3.

In Table 3, F for an acrylamide compound, G or H for a polyfunctional acrylate compound, and I for a monofunctional acrylic compound are as follows. In addition, since two types of polyfunctional acrylate components were used, Table 3 was divided into columns of "first polyfunctional component" and "second polyfunctional component" in "polyfunctional component".
F: N-vinylcaprolactam (manufactured by Tokyo Chemical Industry Co., Ltd.)
G; Ethoxylated (3) trimethylolpropane triacrylate (SR454 D NS, manufactured by Sartomer Japan Co., Ltd.)
H; CN964A85 (urethane acrylate oligomer, average functionality 2, manufactured by Sartomer Japan Co., Ltd.)
I; cyclic trimethylolpropane formal acrylate (SR531, manufactured by Sartomer Japan Co., Ltd.)

The conditions for producing film 10 were the same as those in Example 11, and are shown in Table 4. In addition, a discharge durability test was performed under the above conditions, and Table 4 shows the results.

REFERENCE SIGNS LIST 10, 110, 120 film 11 film material 11A first surface 11B second surface 12, 91, 96, 150 convex portion 15 photocurable compound 30 film manufacturing equipment 31 film roll 32 delivery portion 32a rotary shaft 33 discharge portion 34 curing unit 35 winding section 37A, 37B roller 38 film material roll 41 droplet 42 support roller 44 discharge unit 45 discharge device 45a discharge port 46 support member 47 light source 48 support member 56 turret arm 57 winding shaft 58 winding core 59 guide arm 61 guide Roller 62 Arm mounting shaft 66 Pulse generator 67 Driver 68 System controller 71 Case 72 Opening/closing member 73 Case main body 73a Supply port 74 Bottom member 75 Pressing member 77a, 77b O-ring 78 Sealing member 81 Supply portion 82 Through hole 83 Contact portion 84 Piezoelectric element 85 Axis 91a, 96a Top Dc Movement direction HP Height L Length PL12, PW12, PL45, PW45 Pitch RP, R41 Diameter PS1 Winding position PS2 Winding core replacement position

Claims (15)

In a film manufacturing method for forming a plurality of projections on a long film material that is moving in the longitudinal direction,
a case filled with a liquid containing a photocurable compound; a through hole formed in the case and having one end exposed to the inside and the other end serving as a discharge port for the liquid; and the one end The case of the discharge device is filled with the liquid under pressure, and the opening and closing member moves between an open position in which the one end is opened and a closed position in which the one end is closed. is repeatedly moved from the closed position to the open position, thereby ejecting the liquid filled in the interior as droplets from the ejection port and flying toward the moving film material; ,
The photocurable compound in the droplets adhered to the film material is removed by using a light source that is provided downstream of the discharge device in the moving direction of the film material and emits light for curing the photocurable compound. a curing step of curing the liquid droplets to form the projections;
has
The opening/closing member includes a piezoelectric element, a contact portion fixed to the piezoelectric element and in contact with the ejection port, and a voltage applying portion for applying a voltage to the piezoelectric element. A film manufacturing method in which the contact portion is moved between the open position and the closed position by increasing or decreasing the voltage applied to the element. 2. The film manufacturing method according to claim 1, wherein the discharging step discharges the droplets to a volume within a range of 0.8×10 ⁻¹² m ³ or more and 100.0×10 ⁻¹² m ³ or less. The film manufacturing method according to claim 1 or 2, wherein the viscosity of the liquid is in the range of 20 mPa·s to 1000 mPa·s. 4. The film manufacturing method according to any one of claims 1 to 3, wherein the shape of the convex portion is adjusted by adjusting the movement time of the film material from the ejection device to the light source. 5. The film manufacturing method according to claim 1, wherein the light is ultraviolet rays, and the photocurable compound is an ultraviolet curable compound. 6. The method of manufacturing a film according to claim 5, wherein the ultraviolet curable compound is an acrylamide compound. The film manufacturing method according to any one of claims 1 to 6, wherein the photocurable compound contains a light stabilizer. The film manufacturing method according to any one of claims 1 to 7, wherein the photocurable compound contains a monofunctional acrylic compound. The film manufacturing method according to any one of claims 1 to 8, wherein the photocurable compound contains a polyfunctional acrylate compound. 10. The film manufacturing method according to claim 1, wherein the film material is made of cellulose acylate. In a film manufacturing facility that forms a plurality of protrusions on a long film material that is moving in the longitudinal direction,
a moving mechanism for moving the long film material in the longitudinal direction;
an ejection device for ejecting the liquid containing the photocurable compound, the ejection opening being arranged in a state facing the moving path of the film material;
a light source provided downstream of the ejection device in the movement direction of the film material and emitting light for curing the photocurable compound;
with
The ejection device is
a case filled with the liquid under pressure;
a through hole formed in the case and having one end exposed to the inside and the other end serving as the discharge port;
an open position in which the one end is opened and the liquid is ejected as droplets from the ejection port and is caused to fly toward the moving film material to adhere to the film material; and the one end is closed and the liquid is ejected. an opening/closing member that repeatedly moves between a closing position that stops ejection of droplets;
has
The opening/closing member includes a piezoelectric element, a contact portion fixed to the piezoelectric element and in contact with the ejection port, and a voltage applying portion for applying a voltage to the piezoelectric element. A film manufacturing facility in which the contact portion is moved between the open position and the closed position by increasing or decreasing the voltage applied to the element. a film material formed of cellulose acylate;
One surface of the film material is provided with a plurality of crown-shaped protrusions or protrusions having a recess at the top,
The plurality of convex portions are arranged regularly,
The convex portion has a height within a range of 12 μm or more and 70 μm or less ,
The convex portion has a diameter within a range of 550 μm or more and 800 μm or less,
When HP is the height of the convex portion and RP is the diameter of the convex portion, the ratio HP/RP obtained by dividing the height HP by the diameter RP is in the range of 0.01 or more and 0.5 or less. film. 13. The film according to claim 12, wherein the projections are made of a cured resin that is a polymerization product obtained by curing a photocurable compound. 14. The film according to claim 13, wherein the photocurable compound is an acrylamide compound. 15. The film according to claim 14, wherein the acrylamide-based compound has a structural portion to which the acrylamide compound is additionally bonded.

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