KR102536653B1 - Film manufacturing method and equipment, film - Google Patents

Abstract

A film production method and equipment for efficiently producing a long film having a plurality of larger convex portions, and a film obtained thereby are provided.
The film manufacturing method includes a discharge step and a curing step to form a plurality of projections on a long film material. The discharge device 45 is filled with the photocurable composition 15 and includes a case and an opening/closing member. The case is filled with the photocurable composition 15 in a pressurized state. The opening/closing member discharges the photocurable composition 15 as droplets 41 and makes them fly toward the moving film member 11 . In the curing step, the droplet 41 is formed into the convex portion 12 by curing the photocurable compound of the droplet 41 using the light source 47 .

Description

Film manufacturing method and equipment, film

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

BACKGROUND ART There is known a window film that is applied to windows of buildings (for example, buildings, stores, and houses) and has both visibility and design properties. In such a window film, a large number of convex portions are formed on the surface of the film, thereby preventing visibility when viewing the outside and inside of a building from one to the other, and enhancing the design of the window.

Moreover, it is known that a large number of convex portions are also formed on an optical functional film used for digital signage or screen projection. Such optical functional films are required to have both light transmittance and light scattering properties, and further enhancement of these functions has been requested.

As a method of forming convex portions on a film material, there are a method using screen printing (for example, see Patent Document 1) and a method using inkjet (for example, see Patent Documents 2 and 3). In addition, there is also a so-called needle dispenser system in which the tip of a nozzle for dispensing the liquid for forming the convex portion is placed very close to the film material, and the liquid is dispensed in a state extending from the tip to the film material, thereby attaching it to the film material (for example, For example, see Patent Document 4).

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

However, the method described in Patent Literature 1 can form convex portions for a sheet-like (sheet-leaf) film material, but cannot continuously form convex portions for a long film material. Therefore, it is difficult to manufacture a long film having a plurality of convex portions.

Further, in the methods described in Patent Literatures 2 and 3, the size of the droplet that can be formed is very small, and therefore there is a limit to the size of the convex portion that can be formed with one droplet. The level of each performance required for a functional film is not reached. In the case of forming a convex portion with a large size, it is necessary to perform ejection multiple times in a state in which droplets overlap in order to form one convex portion, resulting in poor efficiency. Also, it is very difficult to adjust the overlapping state of droplets. Therefore, it is difficult to manufacture a film that can be used for each of the above applications. In this way, if the convex portion is formed to be larger and the film can be produced in a long length, the application can be expected to expand.

Therefore, an object of this invention is to provide the film manufacturing method and equipment which form a convex part larger and efficiently manufacture the long film which has a plurality of convex parts, and the film obtained by this.

In order to achieve the above object, the film manufacturing method of the present invention has a discharge step and a curing step, and forms a plurality of convex portions on a long film material moving in the longitudinal direction. The discharge step includes a case into which a liquid containing a photocurable compound is filled, a through hole formed in the case, one end exposed to the inside, and the other end serving as a discharge port for the liquid, and opening and closing to open and close the one end. The case of the discharge device having the member is filled with the liquid in a pressurized state, and the opening/closing member moving between an open position in which the one end is opened and a closed position in which the one end is closed is moved from the closed position to the open position. By repeatedly moving, the liquid filled in the inside is discharged from the discharge port as droplets, and is caused to fly toward the moving film member. The curing step is provided downstream of the ejection device in the moving direction of the film material, and curing the photocurable compound of the liquid droplets adhering to the film material using a light source that emits light for curing the photocurable compound to convex the liquid droplet. make it rich

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

In the discharging step, the liquid droplets are preferably discharged in a volume within a range of 0.8×10 ^-12 m ³ or more and 100.0×10 ^-12 m ³ or less.

It is preferable that the viscosity of the said liquid is in the range of 20 mPa*s or more and 1000 mPa*s or less.

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

The light is ultraviolet, and the photocurable compound is preferably an ultraviolet curable compound. It is preferable that the ultraviolet curable compound is an acrylamide-based compound.

The photocurable compound preferably contains a photostabilizer. Moreover, it is preferable that a photocurable compound contains a monofunctional acrylic compound. Moreover, it is preferable that a photocurable compound contains a polyfunctional acrylate compound.

It is preferable that the film material is formed of cellulose acylate.

Further, the film manufacturing facility 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 moving in the longitudinal direction. The moving mechanism moves the elongated film member in the longitudinal direction. In the discharge device, the discharge port of the liquid containing the photocurable compound is disposed in a state facing the moving path of the film material, and discharges the liquid. A 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 case in which a through hole is formed and an opening and closing member. The case is charged in a state where the liquid is pressurized therein. The through hole formed in the case has one end exposed to the inside and the other end serving as a discharge port. The opening/closing member has an open position in which the one end is opened, the liquid is discharged as droplets from the discharge port and the liquid droplets are ejected toward the moving film material so as to adhere to the film material, and an occluded position in which the one end is closed and discharge of the liquid droplets is stopped. Move repeatedly between positions.

The film of the present invention comprises a film material formed of cellulose acylate, a spherical convex portion on one surface of the film material, a convex portion with a flat top, and a concave portion formed on the top. A plurality of any one of the convex portions are provided.

It is preferable that the some convex part is regularly arranged.

ADVANTAGE OF THE INVENTION According to this invention, the convex part is formed larger and the long film provided with multiple convex parts can be obtained efficiently.

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing of the film which is embodiment of this invention.
2 is an explanatory view of the film, (A) is a plan view, (B) is a cross-sectional view taken along the (IIb)-(IIb) line of (A).
3 is a schematic diagram of a film manufacturing facility.
4 is an explanatory diagram of a discharge device and a light source.
5 is a schematic sectional view of the ejection device.
6 is a schematic sectional view of another convex portion.
7 is a schematic cross-sectional view of another convex portion.
8 is a plan view of another film.
9 is a plan view of another film.
10 is an explanatory view of the shape of a convex portion in evaluation in Examples.

1, the film 10 which is one embodiment of this invention is formed in elongate shape. The film 10 includes a long film member 11 and a plurality of convex portions 12 . The film 10 is a window film having both anti-visibility and design properties attached to windows of buildings (eg, buildings, stores, and houses), and light-transmitting and / Alternatively, it can be used as a light functional film having light scattering properties.

The film material 11 is formed in a so-called flat film shape with both surfaces flat. The thickness T11 (unit: 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 handling properties (handling properties) and winding property as the film 10. do.

The material of the film material 11 is not particularly limited, but in the case of applications as a window film or an optical functional film, it is preferably formed of a transparent polymer. In addition to the polymer, the film material 11 may contain one or two or more additives such as plasticizers, ultraviolet absorbers, or fine particles.

As the polymer forming the film material 11, a thermoplastic resin is preferable. As the thermoplastic resin, a cellulose acylate, polyethylene terephthalate, an acrylic resin, or a cyclic polyolefin resin (e.g., Aton (registered trademark) manufactured by JSR Co., Ltd.) )) and the like are more preferable. Among these, what is formed from cellulose acylate is more preferable, and as a cellulose acylate, cellulose triacetate (TAC), cellulose diacetate (DAC), cellulose acetate propionate, cellulose acetate butyrate, etc. are mentioned. Among cellulose acylates, TAC is particularly preferred. Among cellulose acylates, TAC has transparency, a function that can form the convex portion 12 into a desired shape (convex portion formation property), and adhesion to the convex portion 12 formed of a photocurable resin as described later ( adhesion) is particularly excellent.

The plurality of convex portions 12 are formed in an aspect distributed over the entire surface of one surface (hereinafter referred to as a first surface) 11A of the film material 11, but in FIG. 1, a plurality of convex portions Only part of (12) is drawn. In this example, although the some convex part 12 is formed only on 11 A of 1st surfaces, you may be formed also on the other surface 11B (refer FIG. 2(B)). The plurality of convex portions 12 are arranged regularly, and in this example, as shown in FIG. 1, they are arranged in a square shape. However, the arrangement mode of the plurality of convex portions 12 is not particularly limited, and may be, for example, a matrix or the like, or a so-called irregular arrangement (random arrangement) without regularity.

As shown in FIG. 2, in the film 10 of this example, the convex part 12 is spherical, ie, the cross section is semicircular or the cross section is arcuate. As a result, when light enters the surface on which the convex portion 12 of the film 10 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 anti-visibility. do. Although the convex parts 12 are lined up in a state separated from each other, they may be in contact with each other. Moreover, if the center of the convex part 12 mutually separates when the 1st surface 11A is seen from the vertical direction, the convex part 12 may overlap. In this example, the pitch PW12 of 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 “width direction”) (unit: mm ) is constant, and the pitch PL12 (unit: mm) of the convex portions 12 in the longitudinal direction (also the longitudinal direction of the film material 11, hereinafter simply referred to as “longitudinal direction”) is also 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 convex portion 12 in the longitudinal direction. is the distance between the centers of In addition, in the following description, when pitch PW12 and pitch PL12 are not distinguished, it describes as pitch P12 (unit is mm).

The plurality of convex portions 12 are formed in the same size as each other, but may be formed in different sizes. Moreover, you may arrange the convex part 12 of different sizes with a certain regularity. It is preferable that the diameter RP (unit: μm) of the convex portion 12 when viewing the first surface 11A from the vertical direction is within a range of 50 μm or more and 2000 μm or less. When the diameter RP is 50 μm or more, compared to the case where the diameter RP is less than 50 μm, for example, when the film 10 is used for a window film, visibility when viewing the other side from the outside and inside of the window is 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 feeling of irregularities observed by the plurality of convex portions 12 is small (fine), so the designability this is excellent In addition, although the shape when the convex part 12 sees the 1st surface 11A from the direction perpendicular|vertical is circular, it does not have to be a strict circular shape, and in that case, the equivalent circle diameter is the said diameter D12. . The circle equivalent diameter is the diameter of a circle having the same area.

When the height of the convex portion 12 is HP (unit: µm), the ratio HP/RP obtained by dividing the height HP by the diameter RP is preferably within a range of 0.01 or more and 0.5 or less. Compared with the case where ratio HP/RP is 0.01 or more, compared with the case where it is less than 0.01, light-scattering property becomes high by the convex part 12, and visibility prevention property becomes high. Compared with the case where ratio HP/RP is 0.5 or less, compared with the case where it is larger than 0.5, during handling of the film 10, a part of the convex part 12 is more difficult to scrape off more easily, and also more difficult to detach. In addition, by handling more than expected, even if a part of the convex portion 12 is shaved or the convex portion 12 is detached, the film portion is difficult to observe as uneven, and the design as the film 10 The castle is excellent. In addition, the case where the convex portion 12 is formed with a HP/RP ratio of 0.5 or less is higher than the case where the convex portion 12 is formed with a HP/RP ratio greater than 0.5. Even if it is in contact with the roll 37B between the mounting portions 35, there are merits that it is more difficult to shave and more difficult to come off. In addition, height HP is the distance from the 1st surface 11A to the top of the convex part 12. As shown in FIG.

The convex portion 12 is formed of a cured resin (polymer) that is a polymerization (crosslinking) product obtained by curing a photocurable compound contained in a photocurable composition 15 (see Fig. 3) described later. A photocurable compound is a compound that is cured (including crosslinking) by irradiation of light, and will be described in detail later. As the cured resin, a cured resin in which an ultraviolet curable resin is cured is more preferable.

A film manufacturing facility 30 shown in FIG. 3 is an example of a facility that manufactures the film 10 . In this film production facility 30, the film 10 is obtained as a film roll 31 wound into a roll shape. The film manufacturing facility 30 is configured to supply the delivery unit 32, the delivery unit 33, the curing unit 34, and the take-up unit 35 from the upstream side in the moving direction Dc of the film material 11. provided in order Rollers 37A and 37B are provided in the moving path for moving the film material 11 . Reference numerals 37A are given to rollers in contact with the surface on which the convex portion 12 of the film material 11 is not formed and the surface on which it is not formed, and the surface on which the convex portion 12 of the film material 11 is formed and the film Reference numeral 37B is given to a roller that contacts the surface on the convex portion 12 side of (10). In addition, in the following description, when not distinguishing between roller 37A and roller 37B, it describes as roller 37. Among the plurality of rollers 37, there may be a drive roller that is equipped with a rotation mechanism (not shown) and rotates in the circumferential direction by this rotation mechanism.

The delivery unit 32 is set with a film material roll 38 wound around the film material 11 in a roll shape. The delivery unit 32 has a rotational shaft 32a on which the film material roll 38 is set, and the rotational shaft 32a is rotated by a rotation mechanism (not shown) so that a long film is removed from the film material roll 38. The film material 11 is sent out continuously. By adjusting the rotational speed of the rotating shaft 32a, the moving speed of the film material 11 is adjusted. In this way, the delivery unit 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 the convex portion 12 is positioned at the target position and is reliably determined by the shape. From the viewpoint of formation, it is preferable to be in the range of 2 m/min or more and 200 m/min or less.

The discharge part 33 is for forming the droplet 41 which becomes the convex part 12 (refer FIG. 1, FIG. 2) on the 1st surface 11A of the film material 11. The discharge unit 33 includes a support roller 42 that supports the film material 11 and a discharge unit 44 that discharges the photocurable composition 15 as droplets 41 and the like. The support roller 42 is a driven roller on which the film material 11 is wound around its circumferential surface and rotates when its circumferential surface contacts the film material 11 moving in the longitudinal direction. Moreover, you may provide the rotation mechanism (not shown) to the support roller 42, and may rotate the rotating shaft 42a by this rotation mechanism (not shown).

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

The discharge device 45 directs the discharge port 45a (see Figs. 4 and 5) through which the photocurable composition 15 is discharged toward the circumferential surface of the support roller 42, which is a part of the moving path of the film material 11. placed in position When attention is paid to one of the plurality of ejection devices 45, the photocurable composition 15 intermittently comes out as droplets from the ejection port 45a toward the moving film member 11, so that the droplets 41 have a length. They are applied in order in the direction (discharge step). In this way, the film 10 is manufactured through the discharge process in the discharge part 33 . Details of the discharge device 45 will be described later using other drawings.

The photocurable composition 15 is an example of a liquid containing a photocurable compound, and in this example, it is a mixture containing a liquid or solid photocurable compound. A photocurable compound may be a liquid, and in that case, you may use only a photocurable compound. In addition, 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 a monomer, an oligomer, or a polymer, and is used without a solvent, that is, without using a solvent. Examples of the photocurable compound include compounds having a photocurable ethylenic double bond group such as an acryl group and a styryl group.

As the photocurable compound, an ultraviolet curable compound that is cured by irradiation with ultraviolet rays (wavelength range of 100 nm or more and 400 nm or less) is preferable, and this example is also doing the same. Compared to other photocurable compounds, the ultraviolet curable compound requires a shorter time for curing, it is easier to form the convex portion 12 of the desired shape, and the curing unit 34 performs the curing described below. This is because damage to the film material 11 is more reliably suppressed in the process.

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

As a polyfunctional acrylate compound, the (meth)acrylate compound of polyfunctional alcohol, etc. are mentioned, An alkoxylated polyfunctional (meth)acrylate compound is included, Furthermore, an oligomer is included. For example, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,6 -Hexanedioldi(meth)acrylate, 1,9-nonanedioldi(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 Lycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, bis(4-acryloxypolyethoxyphenyl)propane, or neophene Tyl glycol di(meth)acrylate and the like are preferred.

As the alkoxylated polyfunctional (meth)acrylate compound, ethoxylated (3) trimethylolpropane tri(meth)acrylate (a compound obtained by tri(meth)acrylated trimethylolpropane ethylene oxide 3 mol adduct) ), propoxylation (3) trimethylolpropane tri(meth)acrylate (trimethylolpropane propane tri(meth)acrylate compound), ethoxylation (2) neophene Tylglycoldi(meth)acrylate (a compound obtained by diacrylated adducts of 2 moles of neopentylglycolethylene oxide), or propoxylated (2) neopentylglycoldi(meth)acrylate (neopentylglycoldi(meth)acrylate) compounds obtained by diacrylated adducts of 2 moles of pentyl glycol propylene oxide), etc. are preferred.

Moreover, as an oligomer, polyester (meth)acrylate or urethane (meth)acrylate is preferable, and as others, modified glycerin tri(meth)acrylate, modified bisphenol A di(meth)acrylate, Propylene oxide (PO) adduct di(meth)acrylate of bisphenol A, ethylene oxide (EO) adduct di(meth)acrylate of bisphenol A, or caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc. can be preferred.

Examples of acrylamide-based compounds include hydroxyethyl acrylamide, dimethyl acrylamide, isopropyl acrylamide, diethyl acrylamide, dimethylaminopropyl acrylamide, N-vinyl lactams, specifically N-vinyl pyrrolidone, Alternatively, N-vinyl caprolactam and the like are also preferred.

As a monofunctional acrylic compound, isoamyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth) Acrylate, isoamylsteel (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 LATE, Isobornyl(meth)acrylate, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalic acid, lactone modified flexible (meth)acrylic acid rate, t-butylcyclohexyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclopentenyloxyethyl (meth) acrylate, Dicyclopentenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, or cyclic trimethylolpro Pain formal (meth)acrylate and the like are preferred.

In addition, monofunctional acrylic compounds having a cyclic structure in the molecule are also preferable, and specific examples thereof include acryloylmorpholine, benzyl acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, and cyclophene. tenyl (meth)acrylate, cyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, or cyclic trimethylolpropane formal (meth)acrylate. The monofunctional acrylic compound having a cyclic structure in these molecules can increase the solubility of the photopolymerization initiator or the like in the photocurable composition 15 and also improve the heat resistance of the convex portion 12 after curing.

The multifunctional acrylate compound can improve the hardness and strength of a cured resin product. The acrylamide-based compound shortens the time required for curing, and forms convex portions 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 properties such as the refractive index of the convex portion 12.

The photocurable composition 15 preferably contains an acrylamide-based compound as an ultraviolet curable compound. Thus, when the film material 11 is formed from cellulose acylate, it is particularly preferable that the convex portion 12 contains an acrylamide-based compound among the above in terms of high adhesion to the cellulose acylate.

In addition, the photocurable composition 15 preferably contains an acrylamide-based compound and a polyfunctional acrylate compound as ultraviolet curable compounds. As a result, the ejected droplets are quickly cured by light irradiation, and the convex portions after curing have sufficient strength, so there is no roller contamination due to drop-off of the convex portions during roll contact, and a good convex shape can be continuously formed. . 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 preferred range and the shape of the convex portion can be easily adjusted. Moreover, it is also preferable to further contain a monofunctional acrylic compound in the photocuring composition 15. The photocuring composition 15 can uniformly dissolve a photopolymerization initiator or light stabilizer for improving rapid curing properties and stability, and also adjusts the viscosity to a preferred range to further increase the strength, durability, and heat resistance of convex portions after curing. Because.

It is preferable that the photocurable composition 15 has a viscosity within the range of 20 mPa·s or more and 1000 mPa·s or less. When the viscosity is 20 mPa·s or more, compared to the case of less than 20 mPa·s, the shape of the droplet 41 is less likely to change between the time it is attached to the film material 11 and then cured by the curing unit 34. Therefore, it is easy to adjust the timing of hardening, and it is easy to form the convex part 12 of a target shape. When the viscosity is 1000 mPa·s or less, the volume of the discharged droplet 41 can be easily adjusted compared to the case where the viscosity is greater than 1000 mPa·s. Therefore, it is easy to form the convex part 12 of the target size. The viscosity of the photocurable composition 15 is more preferably in the range of 30 mPa·s or more and 500 mPa·s or less, and more preferably in the range of 40 mPa·s or more and 300 mPa·s or less.

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

Moreover, in order to improve the stability of the liquid containing a photocurable compound (photocurable composition 15 in this example), it is preferable to add a photostabilizer. Examples of light stabilizers include nitroso-based 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), cupperone Al, or hindered amine.

Among these light stabilizers, those having a secondary or tertiary amine structure, which are hindered amine light stabilizers (HALS), are preferred. For example, a structure in which the 1st position of a 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-tetra methylpiperidine 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 particularly preferably in the range of 0.1% by mass or more and 0.8% by mass or less with respect to the photocurable composition 15. Within this range, the stability of the photocurable composition in the ejection device can be improved, the viscosity change and curing in the ejection device can be suppressed, and the photocurability of the droplets after ejection is sufficient, so it is preferable. The photocurable compound can adjust the amount of the polyfunctional acrylate compound, the acrylamide compound, or the monofunctional acryl compound to form a mixture of other compounds and adjust the viscosity. As the viscosity modifier for adjusting the viscosity, there are a high viscosity modifier that increases the viscosity and a low viscosity modifier that lowers the viscosity, and the high viscosity modifier is used in this example.

The said viscosity is the viscosity at the temperature in a discharge process, and since discharge is made at room temperature (25 degreeC) in this example, it is set as the viscosity at 25 degreeC. In this example, the viscosity is measured by a tuning fork type small vibrating viscometer CJV5000 (A&D Co., Ltd.).

The curing unit 34 is for forming the convex portion 12 from the liquid droplet 41 . The curing unit 34 is provided downstream of the discharge unit 33 in the moving direction of the film material 11, and supports a plurality of light sources 47 for emitting light and a plurality of light sources 47. For example, a plate-shaped support member 48 is provided. The number of light sources 47 is determined based on the arrangement of convex portions 12 to be formed, the type of 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 ultraviolet curable compound is used as a component of the photocurable composition 15 as described above, it is set as the light source 47 that emits ultraviolet rays. By emitting light by this light source 47, the photocurable compound contained in the droplet 41 adhering to the film material 11 is cured, and thereby the droplet 41 becomes the convex portion 12 (curing step). ).

The film material 11 in which the convex part 12 is formed is moved downstream by the roller 37A and/or the roller 37B, and is sent to the take-up part 35. In addition, the roller 37 arranged downstream of the curing unit 34 makes the flatness of the film material 11 passing through the curing unit 34 better, or the film in the film manufacturing equipment 30 In order to adjust the conveyance of the ash 11, it arranges suitably.

The winding unit 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 rotates 180 degrees intermittently by an arm drive unit (not shown) to selectively switch the winding core 58 to a winding position PS1 and a winding position PS2. In addition, a guide arm 59 is provided at an intermediate position in the rotational direction of the turret arm 56, and guide rollers 61 are attached to each tip of the guide arm 59. The guide roller 61 moves the film 10 in a state where the film 10 does not come into contact with the turret arm 56 and the arm mounting shaft 62 when the turret arm 56 is rotating. support

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 take-up shaft 57 has a rotation mechanism (not shown), which rotates and winds the film 10 around the set winding core 58 . In this way, the take-up shaft 57 constitutes a moving mechanism together with the delivery unit 32, and cooperates with the delivery unit 32 to move the film material 11 in the longitudinal direction. However, the movement mechanism is not limited to this example, and as described above, at least one part of the plurality of rollers 37 disposed on the movement path may be used as drive rollers, and the drive roller may be configured.

At the winding-up position PS1, the film 10 sent from the roller 37 is wound around the core 58. In addition, at the core exchange position PS2, the film 10 of a certain length is wound up, and the film roll 31 wound entirely is separated from the winding shaft 57 together with the winding core 58, and the winding shaft 57 ), a new empty core 58 is set, and the core 58 is exchanged.

In the winding position PS1, the film 10 is wound around the core 58 from the side of the one end 12A as the end 12A (see Fig. 1) described above as the front end in the moving direction Dc, and the film When the roll 31 is in a state close to full winding of a predetermined length, the turret arm 56 rotates 180 degrees to position the film roll 31 close to full winding at the core exchange position PS2. Further, the empty core 58 is positioned at the winding position PS1. When the film roll 31 has reached a predetermined length, a rewinding device (not shown) operates, and the film 10 is cut. The previous film 10 that has been cut has the rear end in the moving direction Dc as the above-mentioned other end 12B, and this other end 12B is wound around the film roll 31 at the core exchange position PS2. do. Moreover, the cut|disconnected film 10 of the back end makes 12 A of front ends, and from one end 12A, it winds up around the empty core 58 at the winding-up position PS1.

Hereafter, the film 10 sent continuously is obtained as the film roll 31 by similarly winding the film 10 around the core 58.

The film manufacturing facility 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 section 35. The pulse generator 66 generates a pulse whenever the connected roller 37 rotates at a certain angle, that is, whenever the film material 11 is sent for a certain 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 application unit that applies a voltage to a piezoelectric element 84 (see FIG. 5) described later of the ejection device 45. The driver 67 drives the ejection device 45 to start and stop ejection of the liquid droplets 41 . The start of discharge means the start of repeated discharge within a certain period of time, and the stop of discharge means the stop of repeated discharge. 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 discharges from start to stop of discharge becomes one. In this way, repeated discharge includes a case where the number of times of discharge is once.

The system controller 68 collectively controls each part of the film manufacturing facility 30, and forms the target convex part 12 at the target position of the film material 11 by this control. let it The system controller 68 obtains the moving length (conveyance length) of the film material 11 every time a pulse is generated from the pulse generator 66 . The length of the moving path from the discharge port 45a of the discharge device 45 (see Figs. 4 and 5) to the roller 37 to which the pulse generator 66 is connected is input to the system controller 68, Based on this length and the moving length of the film material 11 obtained as described above, the tip (one end 12A (see Fig. 1) of the film material 11 passing through the discharge port 45a in the longitudinal direction) equivalent) to detect the position from When the position of the film material 11 forming the convex portion 12 is input in advance to the system controller 68, and the film material 11 passing through the discharge port 45a reaches the target position. Then, the discharge device 45 is driven through the driver 67.

The system controller 68 may obtain the length of the film 10 wound around the take-up shaft 78 and/or the radius of the film roll 31 based on the above pulses. In these cases, based on the obtained length and/or radius, 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 also includes a cycle for discharging the droplets 41, a flow rate of the photocurable composition 15 supplied to the discharging device 45, a volume of the droplets 41, a moving speed of the film material 11, The timing of cutting the film 10 in the winding unit 35 and/or the timing of rotation of the turret arm 56 are input, and each part of the film production equipment 30 is based on these input signals. is controlled

As shown in FIG. 4 , a plurality of 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 of the discharge devices 45 in the width direction is larger than the pitch PW12, all the discharge devices 45 cannot be arranged in a row in the width direction. For this reason, 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 may be appropriately determined based on the size, pitch PW12, etc. of the discharge device 45, and the pitch PW45 of the discharge ports 45a in the width direction is the pitch ( What is necessary is just to arrange the discharge device 45 in the same state as PW).

Moreover, in this example, since the film 10 provided with the convex part 12 is formed in the whole width direction as mentioned above, the discharge device 45 is arrange|positioned in the whole width direction. In addition, even in the case of manufacturing the film 10, the discharge device 45 is provided so as to be movable in the width direction and a shift mechanism (not shown) for moving the discharge device 45 in the width direction is used. Since it can be displaced in the direction, it is not necessary to necessarily provide a plurality of discharge devices 45 over the entire width direction.

Similarly, the light sources 47 of the curing unit 44 are arranged in a state in which a plurality of light sources are lined up in the width direction. The light source 47 is respectively disposed at a position in the width direction of the discharge port 45a of each discharge device 45 . In this way, light is reliably irradiated to each droplet 41 formed on the film material 11 .

The shape of the droplet 41 on the film material 11 changes until it hardens. For example, the shape changes, such as flattening (the height is lower and the diameter R41 is larger), the top of the droplet 41 is flattened, or the top of the droplet 41 is hollowed out. And the shape of the convex part 12 formed by hardening depends on the shape of the droplet 41. In the film 10 of this example, since the plurality of convex portions 12 have a constant shape as described above, the start of curing of the liquid droplets 41 is also performed at a constant timing.

For this reason, the light sources 47 are each disposed in a state where the distance from the discharge port 45a of the discharge device 45 in which the droplet 41 to be irradiated is formed is constant. For example, in this example, the light source 47 that emits light toward the liquid droplets 41 formed in a row of ejection devices 45 on the upstream side in the moving direction among the plurality of ejection devices 45 is on the downstream side. The light source 47 for emitting light toward the droplet 41 formed in the discharge device 45 of the other row is arranged at a position shifted downstream by the pitch PL45 of the discharge port 45a in the longitudinal direction, there is. In this way, irradiation is started for any droplet 41 after a certain period of time after being formed, and the convex portion 12 having a constant shape is formed. The number of light sources 47 arranged in the moving direction is drawn as three in FIG. 4, but this number depends on the moving speed of the film material 11, the viscosity of the photocurable composition 15 (see FIG. 3), What is necessary is just to decide suitably according to the time required for hardening, etc.

As described above, since the shape of the convex portion 12 changes depending on the start timing of curing of the liquid droplet 41 on the film material 11, the shape of the convex portion 12 can be adjusted by using this. That is, the shape of the convex part 12 can be adjusted by adjusting the moving time of the film material 11 from the discharge device 45 to the light source 47. When forming a flatter spherical convex portion 12, when forming a flat convex portion 91 (see Fig. 6) with a top end, and when forming a convex portion 96 (see Fig. 7) with a top end. In this case, the travel time from the discharge device 45 to the light source 47 may be longer. Moreover, what is necessary is just to shorten the movement time from the discharge device 45 to the light source 47 more, when forming the spherical convex part in the aspect with a higher height and a small floor area.

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

As shown in FIG. 5 , the discharge device 45 includes a case 71 and an opening/closing member 72 . The case 71 is composed of a case main body 73, a bottom member 74, a press member 75, O-rings 77a and 77b, a sealing member (packing) 78, and the like, and has an optical sight inside. The chemical composition 15 is charged in a pressurized state. A supply port 73a of the photocurable composition 15 is formed in the side portion of the case body 73, and a supply unit 81 for supplying the photocurable composition 15 to the supply port 73a at a predetermined flow rate are connected

The case body 73 has open bottom and ceiling surfaces, and a bottom member 74 is fixed to the open portion of the bottom surface, and a pressing member 75 is fixed to the open portion of the top surface, respectively. 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, leakage of the photocurable composition 15 filled therein is blocking A through hole 82 is formed in the bottom member 74, and one end of the through hole 82 is exposed to the inside where the photocurable composition 15 is filled, and the other end serves as a discharge port 45a. . The diameter (unit: μm) of the discharge port 45a is preferably in the range of 30 or more and 300 or less, and more preferably in the range of 50 or more and 150 or less.

The opening and closing member 72 is for opening and closing one end of the inner side of the through hole 82 . As shown in FIG. 5(B), the opening/closing member is between an open position in which the end of the through hole 82 is opened, and a closed position in which the end is closed as shown in FIG. 5(A). It is possible to move from The opening/closing member 72 has an abutting portion 83, a piezoelectric element (piezo element) 84, and the above-described driver 67 (see FIG. 3), and the abutting portion 83 provided at the tip , it abuts against the floor member 74 in a state where the end is closed in the closed position.

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

The photocurable composition 15 is supplied to the inside of the case 71 at a predetermined flow rate from the supply unit 81, and the supply unit 81 is in a state in which the photocurable composition 15 is pressurized inside the case 71. The photocurable composition 15 is supplied until it is filled with. And the supply part 81 supplies the photocurable composition 15 even when the photocurable composition 15 is discharged from the discharge port 45a, for example, and pressurizes the photocurable composition 15 in the inside. keep the status quo In this way, the supply unit 81 also functions as a press mechanism.

By moving the opening/closing member 72 in the closed position to the open position, the photocurable composition 15 filled in a pressurized state passes through the end and goes to the discharge port 45a. Then, by moving the opening/closing member 72 in 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 movement path between the discharge port 45a and the film material 11 (see Fig. 3) is set at a distance larger than the size of the droplet 41, so that the droplet 41 can fly through the space. . As a result, the liquid droplets 41 discharged from the discharge port 45a fly toward the film material 11 from the discharge port 45a and adhere thereto. By moving the opening/closing member 72 from the closed position again to the open position and then returning to the closed position, a new droplet 41 is attached to a different position in the longitudinal direction of the moving film member 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 a pressurized state is discharged as droplets 41 from the discharge port 45a, and the moving film material It is made to fly toward (11) (discharge process).

Further, 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 . The volume of the droplet 41 can be adjusted by adjusting the timing of the 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 again. In addition, the volume of the droplet 41 can also be adjusted by adjusting at least either one of the viscosity of the photocurable composition 15 (see Fig. 3) and the pressure of the photocurable composition 15 inside the case 71. can be adjusted In the discharging step, the liquid droplet 41 is discharged in a volume within a range of 0.8×10 ^-12 m ³ or more and 100.0×10 ^-12 m ³ or less, that is, the photocurable composition 15 is discharged in a volume of 0.8×10 ^-12 m ³ or more. It is preferable to discharge with a volume within the range of 100.0×10 ^-12 m ³ or less, and by being within this range, the size of the convex portion 12 can be more easily adjusted.

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

Although the above example is the opening/closing member 72 provided with the piezoelectric element 84, the opening/closing member is not limited to this example. For example, an opening/closing member that moves the abutting portion biased by a spring by a change in air pressure instead of a change in the shape of the piezoelectric element 84 may be used. Such a discharge device and discharge mechanism are called a jet dispenser and a jet dispenser method, and the Journal of the Korean Society of Electronic Packaging 2004, Vol. 7, no. 6 (page 501), commercially available devices may be used.

In this example, although the spherical convex part 12 is formed, you may change the shape of the convex part 12 according to the function of the target film. For example, as shown in FIG. 6 , the top 91a may be a flat convex portion 91 . The top 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 a top 96a may be sufficient. In either case, the ratio HP/RP is preferably within the above range.

In addition, after repeatedly discharging the photocurable composition 15 multiple times over a long period of time by the discharging device 45, the opening/closing member 72 stops opening and closing during repetition of continuous discharging, and the number of times of discharging is increased. Sometimes it just isn't enough. As this mechanism, it is estimated as follows. That is, in the ejection device 45, since the photocurable composition 15 is repeatedly ejected multiple times over a long period of time, when the opening/closing member 72 reciprocates as shown in (A) and (B) of FIG. 5 , The photocurable composition 15 seeps into the gap between the sealing member 78 and the shaft 85 of the opening/closing member 72, and the photocurable composition 15 accumulates on the portion of the O-ring 77a. Then, friction occurs between the shaft 85 of the sealing member 78 and the opening/closing member 72 and/or between the O-ring 77a and the shaft 85 of the opening/closing member 72, resulting in heat or frictional energy. As a result, the photocurable composition 15 is polymerized within the case 71, and the vicinity of the O-ring 77a in the case 71, the shaft 85 of the opening and closing member 72, and/or the sealing member 78 A reactant of the photocurable composition 15 adheres thereto, making it impossible for the opening/closing member 72 to reciprocate.

With 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 a polymerization reaction within the case 71, in the photocurable composition 15, the addition amount of the photopolymerization initiator is reduced, or 4-hydroxy TEMPO (4-hydroxy- 2,2,6,6-tetramethylpiperidine 1-oxyl etc.) etc. are adjusted in quantity and added, etc. are performed. In addition, it is also preferable to use N-vinyllactams, which are acrylamide-based compounds, as the ultraviolet curable compound in order to more appropriately impart long-term ejection durability and photocurability of droplets after ejection. This is because, compared to other acrylamide-based compounds, N-vinyllactams suppress polymerization reactions due to energy such as friction and have high photopolymerization reactivity. 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 component amount of the photocurable compound in the photocurable composition 15 (acrylamide-based compound, monofunctional The composition ratio of the acrylamide-based compound in the acrylic compound and/or the total amount of polyfunctional acrylate) is within the range of 10% by mass or more and less than 60% by mass, more preferably within the range of 20% by mass or more and less than 50% by mass is also desirable Within this range, the polymerization reaction in the casing due to energy such as friction can be suppressed, and the droplets applied to the film are rapidly photocured, so it is preferable.

The film manufacturing facility 30 (see FIG. 3) is not limited to manufacturing the film 10, and various films can be manufactured by using the above-described pulse generator 66 and system controller 68. there is. For example, the film 110 shown in FIG. 8 can also be manufactured by the film manufacturing facility 30. The film 110 is equipped with the convex part 12 only in the fixed section of both sides of the long film material 11. In addition, the section in the width direction forming the convex part 12 is not limited to both sides, for example, in addition to both sides, or instead, it may be, for example, a certain section in the center in the width direction. .

In the case of manufacturing the film 110, the system controller 68 drives only the discharging device 45 arranged in a certain section at both ends in the width direction through the driver 67. In the same manner for the light source 47, only a part of both ends in the width direction where the droplet 41 is formed is driven by the system controller 68 to emit light. Thus, the convex portion 12 is formed in a predetermined area in the width direction by driving only each part in the width direction among all the ejection devices 45 and light sources 47 by the system controller 68. A variety of films can be produced. However, an aspect in which the discharge device 45 and the light source 47 are disposed only in a section formed by the convex portion 12 in the width direction may be used.

Moreover, the film 120 shown in FIG. 9 can also be manufactured by the film manufacturing facility 30 (refer FIG. 3). The film 120 is equipped with the convex part 12 in the part section of the length direction of the long film material 11. Specifically, the convex part 12 is provided for every fixed section in the longitudinal direction. In the case of manufacturing the film 120, first, the system controller 68 detects the position from the tip in the longitudinal direction of the film material 11 passing through the discharge port 45a by the method described above, 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 to discharge the liquid droplets 41 (see Fig. 3). Similarly, the light source 47 is driven by the system controller 68 when the film 120 on which the droplets 41 are formed is positioned at a target position, and light is emitted to convex portions. (12) is formed.

Example

[Example 1] to [Example 15]

The film 10 was manufactured using the film manufacturing facility 30. The film material 11 is a TAC film formed of TAC. The photocurable composition 15 is a liquid mixture obtained by mixing a high viscosity agent as a viscosity modifier, a photopolymerization initiator, and the like, and was supplied to the discharge device 45 from the supply unit 81 . As the photocurable composition 15, eight types are prepared, and these are hereinafter referred to as liquid mixtures A to H.

Formulations of mixed solutions A to H as the photocurable composition (15) are shown in the "mixture" column of Table 1. Table 1 shows acrylamide-based compounds and their viscosities, polyfunctional acrylate compounds and their viscosities, monofunctional acryl compounds and their viscosities, and the amounts of these compounds and photopolymerization initiators. The photopolymerization initiator is a mass ratio of Irgacure (registered trademark) 907 (manufactured by BASF Japan Co., Ltd.) and 2,4-diethylthioxanthone (KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.) 1 to 1 It is a mixture of 3. Further, 0.2 parts by mass of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (4-hydroxy TEMPO) as a photostabilizer was added to mixed solution A, mixed solution D, and mixed solution H. added

In Table 1, A or B of the acrylamide-based compound, C or D of the polyfunctional acrylate compound, and E of the monofunctional acryl compound are respectively 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)

[Table 1]

Conditions for producing the film 10 are shown in Table 2. In addition, the ejection of the droplet 41 was repeatedly performed at a constant cycle. "Frequency" in Table 2 is the reciprocal number of the cycle of repeatedly ejecting the liquid droplets 41 . The "amount of discharged liquid" in Table 2 is the amount of the liquid mixture discharged from the discharge device 45, and is also the volume of each liquid droplet 41. As the curing unit 34, a commercially available ultraviolet irradiation device HLUV-126UV365 (manufactured by CCS Corporation) 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 0.4 m.

[Table 2]

About each obtained film 10, the diameter (RP) and height (HP) of the convex part 12, 91, 96 were measured, and ratio HP/RP was calculated. Also, the pitch (PW12) was measured. Further, the shape of the convex portion 12 and the degree of contamination of the circumferential surface of the roller 37B between the curing unit 34 and the take-up portion 35 were evaluated. Each evaluation method and criteria are as follows. Each result is shown in Table 2.

(1) Diameter (RP), height (HP), shape of convex part

Diameter (RP) and height (HP) were measured by shape analysis using LEXT OLS4000, a 3D laser microscope manufactured by Olympus. The shape is a shape of the convex portion 12 when viewed from the vertical direction of the first surface 11A (hereinafter referred to as a plan view shape), and when the plan view shape is circular, a shape viewed from a cross section in the thickness direction ( Hereinafter referred to as cross-sectional shape) was evaluated according to the following criteria. The plurality of convex portions smaller than the target convex portion and different in size from each other in D below are generated by the separation of the droplet 41 . A, B, and C pass, D fails.

A; The shape in plan view is circular, and the cross-sectional shape is semi-circular or bow-shaped.

B; The shape in plan view is circular, and the cross-sectional shape has a flat top as shown in FIG. 6 or a concave portion as shown in FIG. 7

C; The shape in plan view was not circular, but a distorted shape as shown in FIG. 10 . In addition, only the convex part is drawn in FIG. 10, and the numeral 150 is attached to the convex part.

D; The shape in plan view cannot be said to be circular, or a plurality of convex portions smaller than the target convex portion and having different sizes are confirmed.

(2) Contamination of roller 37B

After the film 10 is produced, the circumferential surface of the roller 37B between the curing unit 34 and the take-up portion 35 is visually observed under normal room lighting (hereinafter referred to as normal observation), When contamination was not observed by normal observation, it was visually observed 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 the following A to C are considered acceptable.

A; No contamination was confirmed on the rollers in forced observation.

B; With forced observation, very slight contamination was observed

C; Contamination was observed by normal observation

(3) Discharge durability

Using the discharge device 45 of the film manufacturing apparatus 30, a repeated discharge test of the photocurable composition 15 was conducted, 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 the repeated discharge is stopped. In the discharge durability evaluation, the repeated discharge conditions were the same as in each Example except that the frequency was set to 1000 HZ. The discharge durability was evaluated as follows. A to C below are all pass.

A; More than 5 million discharges.

B; 500,000 or more to less than 5,000,000 discharges.

C; Dispensing times 10,000 or more and less than 500,000.

D; Less than 10,000 discharge times.

[Comparative Example 1] to [Comparative Example 2]

Films having a plurality of convex portions were manufactured using a commercially available discharge device of an inkjet method, and were used as Comparative Examples 1 and 2. In addition, the discharge device of the inkjet system does not include an opening and closing member that opens and closes the discharge port 45a like the opening and closing member 72 of this example. In Comparative Example 1, liquid mixture E shown in Table 1 was used as the photocurable composition discharged from the above discharge device. In Comparative Example 2, using the mixture F of the prescription shown in Table 1, the total amount of this mixture 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 The liquid mixture mixed with parts by weight was discharged by the above discharge device. The viscosity of the liquid mixture F was 20 mPa·s or less. Moreover, a dryer was provided between the discharge device 45 of the film manufacturing facility 30 and the curing unit 34 to manufacture a film, and it was set as the comparative example 2. In Comparative Example 2, the convex portions were formed by drying the formed droplets at 100°C for 20 seconds with a dryer and then irradiating light. In any comparative example, the film material used is a TAC film formed of TAC, and is the same as the film material 11 used in the examples.

With respect to 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 convex portions of a fixed shape were not obtained, the diameter (RP), height (HP), and pitch (PW12) of the convex portions were not measured. Further, the shape of the convex portion and the degree of contamination of the circumferential surface of the roller 37B between the curing unit 34 and the take-up portion 35 were evaluated. Each result is shown in Table 2.

[Example 16] to [Example 18]

Film 10 was manufactured in the same manner as in Example 11. The film material 11 is a TAC film formed of TAC. As the photocurable composition 15, three types are prepared, and these are hereinafter referred to as liquid mixtures I to K.

Formulations of mixtures I to K as the photocurable composition (15) are shown in the "mixture" column of Table 3. Table 3 shows acrylamide-based compounds and their viscosities, polyfunctional acrylate compounds and their viscosities, monofunctional acryl compounds and their viscosities, types and amounts of photopolymerization initiators, and amounts of photostabilizers. As the photopolymerization initiator, in Table 3, as photopolymerization initiator A, it is the same as that used in the mixtures A to D described above, and Irgacure (registered trademark) 907 (manufactured by BASF Japan Co., Ltd.) and 2,4-diethyl A mixture of thioxantone (KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.) in a mass ratio of 1:3 was used. In addition, as the photopolymerization initiator B, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Irgacure (registered trademark) 819, manufactured by BASF Japan Co., Ltd.) and 2,4,6-trimethyl A mixture of benzoyldiphenylphosphine oxide (DAROCUR (registered trademark) TPO, manufactured by BASF Japan Co., Ltd.) and isopropylthioxanthone (produced by LAMBSON) at a mass ratio of 4:5:2 was used. Further, as a photostabilizer, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (4-hydroxy TEMPO) was added in an amount shown in Table 3.

In Table 3, F of the acrylamide-based compound, G or H of the polyfunctional acrylate compound, and I of the monofunctional acryl compound are respectively as follows. In addition, since two types of polyfunctional acrylate components were used, they were divided into columns of "first polyfunctional component" and "second polyfunctional component" of "multifunctional component" in Table 3 and described.

F; N-vinyl caprolactam (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

G; Ethoxylation (3) Trimethylolpropane triacrylate (SR454 D NS, manufactured by Sartomer Japan Co., Ltd.)

H; CN964A85 (urethane acrylate oligomer, average functional group number 2, manufactured by Sartomer Japan Co., Ltd.)

I; Cyclic trimethylolpropane formal acrylate (SR531, manufactured by Sartomer Japan Co., Ltd.)

[Table 3]

Conditions for producing the film 10 were performed 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]

10, 110, 120 film
11 Film material
11A first surface
11B second surface
12, 91, 96, 150 convex part
15 photocurable composition
30 Film Manufacturing Facility
31 film rolls
32 Transmitter
32a axis of rotation
33 discharge part
34 curing units
35 winding part
37A, 37B rollers
38 rolls of film material
41 drops
42 support roller
44 discharge unit
45 ejection device
45a outlet
46 support member
47 light source
48 support member
56 turret arm
57 take-up shaft
58
59 guide arm
61 guide roller
62 arm mounting axis
66 pulse generator
67 driver
68 system controller
71 cases
72 opening and closing member
73 case body
73a supply port
74 floor member
75 Press member
77a, 77b O-ring
78 sealing member
81 supply department
82 through holes
83 abutment
84 piezoelectric element
85 axis
91a, 96a Government
Dc moving direction
HP height
L length
PL12, PW12, PL45, PW45 Pitch
RP, R41 diameter
PS1 winding position
PS2 winding core exchange location

Claims (20)

In the film manufacturing method of forming a plurality of convex portions on a long film material moving in the longitudinal direction,
A case in which a liquid containing a photocurable compound is filled, a through hole formed in the case, one end exposed to the inside and the other end serving as a discharge port for the liquid, and an opening and closing member for opening and closing the one end. The case of the discharge device is filled with the liquid in a pressurized state, and the opening/closing member moving between an open position in which the one end is opened and a closed position in which the one end is closed is moved from the closed position to the open position. a discharge step of discharging the liquid filled in the inside as liquid droplets from the discharge port and flying toward the moving film material by repeatedly moving;
The photocurable compound of the droplet adhering to the film material is cured by using a light source that is provided downstream of the ejection device in the moving direction of the film material and emits light for curing the photocurable compound. a curing step of making the droplet the convex portion;
The opening/closing member has a piezoelectric element, an abutting portion fixed to the piezoelectric element and brought into contact with the one end of the through hole, and a voltage application unit for applying a voltage to the piezoelectric element, wherein the voltage application unit is configured to include the piezoelectric element. By increasing or decreasing the voltage applied to the element, the abutting portion is moved between the open position and the closed position;
The photocurable compound is a film manufacturing method comprising N-vinyllactam. delete The method of claim 1,
In the discharging step, the liquid droplet is discharged in a volume within a range of 0.8×10 ⁻¹² m ³ or more and 100.0×10 ⁻¹² m ³ or less. delete The method of claim 1,
The film manufacturing method in which the viscosity of the said liquid is in the range of 20 mPa*s or more and 1000 mPa*s or less. delete The method of claim 3,
The film manufacturing method in which the viscosity of the said liquid is in the range of 20 mPa*s or more and 1000 mPa*s or less. The method of claim 1,
The film manufacturing method of adjusting the shape of the said convex part by adjusting the moving time of the said film material from the said discharge device until it reaches the said light source. delete The method of claim 3,
The film manufacturing method of adjusting the shape of the said convex part by adjusting the moving time of the said film material from the said discharge device until it reaches the said light source. The method of claim 5,
The film manufacturing method of adjusting the shape of the said convex part by adjusting the moving time of the said film material from the said discharge device until it reaches the said light source. According to claim 1, claim 3, claim 5, claim 7, claim 8, claim 10 or claim 11,
The light is an ultraviolet ray, and the photocurable compound is an ultraviolet ray curable compound. The method of claim 12,
The ultraviolet curable compound is a film manufacturing method of an acrylamide-based compound. According to claim 1, claim 3, claim 5, claim 7, claim 8, claim 10 or claim 11,
The photocurable compound is a film manufacturing method comprising a photostabilizer. According to claim 1, claim 3, claim 5, claim 7, claim 8, claim 10 or claim 11,
The photocurable compound is a film manufacturing method comprising a monofunctional acrylic compound. According to claim 1, claim 3, claim 5, claim 7, claim 8, claim 10 or claim 11,
The photocurable compound is a film manufacturing method comprising a multifunctional acrylate compound. According to claim 1, claim 3, claim 5, claim 7, claim 8, claim 10 or claim 11,
The film manufacturing method in which the said film material is formed from cellulose acylate. In a film manufacturing facility for forming a plurality of convex portions on a long film material moving in the longitudinal direction,
A moving mechanism for moving the elongated film material in the longitudinal direction;
a discharge device for discharging the liquid, with a discharge port for a liquid containing a photocurable compound disposed facing the moving path of the film material;
A light source provided downstream of the ejection device in the moving direction of the film material and emitting light for curing the photocurable compound,
The ejection device,
A case in which the liquid is charged while being pressurized therein;
A through hole formed in the case, one end exposed to the inside and the other end serving as the discharge port;
An open position where the one end is opened and the liquid is discharged as droplets from the discharge port and is adhered to the film material by flying toward the moving film material; It has an opening and closing member that repeatedly moves between positions,
The opening/closing member has a piezoelectric element, an abutting portion fixed to the piezoelectric element and brought into contact with the one end of the through hole, and a voltage application unit for applying a voltage to the piezoelectric element, wherein the voltage application unit is configured to include the piezoelectric element. By increasing or decreasing the voltage applied to the element, the abutting portion is moved between the open position and the closed position;
The photocurable compound is a film manufacturing facility containing N-vinyllactam. A film material formed of cellulose acylate;
A spherical convex portion or a plurality of convex portions in which a concave portion is formed at the top is provided on one surface of the film material,
The plurality of convex portions are regularly arranged,
The convex portion has a height of 12 μm or more and 70 μm or less,
The convex portion has a diameter in the range of 550 μm or more and 800 μm or less,
When the height of the convex portion is HP and the diameter of the convex portion 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 film formed from a composition containing a monofunctional acrylic compound having a cyclic structure in the molecule. delete

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