CN112770847B

CN112770847B - Thin film manufacturing method and apparatus, and thin film

Info

Publication number: CN112770847B
Application number: CN201980063389.5A
Authority: CN
Inventors: 佐部利彰人; 山内忠; 田崎大辅
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2018-09-28
Filing date: 2019-09-26
Publication date: 2023-03-24
Anticipated expiration: 2039-09-26
Also published as: JPWO2020067324A1; KR20210047340A; WO2020067324A1; JP7125996B2; TW202026671A; KR102536653B1; TWI821421B; CN112770847A

Abstract

The invention provides a method and equipment for manufacturing a long film with a plurality of convex parts formed in a larger size, and the film obtained by the method and equipment. The film manufacturing method includes a discharge step and a curing step, and forms a plurality of projections on a long film material. The discharge device (45) is filled with a photocurable composition (15) and is provided with a housing and an opening/closing member. The housing is filled with a photocurable composition (15) in a pressurized state. The opening/closing member discharges the photocurable composition (15) in the form of droplets (41) and makes the droplets fly toward the moving film material (11). In the curing step, the photocurable compound of the liquid droplet (41) is cured by a light source (47) to form the liquid droplet (41) into a convex portion (12).

Description

Thin film manufacturing method and apparatus, and thin film

Technical Field

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

Background

Window films that are both visually preventive and designable and that are attached to windows of buildings (e.g., tall buildings, shop buildings, houses, etc.) are known. In such a window film, a plurality of protrusions are formed on the surface of the film, thereby preventing visibility when one of the outside and the inside of a building is viewed from the other, and improving design in a window.

It is also known that a plurality of projections are formed on an optical functional thin film used for Digital Signage (Digital signal) or screen projection. Such an optical functional film is required to have both light transmittance and light scattering properties, and further improvement of these functions is required.

As a method for forming the convex portion on the thin film material, there are a method using screen printing (for example, refer to patent document 1) and a method using ink jet (for example, refer to patent documents 2 and 3). Further, there is a so-called Needle dispensing (Needle dispenser) system as follows: the tip of a nozzle for ejecting a solution for forming the projection is arranged very close to the film material, and the solution is ejected from the tip in a state of spreading over the film material, thereby adhering the solution to the film material (for example, refer to patent document 4).

Prior art documents

Patent literature

Patent document 1: japanese laid-open patent publication No. 2014-012388

Patent document 2: japanese patent laid-open publication No. 2013-227515

Patent document 3: international publication No. 2010/143524

Patent document 4: japanese patent laid-open publication No. 2017-109481

Disclosure of Invention

Technical problem to be solved by the invention

However, in the method described in patent document 1, although the convex portions can be formed on a sheet-like (single sheet) film material, the convex portions cannot be continuously formed on a long film material. Therefore, it is difficult to manufacture a long film having a plurality of projections.

In addition, in the methods described in patent documents 2 and 3, since the size of the liquid droplet that can be formed is very small, the size of the projection that can be formed from one liquid droplet is limited, and the levels of the above-described performances required for the window film and/or the optical functional film are not achieved. Further, when the projection is formed to have a large size, it is necessary to perform ejection a plurality of times in a state where droplets are overlapped in order to form one projection, and efficiency is poor. Further, it is also very difficult to adjust the overlapping state of the droplets. Therefore, it is difficult to produce a film for each of the above applications. In this way, if the film can be manufactured in a long shape by forming the convex portions larger, the application can be expected to be expanded.

Accordingly, an object of the present invention is to provide a method and an apparatus for manufacturing a long film having a large number of projections and capable of efficiently manufacturing a long film having a plurality of projections, and a film obtained thereby.

Means for solving the technical problem

In order to achieve the above object, a film production method of the present invention includes a discharge step and a curing step, and a plurality of projections are formed on a long film material moving in a longitudinal direction. In the discharge step, the solution is charged in a pressurized state into a casing of a discharge device including a casing filled with a solution containing a photocurable compound, a through hole formed in the casing and having one end exposed to the inside and the other end serving as a discharge port for the solution, and an opening/closing member for opening and closing the one end, and the solution charged in the casing is discharged from the discharge port in the form of droplets by repeatedly moving the opening/closing member, which moves between an open position for opening the one end and a closed position for closing the one end, and is caused to fly toward the moving film material. In the curing step, the liquid droplets are formed into the convex portions by curing the photocurable compound adhering to the liquid droplets of the film material 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.

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

In the discharge step, the discharge amount is preferably 0.8X 10 ^-12 m ³ Above and 100.0X 10 ^-12 m ³ The volume in the following range ejects droplets.

The viscosity of the solution is preferably in the range of 20 mPas to 1000 mPas.

Preferably, the shape of the projection is adjusted by adjusting the moving time of the film material from the discharge device to the light source.

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

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

The film material is preferably formed of cellulose acylate.

The film manufacturing apparatus 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 a longitudinal direction. The moving mechanism moves the long film material in the longitudinal direction. The discharge device is disposed in a state in which a discharge port of a solution containing a photocurable compound is directed toward a moving path of a thin film material, and discharges the solution. The light source is provided downstream of the discharge device in the moving direction of the film material, and emits light for curing the photocurable compound. The discharge device has a housing formed with a through hole and an opening/closing member. The housing is filled with the solution in a pressurized state. One end of a through hole formed in the housing is exposed to the inside and the other end serves as a discharge port. The opening/closing member is repeatedly moved between an open position where the one end is opened and the solution is discharged from the discharge port in the form of droplets and flies toward the moving film material to adhere to the film material, and a closed position where the one end is closed and the discharge of the droplets is stopped.

The film of the present invention includes a film material formed of cellulose acylate, and one surface of the film material includes a plurality of convex portions in a spherical crown shape, convex portions with a flat top portion, and convex portions with a recess formed at the top portion.

The plurality of projections are preferably regularly arranged.

Effects of the invention

According to the present invention, a long-length film having a plurality of projections can be efficiently obtained while forming the projections larger.

Drawings

Fig. 1 is an explanatory view of a film as an embodiment of the present invention.

FIG. 2 is an explanatory view of the film, wherein (A) is a plan view and (B) is a sectional view taken along the line (IIb) to (IIb) of (A).

Fig. 3 is a schematic view of a thin film manufacturing apparatus.

Fig. 4 is an explanatory view of the discharge device and the light source.

Fig. 5 is a schematic cross-sectional view of the discharge device.

Fig. 6 is a schematic sectional view of another projection.

Fig. 7 is a schematic sectional view of another projection.

Fig. 8 is a plan view of another film.

FIG. 9 is a plan view of another film.

Fig. 10 is an explanatory view of the shape of the convex portion in the evaluation in the example.

Detailed Description

In fig. 1, a film 10 according to an embodiment of the present invention is formed in a long shape. The film 10 includes a long film material 11 and a plurality of protrusions 12. The film 10 can be used as a window film that is attached to a window of a building (for example, a building for a shop, a house, or the like) and has both visibility prevention and design properties, and an optical functional film having light transmittance and/or light scattering properties used for digital signage or screen projection.

The film material 11 is formed in a so-called flat film shape having two flat surfaces. The thickness T11 (unit is μm) of the film material 11 is not particularly limited, but is preferably in the range of 10 μm to 300 μm from the viewpoints of handling (handleability), windability as the film 10, and the like.

The material of the film material 11 is not particularly limited, but is preferably formed of a transparent polymer when used as a window film or an optical functional film. The film material 11 may contain 1 or 2 or more kinds of various additives such as a plasticizer, an ultraviolet absorber, and fine particles in addition to the polymer.

As the polymer forming the film material 11, a thermoplastic resin is preferable, and as the thermoplastic resin, cellulose acylate, polyethylene terephthalate, an acrylic resin, a cyclic polyolefin resin (for example, ARTON (registered trademark) manufactured by JSR Corporation), and the like are more preferable. Among these, cellulose acylate is more preferably formed of cellulose acylate, and examples of the cellulose acylate include cellulose Triacetate (TAC), cellulose Diacetate (DAC), cellulose acetate propionate, cellulose acetate butyrate, and the like. Among cellulose acylate, TAC is particularly preferable. This is because, among cellulose acylate, particularly preferable are transparency of TAC, a function of being able to form the convex portion 12 into a desired shape (convex portion forming property), and adhesion (adhesive force) with the convex portion 12 formed of a photocurable resin as described later.

The plurality of projections 12 are formed so as to be distributed over the entire area of one surface (hereinafter, referred to as "1 st surface") 11A of the film material 11, but only a part of the plurality of projections 12 is illustrated in fig. 1. In this example, the plurality of projections 12 are formed only on the 1 st surface 11A, but may be formed on the other surface 11B (see fig. 2B). The plurality of projections 12 are regularly arranged, and in this example, are square as shown in fig. 1. However, the arrangement of the plurality of projections 12 is not particularly limited, and may be, for example, a matrix or the like, or may be a so-called irregular arrangement (random arrangement) having no regularity.

As shown in fig. 2, in the film 10 of the present example, the convex portion 12 has a spherical crown shape, that is, a semicircular shape in cross section or an arcuate shape in cross section. Thus, when light enters the surface of the film 10 where the convex portions 12 are formed, the light is reflected and scattered by the circular or arcuate shape of the convex portions 12, and the design and/or visibility prevention are excellent. The projections 12 are arranged in a state of being separated from each other, but may be in contact with each other. When the centers of the convex portions 12 are separated from each other when the 1 st surface 11A is viewed from the vertical direction, the convex portions 12 may overlap each other. In this example, a pitch PW12 (unit is mm) between the convex portions 12 in a width direction of the film 10 (also, a width direction of the film material 11, hereinafter, simply referred to as "width direction") is constant, and a pitch PL12 (unit is mm) between the convex portions 12 in a longitudinal direction (also, a longitudinal direction of the film material 11, hereinafter, simply referred to as "longitudinal direction") is also constant. The pitch PW12 is the center-to-center distance of the projections 12 in the width direction when the 1 st surface 11A is viewed from the vertical direction, and the pitch PL12 is the center-to-center distance of the projections 12 in the longitudinal direction. In the following description, when the pitch PW12 and the pitch PL12 are not distinguished, the pitch P12 (unit is mm) is described.

The plurality of projections 12 are formed to have the same size, but may be formed to have different sizes. The projections 12 having different sizes may be arranged with a certain regularity. The diameter RP (unit is μm) of the projection 12 when the 1 st surface 11A is viewed from the vertical direction is preferably in the range of 50 μm to 2000 μm. When the diameter RP is 50 μm or more, the visibility of the film 10 when viewed from one of the outside and the inside of a window is higher than that when the diameter RP is less than 50 μm, for example, when the other is viewed from the outside or the inside of the window. When the diameter RP is 2000 μm or less, the design is excellent because the uneven feeling observed by the plurality of convex portions 12 is small (thin) when the film is used for a window film as described above, as compared with the case of being larger than 2000 μm. The shape of the convex portion 12 when viewed from the direction perpendicular to the 1 st surface 11A is circular, but it is not necessarily strictly circular, and in this case, the circle-equivalent diameter is defined as the diameter D12. The circle-equivalent diameter is the diameter in a circle of the same area.

When the height of the convex portion 12 is HP (unit is μm), the ratio HP/RP of the height HP divided by the diameter RP is preferably in the range of 0.01 to 0.5. When the HP/RP ratio is 0.01 or more, the light scattering property by the convex portions 12 is improved and the visibility preventing property is improved as compared with the case of less than 0.01. When the HP/RP ratio is 0.5 or less, a part of the projection 12 is less likely to be chipped off and less likely to be detached in the processing of the film 10 than in the case of being larger than 0.5. By performing the above-described complicated process, even when the convex portions 12 are partially chipped off or the convex portions 12 are detached, the thin film portion is not easily observed as unevenness, and the design of the thin film 10 is excellent. Further, when the convex portion 12 is formed to have a ratio HP/RP of 0.5 or less, there are also advantages as follows, compared with the case of forming to have a ratio HP/RP of more than 0.5: even when the convex portion 12 comes into contact with a roller 37B between the curing unit 34 and the winding unit 35, which will be described later, the convex portion is less likely to be chipped off and less likely to be detached. The height HP is a distance from the 1 st surface 11A to the top of the projection 12.

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

The thin film manufacturing apparatus 30 shown in fig. 3 is an example of an apparatus for manufacturing the thin film 10. In the film manufacturing apparatus 30, the film 10 is obtained in the form of a film roll 31 wound in a roll shape. The thin film manufacturing apparatus 30 includes a feeding unit 32, a discharge unit 33, a curing unit 34, and a winding unit 35 in this order from the upstream side in the moving direction Dc of the thin film material 11.

Rollers

37A and 37B are provided in a moving path for moving the film material 11. The roller 37A that contacts the surface of the film material 11 on which the convex portion 12 is not formed and the surface on which the convex portion 12 is not formed is denoted by 37B, and the roller that contacts the surface of the film material 11 on which the convex portion 12 is formed and the surface of the film 10 on the convex portion 12 side is denoted by 37B. In the following description, the roller 37A and the roller 37B are not distinguished from each other, and are referred to as the roller 37. The plurality of rollers 37 may include a drive roller that is provided with a rotation mechanism (not shown) and is rotated in the circumferential direction by the rotation mechanism.

The feeding section 32 is fitted with a film material roll 38 in which the film material 11 is wound in a roll shape. The feeding unit 32 includes a rotary shaft 32a on which the film roll 38 is mounted, and the rotary shaft 32a is rotated by a rotating mechanism (not shown), thereby continuously feeding the long film 11 from the film roll 38. The moving speed of the film material 11 is adjusted by adjusting the rotation speed of the rotating shaft 32 a. In this way, the feeding unit 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 in accordance with the target pitch PL12 and/or the shape of the convex portion 12, but is preferably in the range of 2 m/min to 200 m/min from the viewpoint of more reliably forming the convex portion 12 at the target position and in the target shape.

The ejection portion 33 is for forming the liquid droplets 41 to be the projections 12 (see fig. 1 and 2) on the 1 st surface 11A of the film material 11. The discharge section 33 is composed of a support roller 42 for supporting the film material 11, a discharge unit 44 for discharging the photocurable composition 15 in the form of droplets 41, and the like. The support roller 42 is a driven roller whose circumferential surface is wound with the film material 11 and which rotates by contacting the film material 11 moving in the longitudinal direction. Further, a rotation mechanism (not shown) may be provided on the support roller 42, and the rotation shaft 42a may be rotated by the rotation mechanism (not shown).

The discharge unit 44 includes a plurality of discharge devices 45 that discharge the photocurable composition 15, and a plate-shaped support member 46 that supports the plurality of discharge devices 45, for example. The number of the discharge devices 45 is determined depending on the arrangement of the formed convex portions 12, and the like, and may be 1.

The discharge device 45 is disposed in a posture in which a discharge port 45a (see fig. 4 and 5) for discharging the photocurable composition 15 is directed to the circumferential surface of the support roller 42 which is a part of the moving path of the film material 11. When focusing attention on one of the plurality of discharge devices 45, the photocurable composition 15 is intermittently discharged as droplets from the discharge port 45a toward the moving film material 11, and the droplets 41 are sequentially attached in the longitudinal direction (discharge step). In this manner, the film 10 is manufactured through the discharge step in the discharge section 33. Details of the discharge device 45 will be described later with reference to another drawing.

The photocurable composition 15 is an example of a solution containing a photocurable compound, and in this example, is a mixture containing a liquid or solid photocurable compound. The photocurable compound may be a liquid, and in this case, only the photocurable compound may be used. Further, 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 any of a monomer, an oligomer, and a polymer, and is used in a state of no solvent, that is, in a state of no solvent. Examples of the photocurable compound include compounds containing a photocurable ethylenic double bond group such as an acrylic group and a styryl group.

The photocurable compound is preferably an ultraviolet-curable compound that is cured by irradiation with ultraviolet light (having a wavelength in the range of 100nm to 400 nm), and is also defined in the present example. This is because the time required for curing the ultraviolet curable compound is shorter than that of other photocurable compounds, the convex portion 12 having a desired shape is more easily formed, and damage to the thin-film material 11 can be more reliably suppressed in the curing step described later by the curing unit 34.

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

Examples of the polyfunctional acrylate compound include polyfunctional alcohol-based (meth) acrylate compounds, 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-acryloyloxypolyethoxyphenyl) propane, neopentyl glycol di (meth) acrylate, or the like is preferable.

The alkoxylated multifunctional (meth) acrylate compound is preferably ethoxylated (3) trimethylolpropane tri (meth) acrylate (a compound obtained by tri (meth) acrylating a 3-mol adduct of trimethylolpropane ethylene oxide), propoxylated (3) trimethylolpropane tri (meth) acrylate (a compound obtained by tri (meth) acrylating a 3-mol adduct of trimethylolpropane propylene oxide), ethoxylated (2) neopentyl glycol di (meth) acrylate (a compound obtained by diacrylateing a 2-mol adduct of neopentyl glycol ethylene oxide), or propoxylated (2) neopentyl glycol di (meth) acrylate (a compound obtained by diacrylateing a 2-mol adduct of neopentyl glycol propylene oxide), and the like.

The oligomer is preferably polyester (meth) acrylate, urethane (meth) acrylate or the like, and further preferably includes modified glycerol tri (meth) acrylate, modified bisphenol a di (meth) acrylate, bisphenol a Propylene Oxide (PO) adduct di (meth) acrylate, bisphenol a Ethylene Oxide (EO) adduct di (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate or the like.

The acrylamide compound is preferably hydroxyethyl acrylamide, dimethylacrylamide, isopropylacrylamide, diethylacrylamide, dimethylaminopropyl acrylamide, or N-vinyl lactam, and specifically, N-vinylpyrrolidone or N-vinylcaprolactam is preferable.

The monofunctional acrylic compound is preferably isoamyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isoamylstyrene (meth) acrylate, isostearyl (meth) acrylate, 2-ethylhexyl diethylene glycol (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) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, lactone-modified (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclopentyloxyethyl (meth) acrylate, dicyclopentyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, or the like, 4-hydroxybutyl (meth) acrylate or cyclic trimethylolpropane formal (meth) acrylate.

Further, monofunctional acrylic compounds having a cyclic structure in the molecule are preferable, and specific examples thereof include acryloylmorpholine, benzyl acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclopentenyloxyethyl (meth) acrylate, dicyclopentyl (meth) acrylate, and cyclic trimethylolpropane formal (meth) acrylate. These monofunctional acrylic compounds having a cyclic structure in the molecule can improve the solubility of a photopolymerization initiator or the like in the photocurable composition 15 and improve the heat resistance of the cured projection 12.

The multifunctional acrylate compound can improve the hardness and strength of the cured resin as a product. The acrylamide compound shortens the time required for curing and forms the convex portion 12 having further 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 compound as an ultraviolet-curable compound. Therefore, when the film material 11 is formed of cellulose acylate, the convex portion 12 containing the acrylamide compound is particularly preferable because it has high adhesion to the cellulose acylate.

The photocurable composition 15 preferably contains an acrylamide compound and a polyfunctional acrylate compound as the ultraviolet-curable compound. Thus, the discharged droplets are quickly cured by light irradiation, and the cured projections have sufficient strength, so that the rollers are not contaminated by falling off of the projections when the rollers are in contact with each other, and a good projection shape can be continuously formed. Also, it is preferable to use 2 or more kinds of the multifunctional acrylate compounds. This is because the viscosity of the photocurable composition can be adjusted to a desired range, and the shape of the convex portion can be easily adjusted. Further, the photocurable composition 15 preferably further contains a monofunctional acrylic compound. This is because the viscosity of the photopolymerization initiator or the light stabilizer for improving rapid curability or stability can be uniformly dissolved in the photocurable composition 15, the viscosity can be adjusted to a desired range, and the strength, durability, and heat resistance of the cured convex portion can be improved.

The viscosity of the photocurable composition 15 is preferably in the range of 20mPa · s or more and 1000mPa · s or less. When the viscosity is 20mPa · s or more, the shape of the liquid droplet 41 is less likely to change during the time until the liquid droplet is cured by the curing unit 34 after adhering to the film material 11, as compared with the case of being smaller than 20mPa · s. Therefore, the timing of curing can be easily adjusted, and the convex portion 12 of the target shape can be easily formed. When the viscosity is 1000mPa · s or less, the volume of the discharged droplet 41 can be easily adjusted as compared with the case where the viscosity is more than 1000mPa · s. Therefore, the convex portion 12 of the target size is easily formed. The viscosity of the photocurable composition 15 is more preferably in the range of 30 to 500mPa · s, and still more preferably in the range of 40 to 300mPa · s.

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

Further, in order to improve the stability of the solution (in this example, the photocurable composition 15) contained in the photocurable compound, it is preferable to add a light stabilizer. Examples of the light stabilizer include nitroso polymerization inhibitors, hydroquinone, methoxyhydroquinone, benzoquinone, p-methoxyphenol or TEMPO (2, 6-tetramethylpiperidine 1-oxyl), hydroxyl TEMPO (hydroxyl-2, 6-tetramethylpiperidine 1-oxyl), cupropham Al and hindered amines.

Among these Light Stabilizers, structures of secondary amines or tertiary amines as Hindered Amine Light Stabilizers (HALS, hindered Amine Light Stabilizers) are preferable. 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 4-hydroxy TEMPO (4-hydroxy-2, 6-tetramethylpiperidine 1-oxy) is particularly preferable

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, relative to the photocurable composition 15. Within this range, the stability of the photocurable composition in the discharge device can be improved to suppress a change in viscosity or curing in the discharge device, and the photocurability of the droplets after discharge is sufficient, which is preferable. The photocurable compound can adjust the amount of the multifunctional acrylate compound, the acrylamide compound, or the monofunctional acrylic compound to be in a state of a mixed solution mixed with other compounds, and can adjust the viscosity. As the viscosity adjusting agent for adjusting the viscosity, there are a high viscosity adjusting agent for further increasing the viscosity and a low viscosity adjusting agent for further decreasing the viscosity, and in this example, the high viscosity adjusting agent is used.

The viscosity is a viscosity at a temperature in the discharge step, and in this example, the viscosity is 25 ℃ because the discharge is performed at room temperature (25 ℃). In this example, the viscosity was measured by a tuning-fork type small vibration viscometer CJV5000 (a & D Company, limited).

The solidification unit 34 is for forming the projections 12 from the droplets 41. The curing unit 34 includes a plurality of light sources 47 and, for example, a plate-shaped support member 48 that supports the plurality of light sources 47, and the plurality of light sources 47 are provided downstream of the discharge portion 33 in the moving direction of the film material 11 and emit light. The number of the light sources 47 is determined depending on the arrangement of the formed convex portions 12, the type of the photocurable composition 15, the moving speed of the film material 11, and the like, and may be 1. The wavelength of the light source 47 is determined according to the photocurable composition 15 used. In this example, as described above, since an ultraviolet-curable compound is used as a component of the photocurable composition 15, a light source 47 that emits ultraviolet rays is provided. By emitting light from the light source 47, the photocurable compound contained in the liquid droplets 41 adhering to the film material 11 is cured, whereby the liquid droplets 41 become the convex portions 12 (curing step).

The film material 11 on which the convex portions 12 are formed is moved downstream by the roller 37A and/or the roller 37B, and is conveyed to the winding unit 35. Further, the roller 37 disposed downstream of the curing unit 34 is appropriately disposed in order to make the planarity of the film material 11 passing through the curing unit 34 better or to adjust the transportability of the film material 11 in the film manufacturing apparatus 30.

The winding unit 35 has a turret arm 56, and winds the film 10 around a winding core 58 fitted around a winding shaft 57. The turret arm 56 is intermittently rotated by 180 degrees by an arm driving unit (not shown), and selectively switches the winding core 58 between the winding position PS1 and the winding core replacement position PS2. Further, a guide arm 59 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 end portion of the guide arm 59. When the turret arm 56 rotates, the guide roller 61 supports the film 10 in a state where the film 10 does not contact the turret arm 56 and the arm mounting shaft 62.

A winding shaft 57 is provided at each distal end portion of the turret arm 56, and a winding core 58 is fitted over the winding shaft 57. The winding shaft 57 has a rotation mechanism (not shown) that rotates to wind the film 10 around the winding core 58. In this way, the winding shaft 57 constitutes a moving mechanism together with the feeding section 32, and moves the film material 11 in the longitudinal direction in cooperation with the feeding section 32. However, the moving mechanism is not limited to this example, and as described above, at least a part of the plurality of rollers 37 disposed in the moving path may be a driving roller and may be configured by this driving roller.

At the winding position PS1, the film 10 fed from the roller 37 is wound around the winding core 58. Then, at the core replacement position PS2, the film 10 of a predetermined length is wound, the film roll 31 of a desired roll is removed from the winding shaft 57 together with the core 58, and the core 58 is replaced by fitting a new empty core 58 onto the winding shaft 57.

At the winding position PS1, the film 10 is wound around the winding core 58 from the side of the one end 12A with the front end in the moving direction Dc as the one end 12A (see fig. 1), and when the film roll 31 is in a state close to a desired roll of a predetermined length, the turret arm 56 is rotated 180 degrees, so that the film roll 31 close to a desired roll is located at the core replacement position PS2. Then, the empty winding core 58 is positioned at the winding position PS1. When the film roll 31 reaches a predetermined length, a rewinding device (not shown) operates to cut the film 10. The cut leading film 10 has the rear end in the moving direction Dc as the other end 12B, and the other end 12B is wound around the film roll 31 at the core changing position PS2. The cut film 10 in the succeeding row is wound around the empty winding core 58 from the one end 12A at the winding position PS1 with the leading end as the one end 12A.

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

The thin film manufacturing apparatus 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, i.e., the one closest to the winding section 35. The pulse generator 66 generates a pulse each time the connected roller 37 rotates by a constant angle, that is, each time the film material 11 is conveyed by a constant length.

In fig. 3, only one actuator 67 is shown, but in this example, each discharge device 45 is provided. The actuator 67 is an example of a voltage applying unit that applies a voltage to a piezoelectric element 84 (see fig. 5) of the discharge device 45, which will be described later. The actuator 67 drives the ejection device 45 to start and stop the ejection of the liquid droplets 41. The start of discharge means that repeated discharge is started for a predetermined time, and the stop of discharge means that repeated discharge is stopped. The ejection is repeated at a predetermined cycle. Therefore, when the set cycle is equal to or longer than the predetermined time, the number of times of discharge from the start of discharge to the stop of discharge is 1. In this manner, the repeated discharge also includes a case where the number of times of discharge is 1.

The system controller 68 centrally controls each part of the thin film manufacturing apparatus 30, and forms the target convex portion 12 at the target position of the thin film material 11 by this control. The system controller 68 determines the moving length (transport length) of the film material 11 every time a pulse is generated from the pulse generator 66. The system controller 68 receives the length of the movement path from the discharge port 45a (see fig. 4 and 5) of the discharge device 45 to the roller 37 to which the pulse generator is connected, and detects the position of the leading end (corresponding to the one end 12A (see fig. 1)) of the film material 11 in the longitudinal direction passing through the discharge port 45a from the length and the movement length of the film material 11 determined as described above. The system controller 68 further inputs the position of the film material 11 on which the projection 12 is formed in advance, and drives the discharge device 45 via the driver 67 when the film material 11 passing through the discharge port 45a becomes the target position.

The system controller 68 can determine the length of the film 10 wound on the winding shaft 78 and/or the radius of the film roll 31 from the pulses. In these cases, when the film material 11 passing through the discharge port 45a is at the target position, the discharge device 45 is driven via the actuator 67 in accordance with the determined length and/or radius.

The cycle of discharging the droplets 41, the flow rate of the photocurable composition 15 supplied to the discharge device 45, the volume of the droplets 41, the moving speed of the film material 11, the timing of cutting the film 10 in the winding unit 35, the timing of rotating the turret arm 56, and the like are further input to the system controller 68, and each part of the thin film manufacturing apparatus 30 is controlled based on these input signals.

As shown in fig. 4, the discharge devices 45 of the discharge unit 44 are arranged in a plurality of rows in the width direction. In this example, since the sizes of the ejection devices 45 in the width direction are 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. As described above, the method of disposing the ejection device 45 may be determined appropriately according to the size of the ejection device 45, the pitch PW12, and the like, and the ejection device 45 may be disposed in a state where the pitch PW45 of the ejection port 45a in the width direction is the same as the pitch PW.

In this example, as described above, the film 10 having the convex portions 12 over the entire width direction is formed, and therefore the discharge device 45 is disposed over the entire width direction. Further, even when the film 10 is manufactured, since the discharge device 45 is provided movably in the width direction and the discharge device 45 can be displaced in the width direction by using a displacement mechanism (not shown) that moves the discharge device 45 in the width direction, it is not necessary to 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 plurality of rows in the width direction. The light sources 47 are disposed at positions in the width direction of the discharge ports 45a of the discharge devices 45. This allows each droplet 41 formed on the thin-film material 11 to be reliably irradiated with light.

The shape of the liquid droplets 41 on the film material 11 changes during the period until solidification. For example, the shape changes, such as being flattened (the height becomes lower and the diameter R41 becomes larger), or the top of the droplet 41 being flattened, or the top of the droplet 41 being recessed. The shape of the projection 12 formed by solidification depends on the shape of the droplet 41. As described above, since the shape of the plurality of projections 12 is uniform in the thin film 10 of this example, the solidification of the liquid droplets 41 is started at a fixed timing.

Therefore, the light sources 47 are arranged in a state in which the distance from the discharge port 45a of the discharge device 45 of the droplet 41 to be irradiated is constant. For example, in this example, the light sources 47 emitting light toward the droplets 41 formed by the ejection devices 45 in the other row on the downstream side are arranged at positions shifted downstream by the pitch PL45 of the ejection openings 45a in the longitudinal direction, compared to the light sources 47 emitting light toward the droplets 41 formed by the ejection devices 45 in the row on the upstream side in the moving direction among the plurality of ejection devices 45. Thus, irradiation is started within a certain time after formation of any one of the droplets 41, and the convex portion 12 having a uniform shape is formed. In fig. 4, the number of the light sources 47 arranged in the moving direction is depicted as 3, but the number thereof may be determined as appropriate depending on the moving speed of the film material 11, the viscosity of the photocurable composition 15 (see fig. 3), the time required for curing, and the like.

As described above, the shape of the convex portion 12 changes according to the start timing of solidification of the liquid droplet 41 on the film material 11, and therefore, by utilizing this, the shape of the convex portion 12 can be adjusted. That is, the shape of the convex portion 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 the convex portion 12 having a flatter spherical crown shape is formed, when the convex portion 91 having a flat top portion (see fig. 6) is formed, and when the convex portion 96 having a concave top portion (see fig. 7) is formed, the moving time from the discharge device 45 to the light source 47 may be further extended. When the convex portion of the spherical crown is formed to have a higher height and a smaller bottom area, the moving time from the discharge device 45 to the light source 47 may be further shortened.

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

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

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

The opening/closing member 72 is for opening and closing one end of the through hole 82 on the inner side. The opening/closing member is movable between an opening position for opening the one end of the through-hole 82 as shown in fig. 5 (B) and a closing position for closing the one end as shown in fig. 5 (a). The opening/closing member 72 includes an abutting portion 83, a piezoelectric element (piezo element) 84, and the actuator 67 (see fig. 3), and the abutting portion 83 provided at the tip end abuts against the bottom member 74 in a state where the one end is closed at the closing position.

The contact portion 83 is fixed to the piezoelectric element 84 that is deformed by the applied voltage via a shaft 85. The contact portion 83 moves between the open position and the closed position by increasing or decreasing the voltage applied by the actuator 67 (see fig. 3). The shaft 85 is inserted through the center of each of the pressing member 75 and the seal member 78.

The photocurable composition 15 is supplied from the supply unit 81 to the inside of the housing 71 at a predetermined flow rate, and the photocurable composition 15 is supplied from the supply unit 81 to the inside of the housing 71 until the photocurable composition 15 is filled in a pressurized state. 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 maintains the pressurized state of the photocurable composition 15 inside. In this manner, the supply portion 81 also functions as a pressurizing mechanism.

By moving the opening/closing member 72 located at the closing position to the opening position, the photocurable composition 15 filled in a pressurized state passes through the one end and is directed toward the discharge port 45a. Then, by moving the opening/closing member 72 located at the open position to the closed position, a small amount of the photocurable composition 15 in the through-hole 82 is discharged in the form of the droplet 41. The movement path between the discharge port 45a and the film 11 (see fig. 3) is set to a distance significantly greater than the size of the droplet 41 so that the droplet 41 can fly in the space. Thereby, the liquid droplets 41 discharged from the discharge port 45a fly and adhere to the film material 11 from the discharge port 45a. When the opening/closing member 72 located at the closing position is moved to the opening position again and then returned to the closing position, new droplets 41 are deposited at another position in the longitudinal direction of the moving film material 11. As described above, the photocurable composition 15 filled in a pressurized state is discharged from the discharge port 45a in the form of droplets 41 by repeatedly moving the opening/closing member 72 from the closing position to the opening position, and is made to fly toward the moving film material 11 (discharge step).

Further, the actuator 67 (see fig. 3) adjusts the cycle of discharging each droplet 41, the flow rate of the photocurable composition 15 supplied to the discharge device 45, and the volume of the droplet 41. The volume of the droplet 41 can be adjusted by adjusting the movement timing of the shutter 72. Specifically, the volume of the droplet 41 can be adjusted by adjusting the time taken for the opening/closing member 72 located at the closing position to move to the opening position and return to the closing position again. The volume of the droplet 41 can also be adjusted by adjusting at least one of the viscosity of the photocurable composition 15 (see fig. 3) and the pressure of the photocurable composition 15 inside the housing 71. In the discharge step, the discharge rate is 0.8X 10 ^-12 m ³ Above and 100.0 × 10 ^-12 m ³ The droplets 41 are discharged with a volume within the range of preferably 0.8X 10 ^-12 m ³ Above and 100.0 × 10 ^-12 m ³ The volume of the photocurable composition 15 within the following range allows the size of the convex portion 12 to be more easily adjusted.

The pitch PL12 of the projections 12 (see fig. 2) is adjusted by adjusting at least one of the period of discharging the droplets 41 and the moving speed of the thin-film material 11 (see fig. 3).

The opening/closing member 72 including the piezoelectric element 84 is exemplified above, but the opening/closing member is not limited to this example. For example, instead of changing the shape of the piezoelectric element 84, an opening/closing member may be used that moves the contact portion urged by a spring by a change in air pressure. Such a discharge device and discharge mechanism are called Jet dispensing (Jet dispensing) and Jet dispensing system, and are described in Journal of Japan Institute of Electronics Packaging 2004, vol.7, no.6 (page 501), and commercially available devices can be used.

In this example, the convex portion 12 of the spherical crown shape is formed, but the shape of the convex portion 12 may be changed according to the intended function of the film. For example, as shown in fig. 6, the top 91a may be a flat projection 91. The top 91A of the projection 91 is a plane substantially parallel to the 1 st surface 11A. As shown in fig. 7, the top portion 96a may be a concave convex portion 96. In either case, the ratio HP/RP is preferably within the aforementioned range.

Further, after the photocurable composition 15 is repeatedly discharged a plurality of times by the discharge device 45 for a long period of time, in the process of repeating continuous discharge, the opening and closing of the opening and closing member 72 may be stopped and the number of times of discharge may be insufficient. The mechanism is presumed as follows. That is, since the discharge device 45 repeatedly discharges the photocurable composition 15 a plurality of times over a long period of time, when the opening/closing member 72 reciprocates as shown in fig. 5 (a) and (B), the photocurable composition 15 seeps out into the gap between the seal member 78 and the shaft 85 of the opening/closing member 72, and the photocurable composition 15 accumulates in the portion of the O-ring 77 a. Friction is generated between the sealing member 78 and the shaft 85 of the opening/closing member 72 and/or the O-ring 77a and the shaft 85 of the opening/closing member 72, and the photocurable composition 15 undergoes a polymerization reaction in the housing 71 due to thermal energy or frictional energy, and the reaction product of the photocurable composition 15 adheres to the O-ring 77a in the housing 71, the shaft 85 of the opening/closing member 72, and/or the vicinity of the sealing member 78, so that the opening/closing member 72 cannot reciprocate.

The discharge device 45 and the photocurable composition 15 with the adjusted composition and the like can achieve repeated discharge performance for a plurality of times during the growth period. For example, from the viewpoint of preventing the polymerization reaction from proceeding in the housing 71, a method of adding a photopolymerization initiator to the photocurable composition 15 by reducing the amount of the photopolymerization initiator or adjusting the amount of hydroxyl TEMPO (4-hydroxy-2, 6-tetramethylpiperidine 1-oxyl or the like) as a light stabilizer is performed. In addition, in order to more suitably impart discharge durability over a long period of time and photocurability of droplets after discharge, it is also preferable to use N-vinyllactams as the acrylamide-based compounds as the ultraviolet-curable compounds. This is because N-vinyl lactams can suppress polymerization reaction due to energy such as friction and have high photopolymerization reactivity as compared with other acrylamide compounds. In order to improve the photopolymerization reactivity, when a mixture of a plurality of liquid photocurable compounds is used as the photocurable composition 15, the composition ratio of the acrylamide compound in the amount of the photocurable compound component (the total amount of the acrylamide compound, the monofunctional acrylic compound, and/or the polyfunctional acrylate) in the photocurable composition 15 is set to be within a range of 10% by mass or more and 60% by mass or less, and more preferably within a range of 20% by mass or more and 50% by mass or less. Within this range, it is preferable to suppress a polymerization reaction in the outer shell due to energy such as friction and to rapidly photocure the droplets applied to the film.

The thin film manufacturing apparatus 30 (see fig. 3) is not limited to the case of manufacturing the thin film 10, and various thin films can be manufactured by using the pulse generator 66, the system controller 68, and the like. For example, the film 110 shown in fig. 8 can also be manufactured by the film manufacturing apparatus 30. The film 110 includes the convex portions 12 only in a certain section on both sides of the long film material 11. The section in the width direction in which the convex portion 12 is formed is not limited to both sides, and may be, for example, a fixed section in the center in the width direction, in addition to or instead of both sides.

When the film 110 is manufactured, only the discharge devices 45 arranged in a fixed interval at both ends in the width direction are driven by the system controller 68 via the driver 67. Similarly, the light source 47 is also driven by the system controller 68 to emit light by driving only a part of both ends in the width direction where the liquid droplets 41 are formed. In this manner, by driving only a part of all the discharge devices 45 and the light sources 47 in the width direction by the system controller 68, various types of thin films having the convex portions 12 formed in a predetermined region in the width direction can be manufactured. However, the discharge device 45 and the light source 47 may be arranged only in the section where the convex portion 12 is formed in the width direction.

Further, the thin film 120 shown in fig. 9 can also be manufactured by the thin film manufacturing apparatus 30 (refer to fig. 3). The film 120 includes a convex portion 12 in a partial section in the longitudinal direction of the long film material 11. Specifically, the convex portion 12 is provided for each fixed section in the longitudinal direction. When the film 120 is manufactured, first, the position of the tip end of the film material 11 passing through the discharge port 45a in the longitudinal direction is detected by the system controller 68 by the aforementioned method, and when the film material 11 passing through the discharge port 45a becomes the target position, the discharge device 45 is driven via the driver 67 to discharge the droplets 41 (see fig. 3). Similarly, with respect to the light source 47, when the thin film 120 on which the liquid droplets 41 are formed is at the target position, the system controller 68 is driven to emit light to form the convex portions 12.

Examples

[ example 1] to [ example 15]

The thin film 10 is manufactured using the thin film manufacturing apparatus 30. The film material 11 is a TAC film formed of TAC. The photocurable composition 15 is a mixture of a high viscosity agent as a viscosity modifier, a photopolymerization initiator, and the like, and is supplied from the supply unit 81 to the discharge device 45. As the photocurable compositions 15, 8 types were prepared, and these are hereinafter referred to as mixed liquids a to H.

The formulations of the mixed liquids a to H as the photocurable composition 15 are shown in the column of "mixed liquid" in table 1. Table 1 shows the acrylamide compound and its viscosity, the multifunctional acrylate compound and its viscosity, the monofunctional acrylic compound and its viscosity, and the amounts of these compounds and the photopolymerization initiator. The photopolymerization initiator was a mixture of IRGACURE (registered trademark) 907 (manufactured by BASF Japan ltd.) and 2, 4-diethylthioxanthone (KAYACURE DETX-S, nippon Kayaku co., ltd.) in a mass ratio of 1 to 3. Further, 0.2 part by mass of 4-hydroxy-2, 6-tetramethylpiperidine 1-oxyl (4-hydroxy TEMPO) as a light stabilizer was added to the liquid mixture A, the liquid mixture D and the liquid mixture H.

In Table 1, A or B of the acrylamide compound, C or D of the polyfunctional acrylate compound, and E of the monofunctional acrylic compound are as follows.

A: dimethylacrylamide, DMAA (manufactured by KJ Chemicals Corporation)

B: hydroxyethyl acrylamide, HEAA (manufactured by KJ Chemicals Corporation)

C: polypropylene glycol diacrylate, ARONIX M220 (TOAGOSEI co., ltd., manufactured by

D: mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (PETA/PETTA), KAYARAD PET-30 (Nippon Kayaku Co., manufactured by Ltd.)

E: acryloylmorpholine, ACMO (manufactured by KJ Chemicals Corporation)

The conditions for producing the film 10 are shown in table 2. Further, the ejection of the droplets 41 is repeated at a constant cycle. The "frequency" in table 2 is the reciprocal of the cycle of repeatedly ejecting the droplets 41. The "discharge liquid amount" in table 2 is the amount of the above-mentioned mixed liquid discharged from the discharge device 45 and is the volume of each droplet 41. As the curing unit 34, a commercially available ultraviolet irradiation apparatus HLUV-126UV365 (manufactured by CCS inc.) having a Light Emitting Diode (LED) in a light source 47 is used. The length L from the discharge port 45a to the light source 47 is set to 0.4m.

The diameter RP and height HP of the

projections

12, 91, 96 were measured for each of the obtained films 10, and the ratio HP/RP was calculated. Then, the pitch PW12 was measured. In addition, the shape of the convex portion 12 and the degree of contamination of the peripheral surface of the roller 37B between the curing unit 34 and the winding section 35 were evaluated. The evaluation methods and criteria are as follows. The results are shown in Table 2.

(1) Diameter RP, height HP, shape of the convex portion

The diameter RP and the height HP were measured by shape analysis using a 3D laser microscope LEXT OLS4000 manufactured by Olympus Corporation. Regarding the shape, the shape of the convex portion 12 when viewed from the direction perpendicular to the 1 st surface 11A (hereinafter referred to as a planar shape) and the shape of a cross section in the thickness direction when viewed from the plane is a circle (hereinafter referred to as a cross-sectional shape) were evaluated according to the following criteria. A plurality of projections having a size different from each other and smaller than the target projection in D described below are generated by separation of the liquid droplet 41. A. B and C are qualified, D is unqualified.

A: the planar view shape is circular, and the section shape is semicircular or arched.

B: the plan view shape is circular, and the sectional shape is flat at the top as shown in fig. 6 or has a depression as shown in fig. 7.

C: the planar shape is not circular, but is a deformed shape as shown in fig. 10. In fig. 10, only the convex portion is shown, and the convex portion is denoted by reference numeral 150.

D: the shape in plan view cannot be said to be circular, or a plurality of projections having different sizes and smaller than the target projection are observed.

(2) Contamination of the roller 37B

After the production of the film 10, the peripheral surface of the roll 37B between the curing unit 34 and the winding unit 35 is visually observed under normal room lighting (hereinafter, referred to as normal observation), and when no contamination is observed by normal observation, visual observation (hereinafter, referred to as forced observation) is performed under strong illumination light. Since this evaluation was not related to the properties of the obtained film 10 itself, the following A to C were all acceptable.

A: in the forced observation, no contamination was confirmed on the roll.

B: minimal contamination was observed in the forced observations.

C: contamination was observed in the usual observations.

(3) Discharge durability

Repeated discharge tests of the photocurable composition 15 were performed using the discharge device 45 of the thin film manufacturing apparatus 30, and the number of continuous discharges was measured. The continuous discharge frequency is the number of times of discharge from the start of discharge to just before stopping of the repeated discharge. The discharge durability evaluation was performed in the same manner as in each example except that the frequency was set to 1000HZ for the repeated discharge conditions. The discharge durability was evaluated as follows. The following A to C were all acceptable.

A: the number of times of discharge was 500 ten thousand or more.

B: the number of times of discharge is 50 ten thousand or more and less than 500 ten thousand.

C: the number of times of discharge is 1 ten thousand or more and less than 50 ten thousand.

D: the number of spitting was less than 1 ten thousand.

Comparative examples 1 to 2

Films having a plurality of projections were produced by a commercially available discharge device of an ink jet system, and these were used as comparative examples 1 and 2. The ink jet type discharge device does not include an opening/closing member for opening/closing the discharge port 45a, as in the opening/closing member 72 of the present example. In comparative example 1, as the photocurable composition discharged from the discharge device, a mixed liquid E shown in table 1 was used. In comparative example 2, a mixed solution F having a formulation shown in table 1 was used, the total amount of the mixed solution F was set to 100 parts by weight, and a mixed solution obtained by mixing the mixed solution F, 30 parts by weight of propylene glycol monomethyl ether, and 100 parts by weight of methyl ethyl ketone was discharged from the discharge apparatus. The viscosity of the mixed solution F is 20 mPas or less. A dryer was provided between the discharge device 45 and the curing unit 34 of the thin film manufacturing apparatus 30 to manufacture a thin film, which was taken as comparative example 2. In comparative example 2, the formed droplets were dried at 100 ℃ for 20 seconds by a dryer, and then, convex portions were formed by irradiating light. In any of the comparative examples, the film material used was a TAC film formed of TAC, which was the same as the film material 11 used in the examples.

For the film obtained in comparative example 2, the diameter RP and height HP of the convex portion were measured, and the ratio HP/RP was calculated. Then, the pitch PW12 was measured. In comparative example 1, since a convex portion having a constant shape could not be obtained, the diameter RP, height HP, and pitch PW12 of the convex portion were not measured. In addition, the shape of the convex portion and the degree of contamination of the peripheral surface of the roller 37B between the curing unit 34 and the winding section 35 were evaluated. The results are shown in Table 2.

Examples 16 to 18

A film 10 was produced in the same manner as in example 11. The film material 11 is a TAC film formed of TAC. 3 types of photocurable compositions 15 were prepared, and these are hereinafter referred to as mixed solutions I to K.

The formulations of the mixed liquids I to K as the photocurable composition 15 are shown in the column of "mixed liquids" in table 3. Table 3 shows the acrylamide compound and its viscosity, the polyfunctional acrylate compound and its viscosity, the monofunctional acrylic compound and its viscosity, the kind and amount of the photopolymerization initiator, and the amount of the light stabilizer. As the photopolymerization initiator a, in table 3, a mixture of IRGACURE (registered trademark) 907 (manufactured by BASF Japan ltd.) and 2, 4-diethylthioxanthone (KAYACURE DETX-S, nippon Kayaku co., ltd.) in a mass ratio of 1 to 3 was used as the photopolymerization initiator a, similarly to the photopolymerization initiators used in the mixed liquids a to D. Further, as the photopolymerization initiator b, a mixture of bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (IRGACURE (registered trademark) 819, manufactured by BASF Japan Ltd.), 2,4, 6-trimethylbenzoyl diphenylphosphine oxide (DAROCUR (registered trademark) TPO, manufactured by BASF Japan Ltd.) and isopropyl thioxanthone (manufactured by lammson corporation) in a mass ratio of 4 to 5 to 2 was used. Further, 4-hydroxy-2, 6-tetramethylpiperidine 1-oxyl (4-hydroxy TEMPO) was added as a light stabilizer in an amount shown in Table 3.

In Table 3, F of the acrylamide compound, G or H of the polyfunctional acrylate compound, and I of the monofunctional acrylic compound are as follows. In addition, since 2 kinds of the polyfunctional acrylate components are used, in table 3, the columns of "1 st polyfunctional component" and "2 nd polyfunctional component" which are classified as "polyfunctional components" are described.

F: n-vinylcaprolactam (manufactured by Tokyo Chemical Industry Co., ltd.)

G: ethoxylated (3) trimethylolpropane triacrylate (SR 454D NS, manufactured by Sartomer Japan Inc.)

H: CN964A85 (urethane acrylate oligomer, average number of functional groups 2, manufactured by Sartomer Japan Inc.)

I: cyclic trimethylolpropane formal acrylate (SR 531, manufactured by Sartomer Japan Inc.)

The conditions for producing the film 10 were the same as those in example 11 and are shown in Table 4. The discharge durability test was evaluated under the above conditions and is shown in table 4.

Description of the symbols

10. 110, 120-film, 11-film material, 11A-surface 1, 11B-surface 2, 12, 91, 96, 150-protrusion, 15-photocurable composition, 30-film production equipment, 31-film roll, 32-feeding section, 32 a-rotation axis, 33-discharging section, 34-curing unit, 35-winding section, 37A, 37B-roll, 38-film roll, 41-droplet, 42-backup roll, 44-discharging unit, 45-discharging device, 45 a-discharging port, 46-support member, 47-light source, 48-support member, 56-turret arm, 57-winding axis, 58-winding core, 59-guide arm, 61-guide roller, 62-arm mounting shaft, 66-pulse generator, 67-drive, 68-system controller, 71-housing, 72-opening and closing member, 73-housing body, 73 a-feed port, 74-bottom member, 75-pressing member, 77A, 77B-O-ring, 78-sealing member, 81-feed, 82-through hole, 83-abutment, 84-piezoelectric element, 85-shaft, 91A, 96 a-top, dc-moving direction, HP-height, L-length, PL12, PW12, PL45, PW 45-pitch, RP, R41-diameter, PS 1-winding position, PS 2-core replacement position.

Claims

1. A thin film manufacturing method for forming a plurality of projections on a long thin film material moving in a longitudinal direction, the thin film manufacturing method comprising:

a discharge step of filling a pressurized state of a solution into a housing of a discharge device including a housing filled with the solution containing a photocurable compound therein, a through-hole formed in the housing and having one end exposed to the inside and the other end serving as a discharge port of the solution, and an opening/closing member for opening and closing the one end, and repeatedly moving the opening/closing member, which moves between an open position for opening the one end and a closed position for closing the one end, from the closed position to the open position to discharge the solution filled in the inside from the discharge port in the form of droplets and fly the solution toward the moving thin film material; and

a curing step of curing the photocurable compound adhering to the liquid droplet of the film material using a light source that is provided downstream of the discharge device in a moving direction of the film material and emits light for curing the photocurable compound to form the liquid droplet into the convex portion,

the opening/closing member has a piezoelectric element, a contact portion fixed to the piezoelectric element and contacting the discharge port, and a voltage application portion applying a voltage to the piezoelectric element, and moves the contact portion between the open position and the closed position by increasing or decreasing the voltage applied to the piezoelectric element by the voltage application portion,

the viscosity of the solution is in the range of 20 mPas to 1000 mPas at room temperature,

the shape of the projection is adjusted by adjusting the moving time of the film material from the discharge device to the light source.

2. The thin film production method according to claim 1,

in the discharge step, the discharge amount is 0.8X 10 ^-12 m ³ Above and 100.0 × 10 ^-12 m ³ The droplets are ejected with a volume in the following range.

3. The thin film production method according to claim 1 or 2,

the light is ultraviolet light, and the photocurable compound is an ultraviolet curable compound.

4. The film production method according to claim 3,

the ultraviolet-curable compound is an acrylamide compound.

5. The thin film production method according to claim 1 or 2,

the photocurable compound includes a light stabilizer.

6. The thin film production method according to claim 1 or 2,

the photocurable compound includes a monofunctional acrylic compound.

7. The thin film production method according to claim 1 or 2,

the photocurable compound includes a multifunctional acrylate compound.

8. The thin film production method according to claim 1 or 2,

the film material is formed of cellulose acylate.

9. A thin film manufacturing apparatus that forms a plurality of convex portions on an elongated thin film material that moves in a longitudinal direction, the thin film manufacturing apparatus comprising:

a moving mechanism for moving the long film material along the length direction;

a discharge device which is arranged in a state that a discharge port of a solution containing a photocurable compound faces a moving path of the thin film material and discharges the solution; and

a light source which is provided downstream of the discharge device by a distance L in a moving direction of the film material and emits light for curing the photocurable compound,

the discharge device includes:

a housing filled with the solution in a pressurized state;

a through hole formed in the housing, one end of the through hole being exposed to the inside of the housing and the other end of the through hole serving as the discharge port; and

an opening/closing member that repeatedly moves between an open position and a closed position, wherein the open position opens the one end, discharges the solution from the discharge port in the form of droplets, and flies toward the moving film material to adhere the solution to the film material, and the closed position closes the one end to stop the discharge of the droplets,

the shape of the projection is adjusted by adjusting the moving time of the film material from the discharge device to the light source by setting the moving speed of the moving mechanism and the distance L.

10. A film comprising a film material comprising a cellulose acylate,

and a plurality of convex parts in the shape of a spherical crown, a convex part with a flat top and a convex part with a concave part formed on the top are arranged on one surface of the film material,

the diameter RP of the convex part is in the range of 400-800 μm,

the height HP of the convex part is in the range of more than 12 μm and less than 70 μm,

the ratio HP/RP of the height HP of the convex part divided by the diameter RP is in the range of 0.03-0.10.

11. The film of claim 10, wherein,

the plurality of projections are regularly arranged.